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Keith, Lawrence H.

"P, R, S"
Compilation of EPA's Sampling and Analysis Methods
Edited by Lawrence H. Keith
Boca Raton: CRC Press LLC,1996
P
Paraldehyde EPA Method 8015 MATRIX This method is applicable to the determination of
CAS #123-3-7 certain nitrogen and phosphorus-containing pesticides in fin-
ished drinking water and groundwater.
TITLE Nonhalogenated Volatile Organics
METHOD SUMMARY Method 507 covers 46 nitrogen- and
MATRIX Groundwater, soils, sludges, water miscible liquid phosphorus-containing pesticides. A 1-L sample is fortified
wastes, and non-water miscible wastes. with a surrogate standard, salted, buffered, extracted with
methylene chloride, and concentrated; then the solvent is
APPLICATION This method is used for the analysis of 6
exchanged with methyl tert-butyl ether (MTBE) and concen-
nonhalogenated VOCs. Samples are analyzed using direct injec-
trated again, and a 2-L aliquot of a sample extract is injected
tion or purge-and-trap methods. Groundwater must be ana-
into a GC system equipped with a selective nitrogen-phospho-
lyzed by the purge-and-trap method. The method provides an
rus detector and a capillary column for analysis.
optional GC column that may help resolve analytes from inter-
ferences and which is also used for analyte confirmation. INTERFERENCES Method interferences may be caused by
contaminants in solvents, reagents, glassware, and other sample
INTERFERENCES There can be carryover contamination processing apparatus. Interfering contamination may occur
with high- and low-level samples. Impurities may come from when a sample containing low concentrations of analytes is
the purge-and-trap apparatus, organic compounds outgassing analyzed immediately following a sample containing relatively
from the plumbing ahead of trap, diffusion of VOCs through high concentrations. One or more injections of MTBE should
the sample bottle septum during shipping or storage, or from be made following the analysis of a sample with high concen-
solvent vapors in the lab. trations of analytes to check for analyte carryover. Matrix inter-
INSTRUMENTATION GC capable of on-column injections ferences may be caused by contaminants that are coextracted
or purge-and-trap sample introduction and a flame ionization from the sample. The extent of matrix interferences will vary
detector (FID). Column 1: an 8 ft by 0.1 in 1% SP-1000 on considerably from source to source, depending upon the water
Carbopack-B column. Column 2: a 6 ft by 0.1 in bonded n- sampled.
octane on Porasil-C. INSTRUMENTATION A gas chromatograph system (GC)
RANGE Not available. equipped with a nitrogen-phosphorus detector (NPD) is
needed.
MDL Not available.
Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
PRECISION Not available. umn, 0.25 m film thickness, or equivalent.
ACCURACY Not available. Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
column, 0.25 m film thickness, or equivalent.
SAMPLING METHOD For water and liquid samples; use
glass 40-mL vials with Teflon®-lined septum caps and collect PRECISION & ACCURACY This method has been validated
two vials per sample location with no headspace. For solids in a single lab and estimated detection limits (EDLs) have been
and concentrated waste samples; use widemouth glass bottles determined for each analyte. Observed detection limits may
vary among waters, depending upon the nature of the inter-
with Teflon® liners. Cool all samples to 4C
ferences in the sample matrix and the specific instrumentation
STABILITY For concentrated wastes, soils, sediments, or used. Analytes that are not separated chromatographically can-
sludges: cool to 4C. For liquids: add 4 drops of concentrated not be individually identified and measured unless an alterna-
hydrochloric acid, cool to 4C. tive technique for identification and quantification exist.
MHT 14 days. The estimated detection limit (in g/L) was 0.13. The EDL is
defined as either method detection limit or a level of compound
QUALITY CONTROL Analyze a reagent blank, matrix spike,
in a sample yielding a peak in the final extract with signal-to-
and matrix spike duplicate/duplicate for each analytical batch noise ratio of approximately 5, whichever value is higher.
(up to 20 samples). Demonstrate the purity of glassware and
reagents by analyzing a reagent water method blank. Internal, The concentration used for these measurements (in g/L) was
surrogate, and five concentration level calibration standards are 1.3.
used. The accuracy (as % recovery) was 94.
The precision (% RSD) was 9.
REFERENCE Method 8015, SW-846, 3rd ed., Nov.1986.
SAMPLING METHOD Grab samples are collected in 1-L
glass sample bottles (prewashed with detergent and hot tap
water, rinsed with reagent water, and dried in an oven at 400C
Pebulate EPA Method 507 for 1 h) with screw caps lined with PTFE-fluorocarbon.
CAS #1114-71-2
SAMPLE PRESERVATION Add mercuric chloride to the
TITLE Determination of Nitrogen and Phosphorus- sample bottle in amounts to produce a concentration of
Containing Pesticides in Water by GC/NPD 10 mg/L. If residual chlorine is present, add 80 mg of sodium

©1996 CRC Press LLC


thiosulfate/L of sample to the sample bottle prior to collection. Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
After collection, seal bottle and shake vigorously for 1 min, then Order Number is PB91-231480.
cool the sample to 4C immediately and store it at 4C in the
dark until extraction.
MHT Maximum holding time of the samples, and in some 1,2,3,4,7-PeCDD EPA Method 8280
cases the extracts, is 14 days. CAS #39227-61-7
SAMPLE PREPARATION Fortify the sample with 50 L of
TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins
the surrogate standard solution, adjust to pH 7 with phosphate
and Polychlorinated Dibenzofurans.
buffer, add 100 g NaCl to the sample, and seal and shake to
dissolve the salt; then extract with methylene chloride in a MATRIX This method is appropriate for the determination
separatory funnel or in a mechanical tumbler bottle. Dry the of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo-
extract by pouring it through a solvent-rinsed drying column p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical
containing about 10 cm of anhydrous sodium sulfate. Collect wastes including still bottoms, fuel oils, sludges, fl ash, reactor
the extract in a Kuderna-Danish (K-D) concentrator and rinse residues, soil and water.
the column with 20–30 mL methylene chloride. Concentrate
METHOD SUMMARY This method covers 22 PCDD and
the extract to about 2 mL and rinse the flask and its lower joint PCDF compounds and it uses a high resolution capillary GC
into the concentrator tube with 1 to 2 mL of methyl t-butyl
column with low resolution mass spectrometry. Samples are
ether (MTBE). Add 5–10 mL of MTBE and concentrate the extracted and concentrated by several methods that vary
extract twice (adding more MTBE) to a final volume of 5.0 mL
depending on the matrix involved. The organic extracts are
and store it at 4C until analysis. cleaned-up by washing with aqueous basic and acid solutions
Note: If methylene chloride is not completely removed from and then separated into fractions using a column of neutral
the final extract, it may cause detector problems. alumina. The fraction containing the PCDDs and PCDFs is
then further cleaned-up using a column of activated carbon.
QUALITY CONTROL Minimum quality control require- The final extract is concentrated and Carbon-13 labeled inter-
ments are initial demonstration of lab capability, determina- nal standards are added prior to analysis by GC/MS using a
tion of surrogate compound recoveries in each sample and capillary GC column and selected ion monitoring using five
blank, monitoring internal standard peak area or height in each sets of ions that are detailed in the method. Certain 2,3,7,8-
sample and blank, analysis of lab reagent blanks, lab fortified substituted congeners are used to provide calibration and
samples, lab fortified blanks, and other QC samples. A lab method recovery information. Proper column selection and
reagent blank is analyzed to demonstrate that all glassware and access to reference isomer standards, may in certain cases, pro-
reagent interferences are under control. vide isomer specific data.
Initial demonstration of capability is fulfilled by analyzing four INTERFERENCES Solvents, reagents, glassware, and other
fortified reagent water samples with the recovery value for each sample processing hardware may yield discrete artifacts and/or
analyte falling within the acceptable range ( 30% average elevated baselines which may cause misinterpretation of chro-
recovery). Surrogate recoveries from samples or method blanks matographic data. Use high purity reagents and solvents to
must be 70–130%. The internal standard response for any sam- minimize interference problems. Interferents coextracted from
ple chromatogram should not deviate from the daily calibra- the sample will vary considerably from source to source.
tion check standard’s internal standard response by more than PCDDs and PCDFs are often associated with other interfering
30% or lab fortified blanks and sample matrices are used to chlorinated compounds such as PCBs and polychlorinated
assess lab performance and analyte recovery, respectively. diphenyl ethers which may be found at concentrations several
If the response for the target analyte peak exceeds the working orders of magnitude higher than that of the analytes of interest.
range of the system, dilute the extract and reanalyze.Alternative INSTRUMENTATION A low resolution GC/MS utilizing 70
techniques such as an alternate detector or second chromatog- ev must be capable of selected ion monitoring (SIM) for at
raphy column should be used to confirm peak identification least 11 ions simultaneously, with a cycle time of 1 second or
when sample components are not resolved adequately. less. Minimum integration time for SIM is 50 ms per m/z. Also
EPA CONTACT & HOTLINE For technical questions contact required is a GC-to-MS interface constructed of all glass or
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and glass-lined materials. One of the following GC columns is
Drinking Water (WH-550D), 401 M St. SW, Washington, DC required:
20460. Tel. (202) 260-3040. For further information the EPA Column 1: 50 m CP-Sil-88 fused silica capillary column.
Safe Drinking Water Hotline may be called at: (800) 426-4791. Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick-
REFERENCE Methods for the Determination of Organic ness) fused silica capillary column.
Compounds in Drinking Water, EPA/600/4-88/039 (revised Column 3: 30 m SP-2250 fused silica capillary column.
July 1991). U.S. EPA Environmental Monitoring Systems Lab- When toluene is employed as the final solvent, use of a bonded
oratory, Cincinnati, OH, 45268, U.S.A. Available from the phase column is recommended. Solvent exchange into tride-
National Technical Information Service (NTIS), 5285 Port cane is required for other liquid phases or nonbonded columns

©1996 CRC Press LLC


such as CP-Sil-88. Chromatographic conditions must be column with 15 mL of 60 percent (v/v) methylene chloride in
adjusted to account for solvent boiling points. hexane and collect this second fraction in a conical shaped
concentrator tube.
PRECISION & ACCURACY Accuracy, precision, MDLs and
concentration ranges for the compounds covered by this Carbon column clean-up — Using a carefully regulated stream
method have not been determined or published by EPA yet. of nitrogen, concentrate the first 8 percent fraction (methylene
The sensitivity of this method is dependent upon the level of chloride in hexane) from the alumina column to about 1 mL.
interferents within a given matrix. Proposed quantification lev- Save this 8 percent concentrate for GC/MS analysis to check
els for target analytes were 2 ppb in soil samples, up to 10 ppb for breakthrough of PCDDs and PCDFs. Concentrate the sec-
in other solid wastes and 10 ppt in water. Actual values have ond 60 percent fraction (methylene chloride in hexane) to
been shown to vary by homologous series and, to a lesser about 2 to 3 mL. Prepare a carbon column and rinse the carbon
degree, by individual isomer. with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
forward direction of flow and then in the reverse direction of
SAMPLING METHOD Grab and composite samples must
flow. While still in the reverse direction of flow, transfer the
be collected in 1 L or 1-quart amber glass bottles with Teflon®-
sample concentrate to the column and elute with 10 mL of
lined screw-caps that have been acid-washed and solvent rinsed
methylene chloride/methanol/benzene (75:20:5, v/v). Save all
before use. If compositing equipment is used, the system must
above eluates and combine them (this fraction may be used as
incorporate glass sample containers for the collection of a min-
a check on column efficiency). Next, turn the column over and,
imum of 250 mL. samples.
in the direction of forward flow, elute the PCDD/PCDF frac-
SAMPLE PRESERVATION Samples must be cooled and tion with 20 mL toluene. Evaporate the toluene fraction to
stored at 4C. about 1 mL on a rotary evaporator and transfer this concen-
trate to a 2.0-mL Reacti-vial. Concentrate the sample using a
MHT Samples must be extracted within 30 days and analyzed stream of nitrogen gas. The final volume will depend on the
within 45 days of collection.
relative concentration of target analytes but it is typically
SAMPLE PREPARATION 100 L for soil samples and 500 L for sludge, still bottom, and
Soil Samples — Extract 20 g of a 1:1 soil and anhydrous sodium fl ash samples. Extracts which are determined to be outside
sulfate mixture with 1:4 methanol-petroleum ether for 2 h in the calibration range for individual analytes must be diluted or
a wrist-action shaker. Concentrate the extract in a K-D and a smaller portion of the sample must be re-extracted.
then exchange the solvent with hexane in the K-D. The final
An alternate carbon column clean-up also may be used with a
volume is 15 mL of hexane.
1 mL HPLC injector loop. The injector loop is connected to
Aqueous samples — Extract a 1 L sample with methylene chlo- the optional HPLC column.
ride, dry it with anhydrous sodium sulfate and concentrate it
QUALITY CONTROL Demonstrate, using a method blank,
in a K-D followed by exchange with hexane in the K-D. A
that all glassware and reagents are interferent-free at the MDL
continuous liquid-liquid extractor may be used in place of a
of the matrix of interest. A “method blank” must be run with
separatory funnel to avoid emulsions. The final volume is
each 20 or fewer samples. The method blank is also dosed with
15 mL of hexane.
the internal standards. For water samples, 1 L of deionized
Alumina column clean-up — The clean-up procedure and/or distilled water should be used as the method blank.
described below consists of two phases. The first phase involves Mineral oil may be used as the method blank for other matrices.
a sequential basic and acid washing of the extract that contains
Calculate response factors for standards relative to the internal
the analytes.
standards. Add a recovery standard to the samples prior to
Wash the 15 mL hexane extract with 20% potassium hydroxide injection. The concentration of the recovery standard in the
in a separatory funnel. Repeat the washing until no color is sample extract must be the same as that in the calibration
visible in the bottom layer but no more than four times because standards used to measure the response factors.
strong base is known to degrade certain PCDDs/PCDFs, so
Field duplicates (individual samples taken from the same loca-
contact time must be minimized. Next, partition the 15 mL
tion at the same time) should be analyzed periodically to deter-
hexane against 40 mL of 5% sodium chloride. Next, partition
mine the total precision (field and lab). Where appropriate,
the 15 mL hexane against 40 mL of concentrated sulfuric acid.
field blanks should be provided to monitor for possible cross-
Repeat the acid washings until no color is visible in the acid
contamination of samples in the field. GC column performance
layer (but no more than four times). Finally, partition the
must be demonstrated initially and verified prior to analyzing
15 mL hexane against 40 mL of 5% sodium chloride. Dry the
any sample in a 12-hr period. The GC column performance
organic layer with anhydrous sodium sulfate and concentrate
check solution must be analyzed under the same chromato-
it to near dryness with a rotary evaporator. Dissolve the hexane
graphic and mass spectrometric conditions used for other sam-
residue from the first phase of the clean-up in 2 mL of hexane
ples and standards.
and apply it carefully to the top of a pre-eluted Woelm super
1 neutral alumina column. Elute the column with 10 mL of 8 Retention times of target analytes must be verified using refer-
percent (v/v) methylene chloride in hexane. Check by GC/MS ence standards. These values must correspond to the retention
analysis that no PCDDs of PCDFs are elute in this fraction time windows established. While certain cleanup techniques
before discarding it. Elute the PCDDs and PCDFs from the are provided as part of this method, unique samples may

©1996 CRC Press LLC


require additional cleanup techniques to achieve the method When toluene is employed as the final solvent, use of a bonded
detection limit. phase column is recommended. Solvent exchange into tride-
cane is required for other liquid phases or nonbonded columns
REFERENCE Test Methods for Evaluating Solid Waste (SW-
such as CP-Sil-88. Chromatographic conditions must be
846). U.S.E.P.A., 1986. Method 8280, Rev. 0, Sept. 1986. Office
adjusted to account for solvent boiling points.
of Solid Wastes, Washington, DC.
PRECISION & ACCURACY Accuracy, precision, MDLs and
concentration ranges for the compounds covered by this
method have not been determined or published by EPA yet.
1,2,3,7,8-PeCDD EPA Method 8280 The sensitivity of this method is dependent upon the level of
CAS #40321-76-4 interferents within a given matrix. Proposed quantification lev-
els for target analytes were 2 ppb in soil samples, up to 10 ppb
TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins in other solid wastes and 10 ppt in water. Actual values have
and Polychlorinated Dibenzofurans. been shown to vary by homologous series and, to a lesser
MATRIX This method is appropriate for the determination degree, by individual isomer.
of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo- SAMPLING METHOD Grab and composite samples must
p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical be collected in 1 L or 1-quart amber glass bottles with Teflon®-
wastes including still bottoms, fuel oils, sludges, fl ash, reactor lined screw-caps that have been acid-washed and solvent rinsed
residues, soil and water. before use. If compositing equipment is used, the system must
METHOD SUMMARY This method covers 22 PCDD and incorporate glass sample containers for the collection of a min-
PCDF compounds and it uses a high resolution capillary GC imum of 250 mL. samples.
column with low resolution mass spectrometry. Samples are SAMPLE PRESERVATION Samples must be cooled and
extracted and concentrated by several methods that vary stored at 4C.
depending on the matrix involved. The organic extracts are
cleaned-up by washing with aqueous basic and acid solutions MHT Samples must be extracted within 30 days and analyzed
and then separated into fractions using a column of neutral within 45 days of collection.
alumina. The fraction containing the PCDDs and PCDFs is SAMPLE PREPARATION
then further cleaned-up using a column of activated carbon. Soil Samples — Extract 20 g of a 1:1 soil and anhydrous sodium
The final extract is concentrated and Carbon-13 labeled inter- sulfate mixture with 1:4 methanol-petroleum ether for 2 h in
nal standards are added prior to analysis by GC/MS using a a wrist-action shaker. Concentrate the extract in a K-D and
capillary GC column and selected ion monitoring using five then exchange the solvent with hexane in the K-D. The final
sets of ions that are detailed in the method. Certain 2,3,7,8- volume is 15 mL of hexane.
substituted congeners are used to provide calibration and
method recovery information. Proper column selection and Aqueous samples — Extract a 1 L sample with methylene chlo-
access to reference isomer standards, may in certain cases, pro- ride, dry it with anhydrous sodium sulfate and concentrate it
vide isomer specific data. in a K-D followed by exchange with hexane in the K-D. A
continuous liquid-liquid extractor may be used in place of a
INTERFERENCES Solvents, reagents, glassware, and other separatory funnel to avoid emulsions. The final volume is
sample processing hardware may yield discrete artifacts and/or 15 mL of hexane.
elevated baselines which may cause misinterpretation of chro-
Alumina column clean-up — The clean-up procedure
matographic data. Use high purity reagents and solvents to
described below consists of two phases. The first phase involves
minimize interference problems. Interferents coextracted from
a sequential basic and acid washing of the extract that contains
the sample will vary considerably from source to source.
the analytes.
PCDDs and PCDFs are often associated with other interfering
chlorinated compounds such as PCBs and polychlorinated Wash the 15 mL hexane extract with 20% potassium hydroxide
diphenyl ethers which may be found at concentrations several in a separatory funnel. Repeat the washing until no color is
orders of magnitude higher than that of the analytes of interest. visible in the bottom layer but no more than four times because
strong base is known to degrade certain PCDDs/PCDFs, so
INSTRUMENTATION A low resolution GC/MS utilizing 70
contact time must be minimized. Next, partition the 15 mL
ev must be capable of selected ion monitoring (SIM) for at hexane against 40 mL of 5% sodium chloride. Next, partition
least 11 ions simultaneously, with a cycle time of 1 second or the 15 mL hexane against 40 mL of concentrated sulfuric acid.
less. Minimum integration time for SIM is 50 ms per m/z. Also Repeat the acid washings until no color is visible in the acid
required is a GC-to-MS interface constructed of all glass or layer (but no more than four times). Finally, partition the
glass-lined materials. One of the following GC columns is 15 mL hexane against 40 mL of 5% sodium chloride. Dry the
required: organic layer with anhydrous sodium sulfate and concentrate
Column 1: 50 m CP-Sil-88 fused silica capillary column. it to near dryness with a rotary evaporator. Dissolve the hexane
Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick- residue from the first phase of the clean-up in 2 mL of hexane
ness) fused silica capillary column. and apply it carefully to the top of a pre-eluted Woelm super
Column 3: 30 m SP-2250 fused silica capillary column. 1 neutral alumina column. Elute the column with 10 mL of 8

©1996 CRC Press LLC


percent (v/v) methylene chloride in hexane. Check by GC/MS Retention times of target analytes must be verified using refer-
analysis that no PCDDs of PCDFs are elute in this fraction ence standards. These values must correspond to the retention
before discarding it. Elute the PCDDs and PCDFs from the time windows established. While certain cleanup techniques
column with 15 mL of 60 percent (v/v) methylene chloride in are provided as part of this method, unique samples may
hexane and collect this second fraction in a conical shaped require additional cleanup techniques to achieve the method
concentrator tube. detection limit.

Carbon column clean-up — Using a carefully regulated stream REFERENCE Test Methods for Evaluating Solid Waste (SW-
of nitrogen, concentrate the first 8 percent fraction (methylene 846). U.S.E.P.A., 1986. Method 8280, Rev. 0, Sept. 1986. Office
chloride in hexane) from the alumina column to about 1 mL. of Solid Wastes, Washington, DC.
Save this 8 percent concentrate for GC/MS analysis to check
for breakthrough of PCDDs and PCDFs. Concentrate the sec-
ond 60 percent fraction (methylene chloride in hexane) to 1,2,3,7,8-PeCDD EPA Method 8290
about 2 to 3 mL. Prepare a carbon column and rinse the carbon CAS #40321-76-4
with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
forward direction of flow and then in the reverse direction of TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly-
flow. While still in the reverse direction of flow, transfer the chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
sample concentrate to the column and elute with 10 mL of Chromatography/High-Resolution Mass Spectrometry
methylene chloride/methanol/benzene (75:20:5, v/v). Save all (HRGC/HRMS).
above eluates and combine them (this fraction may be used as
MATRIX This method is applicable with a variety of envi-
a check on column efficiency). Next, turn the column over and,
ronmental matrices including: water, soil, sediment, paper
in the direction of forward flow, elute the PCDD/PCDF frac- pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil,
tion with 20 mL toluene. Evaporate the toluene fraction to chemical reactor residue, and still bottoms.
about 1 mL on a rotary evaporator and transfer this concen-
trate to a 2.0-mL Reacti-vial. Concentrate the sample using a METHOD SUMMARY This method provides procedures for
stream of nitrogen gas. The final volume will depend on the the detection and quantitative measurement of polychlorinated
relative concentration of target analytes but it is typically dibenzo-p-dioxins (tetra- through octachlorinated homo-
100 L for soil samples and 500 L for sludge, still bottom, and logues; PCDDs), and polychlorinated dibenzofurans (tetra-
fl ash samples. Extracts which are determined to be outside through octachlorinated homologues; PCDFs) in a variety of
the calibration range for individual analytes must be diluted or environmental matrices and at part-per-trillion (ppt) to part-
per-quadrillion (ppq) concentrations. High-resolution gas
a smaller portion of the sample must be re-extracted.
chromatography and high-resolution mass spectrometry
An alternate carbon column clean-up also may be used with a (HRGC/HRMS) on purified sample extracts provides highly
1 mL HPLC injector loop. The injector loop is connected to specific identification of each analyte. Quantification is pro-
the optional HPLC column. vided using calibration standards.
QUALITY CONTROL Demonstrate, using a method blank, INTERFERENCES Solvents, reagents, glassware, and other
that all glassware and reagents are interferent-free at the MDL sample processing hardware may yield discrete artifacts that
of the matrix of interest. A “method blank” must be run with may cause misinterpretation of the chromatographic data.
each 20 or fewer samples. The method blank is also dosed with Analysts should avoid using PVC gloves. Interferants coex-
the internal standards. For water samples, 1 L of deionized tracted from the sample will vary considerably from matrix to
and/or distilled water should be used as the method blank. matrix. PCDDs and PCDFs are often associated with other
Mineral oil may be used as the method blank for other matrices. interfering chlorinated substances such as polychlorinated
biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs),
Calculate response factors for standards relative to the internal polychlorinated naphthalenes, and polychlorinated alkyldiben-
standards. Add a recovery standard to the samples prior to zofurans that may be found at concentrations several orders of
injection. The concentration of the recovery standard in the magnitude higher than the PCDDs or PCDFs.
sample extract must be the same as that in the calibration
A high-resolution capillary column is used in this method.
standards used to measure the response factors.
However, no single column is known to resolve all isomers. The
Field duplicates (individual samples taken from the same loca- 60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer
tion at the same time) should be analyzed periodically to deter- specificity. In order to determine the concentration of the
mine the total precision (field and lab). Where appropriate, 2,3,7,8-TCDD (if detected on the DB-5 column), the sample
field blanks should be provided to monitor for possible cross- extract must be reanalyzed on a column capable of
contamination of samples in the field. GC column performance 2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP-
must be demonstrated initially and verified prior to analyzing 2331, or equivalent).
any sample in a 12-hr period. The GC column performance INSTRUMENTATION High-Resolution Gas Chromato-
check solution must be analyzed under the same chromato- graph/High-Resolution Mass Spectrometer/Data System
graphic and mass spectrometric conditions used for other sam- (HRGC/HRMS/DS) equipped with a GC injection port
ples and standards. designed so that the separation of 2,3,7,8-TCDD from the other

©1996 CRC Press LLC


TCDD isomers achieved in the gas chromatographic column down and the PCDD/PCDF fraction is eluted with toluene.
is not appreciably degraded. The toluene fraction is concentrated and stored in the dark at
room temperature until analysis.
Column 1: 60 m DB-5 fused silica capillary column.
Column 2: 30 m DB-225 fused silica capillary column, or QUALITY CONTROL Demonstrate, through the analysis of
equivalent. a reagent water blank, that interferences from the analytical
PRECISION & ACCURACY Precision, bias and concentra- system, glassware, and reagents are under control. For each
tion ranges for the compounds covered by this method have analytical batch (up to 20 samples), a reagent blank, matrix
not been determined yet. The sensitivity of Method 8290 is spike, and matrix spike duplicate/duplicate must be analyzed
dependent upon the level of interferences within a given (the frequency of the spikes may be different for different mon-
matrix. Samples containing concentrations of specific conge- itoring programs). The blank and spiked samples must be car-
neric analytes of PCDDs and PCDFs that are greater than ten ried through all stages of the sample preparation and
times the upper method calibration limits must be analyzed by measurement steps.
a protocol designed for such concentration levels, e.g., EPA A GC column performance check is required at the beginning
Method 8280. of each 12-h period during which samples are analyzed. An
SAMPLE PREPARATION HRGC/HRMS method blank run is required between a cali-
Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil bration run and the first sample run. The same method blank
samples by refluxing a sample with toluene using a Dean-Stark extract may thus be analyzed more than once if the number of
water separator until all the water is removed. Filter the toluene samples within a batch requires more than 12 h of analyses.
extract through a glass fiber filter, or equivalent, and concen- At the beginning of each 12-h period during which samples
trate it to near dryness either on a rotary evaporator using an are to be analyzed, an aliquot of the 1) GC column performance
inert gas. Transfer the concentrate to a separatory funnel using
check solution and 2) a high-resolution concentration calibra-
hexane and wash it with 5% sodium chloride solution. Proceed
tion must be analyzed to demonstrate adequate GC resolution
to clean up.
and sensitivity, response factor reproducibility, and mass range
Soil/sediment — If the sample is wet, add anhydrous powdered calibration, and to establish the PCDD/PCDF retention time
sodium sulfate to it until a free flowing mixture is obtained. windows. A mass resolution check must also be performed to
Place the soil/sodium sulfate mixture in the Soxhlet apparatus, demonstrate adequate mass resolution using an appropriate
add toluene, and reflux for 16 h. The solvent must cycle com- reference compound (perfluorokerosene (PFK) is recom-
pletely through the system five times per h. Cool and filter the mended). If the required criteria are not met, remedial action
extract through a glass fiber filter and concentrate to near dry- must be taken before any samples are analyzed.
ness on a rotary evaporator. Transfer the residue to a separatory
funnel, using hexane. Proceed to clean up. Routine or continuing calibration (using a high resolution cal-
ibration solution) and the mass resolution check must also be
Aqueous samples — Use a 1-L sample; the method may require performed at the end of each 12 h period. Furthermore, a
acetone to be added to it. When the sample is judged to contain HRGC/HRMS method blank analysis must be recorded follow-
1% or more solids, it must be filtered through a glass fiber filter ing a calibration analysis and the first sample analysis.
that has been rinsed with toluene. If the suspended solids con-
tent is too great to filter, centrifuge the sample, decant, and To evaluate the performance of the analytical method, the QC
then filter the aqueous phase. Combine the solids from the check samples must be handled in exactly the same manner as
centrifuge bottle(s) with the particulates on the filter and with actual samples. Therefore, 1.0 mL of the QC check sample
the filter itself and proceed with Soxhlet extraction for soil/sed- concentrate is spiked into each of four 1 L aliquots of reagent
iment. Extract the aqueous filtrate with methylene chloride in water (which becomes the QC check sample), extracted, and
a separatory funnel, filter the extract through anhydrous then analyzed by GC. The variety of semivolatile analytes which
sodium sulfate, and concentrate it using a K-D apparatus or a may be analyzed by GC is such that the concentration of the
rotary evaporator. Exchange the solvent with hexane and pro- QC check sample concentrate is different for the different ana-
ceed to clean up. lytical techniques presented in the full method.
Clean up — The sample extract is cleaned up utilizing a num- The analyst must demonstrate also that the compounds of
ber of different techniques. Partition cleanup is where the sam- interest are being quantitatively recovered by the cleanup tech-
ple extract is partitioned with concentrated sulfuric acid, 5% nique before the cleanup is applied to actual samples. For sam-
aqueous sodium chloride, and 20% aqueous potassium ple extracts that are cleaned up, the associated quality control
hydroxide. Silica/alumina column cleanup involves packing samples (e.g., spikes, blanks, and duplicates) must also be pro-
gravity columns with silica gel and alumina and sequentially cessed through the same cleanup procedure. The analysis using
eluting the residue from the partition cleanup. Carbon column each determinative method (GC, GC/MS, HPLC) specifies
cleanup involves packing a column with a mixture of AX–21 instrument calibration procedures using stock standards. It is
and Celite 545 and sequentially eluting the sample concentrate recommended that cleanup also be performed on a series of
from the silica/alumina cleanup with hexane, cyclohex- the same type of standards to validate chromatographic elution
ane/methylene chloride (50:50), and methylene chloride/meth- patterns for the compounds of interest and to verify the absence
anol/toluene (75:20:5). Then the column is turned upside of interferences from reagents.

©1996 CRC Press LLC


REFERENCE Test Methods for Evaluating Solid Waste (SW- such as CP-Sil-88. Chromatographic conditions must be
846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office adjusted to account for solvent boiling points.
of Solid Wastes, Washington, DC.
PRECISION & ACCURACY Accuracy, precision, MDLs and
concentration ranges for the compounds covered by this
method have not been determined or published by EPA yet.
1,2,3,7,8-PeCDF EPA Method 8280 The sensitivity of this method is dependent upon the level of
CAS #57117-41-6 interferents within a given matrix. Proposed quantification lev-
els for target analytes were 2 ppb in soil samples, up to 10 ppb
TITLE The Analysis of Polychlorinated Dibenzo-P-Dioxins in other solid wastes and 10 ppt in water. Actual values have
and Polychlorinated Dibenzofurans. been shown to vary by homologous series and, to a lesser
degree, by individual isomer.
MATRIX This method is appropriate for the determination
of tetra-, penta-, hexa-, hepta-, and octachlorinated dibenzo- SAMPLING METHOD Grab and composite samples must
p-dioxins (PCDDs) and dibenzofurans (PCDFs) in chemical be collected in 1 L or 1-quart amber glass bottles with Teflon®-
wastes including still bottoms, fuel oils, sludges, fl ash, reactor lined screw-caps that have been acid-washed and solvent rinsed
residues, soil and water. before use. If compositing equipment is used, the system must
incorporate glass sample containers for the collection of a min-
METHOD SUMMARY This method covers 22 PCDD and
imum of 250 mL. samples.
PCDF compounds and it uses a high resolution capillary GC
column with low resolution mass spectrometry. Samples are SAMPLE PRESERVATION Samples must be cooled and
extracted and concentrated by several methods that vary stored at 4C.
depending on the matrix involved. The organic extracts are
cleaned-up by washing with aqueous basic and acid solutions MHT Samples must be extracted within 30 days and analyzed
and then separated into fractions using a column of neutral within 45 days of collection.
alumina. The fraction containing the PCDDs and PCDFs is SAMPLE PREPARATION
then further cleaned-up using a column of activated carbon. Soil Samples — Extract 20 g of a 1:1 soil and anhydrous sodium
The final extract is concentrated and Carbon-13 labeled inter- sulfate mixture with 1:4 methanol-petroleum ether for 2 h in
nal standards are added prior to analysis by GC/MS using a a wrist-action shaker. Concentrate the extract in a K-D and
capillary GC column and selected ion monitoring using five then exchange the solvent with hexane in the K-D. The final
sets of ions that are detailed in the method. Certain 2,3,7,8- volume is 15 mL of hexane.
substituted congeners are used to provide calibration and
method recovery information. Proper column selection and Aqueous samples — Extract a 1 L sample with methylene chlo-
access to reference isomer standards, may in certain cases, pro- ride, dry it with anhydrous sodium sulfate and concentrate it
vide isomer specific data. in a K-D followed by exchange with hexane in the K-D. A
continuous liquid-liquid extractor may be used in place of a
INTERFERENCES Solvents, reagents, glassware, and other separatory funnel to avoid emulsions. The final volume is
sample processing hardware may yield discrete artifacts and/or 15 mL of hexane.
elevated baselines which may cause misinterpretation of chro-
matographic data. Use high purity reagents and solvents to Alumina column clean-up — The clean-up procedure
minimize interference problems. Interferents coextracted from described below consists of two phases. The first phase involves
the sample will vary considerably from source to source. a sequential basic and acid washing of the extract that contains
PCDDs and PCDFs are often associated with other interfering the analytes.
chlorinated compounds such as PCBs and polychlorinated Wash the 15 mL hexane extract with 20% potassium hydroxide
diphenyl ethers which may be found at concentrations several in a separatory funnel. Repeat the washing until no color is
orders of magnitude higher than that of the analytes of interest. visible in the bottom layer but no more than four times because
INSTRUMENTATION A low resolution GC/MS utilizing 70 strong base is known to degrade certain PCDDs/PCDFs, so
ev must be capable of selected ion monitoring (SIM) for at contact time must be minimized. Next, partition the 15 mL
least 11 ions simultaneously, with a cycle time of 1 second or hexane against 40 mL of 5% sodium chloride. Next, partition
less. Minimum integration time for SIM is 50 ms per m/z. Also the 15 mL hexane against 40 mL of concentrated sulfuric acid.
required is a GC-to-MS interface constructed of all glass or Repeat the acid washings until no color is visible in the acid
glass-lined materials. One of the following GC columns is layer (but no more than four times). Finally, partition the
required: 15 mL hexane against 40 mL of 5% sodium chloride. Dry the
organic layer with anhydrous sodium sulfate and concentrate
Column 1: 50 m CP-Sil-88 fused silica capillary column. it to near dryness with a rotary evaporator. Dissolve the hexane
Column 2: DB-5 (30 m  0.25 mm I.D., 0.25-um film thick- residue from the first phase of the clean-up in 2 mL of hexane
ness) fused silica capillary column. and apply it carefully to the top of a pre-eluted Woelm super
Column 3: 30 m SP-2250 fused silica capillary column. 1 neutral alumina column. Elute the column with 10 mL of 8
When toluene is employed as the final solvent, use of a bonded percent (v/v) methylene chloride in hexane. Check by GC/MS
phase column is recommended. Solvent exchange into tride- analysis that no PCDDs of PCDFs are elute in this fraction
cane is required for other liquid phases or nonbonded columns before discarding it. Elute the PCDDs and PCDFs from the

©1996 CRC Press LLC


column with 15 mL of 60 percent (v/v) methylene chloride in require additional cleanup techniques to achieve the method
hexane and collect this second fraction in a conical shaped detection limit.
concentrator tube.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
Carbon column clean-up — Using a carefully regulated stream 846). U.S.E.P.A., 1986. Method 8280, Rev. 0, Sept. 1986. Office
of nitrogen, concentrate the first 8 percent fraction (methylene of Solid Wastes, Washington, DC.
chloride in hexane) from the alumina column to about 1 mL.
Save this 8 percent concentrate for GC/MS analysis to check
for breakthrough of PCDDs and PCDFs. Concentrate the sec-
ond 60 percent fraction (methylene chloride in hexane) to 1,2,3,7,8-PeCDF EPA Method 8290
CAS #57117-41-6
about 2 to 3 mL. Prepare a carbon column and rinse the carbon
with 5 mL cyclohexane/methylene chloride (50:50 v/v) in the
TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly-
forward direction of flow and then in the reverse direction of
chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas
flow. While still in the reverse direction of flow, transfer the
Chromatography/High-Resolution Mass Spectrometry
sample concentrate to the column and elute with 10 mL of
(HRGC/HRMS).
methylene chloride/methanol/benzene (75:20:5, v/v). Save all
above eluates and combine them (this fraction may be used as MATRIX This method is applicable with a variety of envi-
a check on column efficiency). Next, turn the column over and, ronmental matrices including: water, soil, sediment, paper
in the direction of forward flow, elute the PCDD/PCDF frac- pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil,
tion with 20 mL toluene. Evaporate the toluene fraction to chemical reactor residue, and still bottoms.
about 1 mL on a rotary evaporator and transfer this concen-
METHOD SUMMARY This method provides procedures for
trate to a 2.0-mL Reacti-vial. Concentrate the sample using a
the detection and quantitative measurement of polychlorinated
stream of nitrogen gas. The final volume will depend on the
dibenzo-p-dioxins (tetra- through octachlorinated homo-
relative concentration of target analytes but it is typically
logues; PCDDs), and polychlorinated dibenzofurans (tetra-
100 L for soil samples and 500 L for sludge, still bottom, and
through octachlorinated homologues; PCDFs) in a variety of
fl ash samples. Extracts which are determined to be outside
environmental matrices and at part-per-trillion (ppt) to part-
the calibration range for individual analytes must be diluted or
per-quadrillion (ppq) concentrations. High-resolution gas
a smaller portion of the sample must be re-extracted.
chromatography and high-resolution mass spectrometry
An alternate carbon column clean-up also may be used with a (HRGC/HRMS) on purified sample extracts provides highly
1 mL HPLC injector loop. The injector loop is connected to specific identification of each analyte. Quantification is pro-
the optional HPLC column. vided using calibration standards.
QUALITY CONTROL Demonstrate, using a method blank, INTERFERENCES Solvents, reagents, glassware, and other
that all glassware and reagents are interferent-free at the MDL sample processing hardware may yield discrete artifacts that
of the matrix of interest. A “method blank” must be run with may cause misinterpretation of the chromatographic data.
each 20 or fewer samples. The method blank is also dosed with Analysts should avoid using PVC gloves. Interferants coex-
the internal standards. For water samples, 1 L of deionized tracted from the sample will vary considerably from matrix to
and/or distilled water should be used as the method blank. matrix. PCDDs and PCDFs are often associated with other
Mineral oil may be used as the method blank for other matrices. interfering chlorinated substances such as polychlorinated
biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs),
Calculate response factors for standards relative to the internal
polychlorinated naphthalenes, and polychlorinated alkyldiben-
standards. Add a recovery standard to the samples prior to
zofurans that may be found at concentrations several orders of
injection. The concentration of the recovery standard in the
magnitude higher than the PCDDs or PCDFs.
sample extract must be the same as that in the calibration
standards used to measure the response factors. A high-resolution capillary column is used in this method.
However, no single column is known to resolve all isomers. The
Field duplicates (individual samples taken from the same loca-
60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer
tion at the same time) should be analyzed periodically to deter-
specificity. In order to determine the concentration of the
mine the total precision (field and lab). Where appropriate,
2,3,7,8-TCDD (if detected on the DB-5 column), the sample
field blanks should be provided to monitor for possible cross-
extract must be reanalyzed on a column capable of
contamination of samples in the field. GC column performance
2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP-
must be demonstrated initially and verified prior to analyzing
2331, or equivalent).
any sample in a 12-hr period. The GC column performance
check solution must be analyzed under the same chromato- INSTRUMENTATION High-Resolution Gas Chromato-
graphic and mass spectrometric conditions used for other sam- graph/High-Resolution Mass Spectrometer/Data System
ples and standards. (HRGC/HRMS/DS) equipped with a GC injection port
designed so that the separation of 2,3,7,8-TCDD from the other
Retention times of target analytes must be verified using refer-
TCDD isomers achieved in the gas chromatographic column
ence standards. These values must correspond to the retention
is not appreciably degraded.
time windows established. While certain cleanup techniques
are provided as part of this method, unique samples may Column 1: 60 m DB-5 fused silica capillary column.

©1996 CRC Press LLC


Column 2: 30 m DB-225 fused silica capillary column, or QUALITY CONTROL Demonstrate, through the analysis of
equivalent. a reagent water blank, that interferences from the analytical
system, glassware, and reagents are under control. For each
PRECISION & ACCURACY Precision, bias and concentra-
analytical batch (up to 20 samples), a reagent blank, matrix
tion ranges for the compounds covered by this method have
spike, and matrix spike duplicate/duplicate must be analyzed
not been determined yet. The sensitivity of Method 8290 is
(the frequency of the spikes may be different for different mon-
dependent upon the level of interferences within a given
itoring programs). The blank and spiked samples must be car-
matrix. Samples containing concentrations of specific conge-
neric analytes of PCDDs and PCDFs that are greater than ten ried through all stages of the sample preparation and
times the upper method calibration limits must be analyzed by measurement steps.
a protocol designed for such concentration levels, e.g., EPA A GC column performance check is required at the beginning
Method 8280. of each 12-h period during which samples are analyzed. An
SAMPLE PREPARATION HRGC/HRMS method blank run is required between a cali-
Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil bration run and the first sample run. The same method blank
samples by refluxing a sample with toluene using a Dean-Stark extract may thus be analyzed more than once if the number of
water separator until all the water is removed. Filter the toluene samples within a batch requires more than 12 h of analyses.
extract through a glass fiber filter, or equivalent, and concen- At the beginning of each 12-h period during which samples
trate it to near dryness either on a rotary evaporator using an are to be analyzed, an aliquot of the 1) GC column performance
inert gas. Transfer the concentrate to a separatory funnel using check solution and 2) a high-resolution concentration calibra-
hexane and wash it with 5% sodium chloride solution. Proceed tion must be analyzed to demonstrate adequate GC resolution
to clean up. and sensitivity, response factor reproducibility, and mass range
Soil/sediment — If the sample is wet, add anhydrous powdered calibration, and to establish the PCDD/PCDF retention time
sodium sulfate to it until a free flowing mixture is obtained. windows. A mass resolution check must also be performed to
Place the soil/sodium sulfate mixture in the Soxhlet apparatus, demonstrate adequate mass resolution using an appropriate
add toluene, and reflux for 16 h. The solvent must cycle com- reference compound (perfluorokerosene (PFK) is recom-
pletely through the system five times per h. Cool and filter the mended). If the required criteria are not met, remedial action
extract through a glass fiber filter and concentrate to near dry- must be taken before any samples are analyzed.
ness on a rotary evaporator. Transfer the residue to a separatory Routine or continuing calibration (using a high resolution cal-
funnel, using hexane. Proceed to clean up. ibration solution) and the mass resolution check must also be
Aqueous samples — Use a 1-L sample; the method may require performed at the end of each 12 h period. Furthermore, a
acetone to be added to it. When the sample is judged to contain HRGC/HRMS method blank analysis must be recorded follow-
1% or more solids, it must be filtered through a glass fiber filter ing a calibration analysis and the first sample analysis.
that has been rinsed with toluene. If the suspended solids con- To evaluate the performance of the analytical method, the QC
tent is too great to filter, centrifuge the sample, decant, and check samples must be handled in exactly the same manner as
then filter the aqueous phase. Combine the solids from the actual samples. Therefore, 1.0 mL of the QC check sample
centrifuge bottle(s) with the particulates on the filter and with concentrate is spiked into each of four 1 L aliquots of reagent
the filter itself and proceed with Soxhlet extraction for soil/sed- water (which becomes the QC check sample), extracted, and
iment. Extract the aqueous filtrate with methylene chloride in
then analyzed by GC. The variety of semivolatile analytes which
a separatory funnel, filter the extract through anhydrous
may be analyzed by GC is such that the concentration of the
sodium sulfate, and concentrate it using a K-D apparatus or a
QC check sample concentrate is different for the different ana-
rotary evaporator. Exchange the solvent with hexane and pro-
lytical techniques presented in the full method.
ceed to clean up.
The analyst must demonstrate also that the compounds of
Clean up — The sample extract is cleaned up utilizing a num-
interest are being quantitatively recovered by the cleanup tech-
ber of different techniques. Partition cleanup is where the sam-
nique before the cleanup is applied to actual samples. For sam-
ple extract is partitioned with concentrated sulfuric acid, 5%
ple extracts that are cleaned up, the associated quality control
aqueous sodium chloride, and 20% aqueous potassium
samples (e.g., spikes, blanks, and duplicates) must also be pro-
hydroxide. Silica/alumina column cleanup involves packing
cessed through the same cleanup procedure. The analysis using
gravity columns with silica gel and alumina and sequentially
each determinative method (GC, GC/MS, HPLC) specifies
eluting the residue from the partition cleanup. Carbon column
instrument calibration procedures using stock standards. It is
cleanup involves packing a column with a mixture of AX–21
recommended that cleanup also be performed on a series of
and Celite 545 and sequentially eluting the sample concentrate
from the silica/alumina cleanup with hexane, cyclohex- the same type of standards to validate chromatographic elution
ane/methylene chloride (50:50), and methylene chloride/meth- patterns for the compounds of interest and to verify the absence
anol/toluene (75:20:5). Then the column is turned upside of interferences from reagents.
down and the PCDD/PCDF fraction is eluted with toluene. REFERENCE Test Methods for Evaluating Solid Waste (SW-
The toluene fraction is concentrated and stored in the dark at 846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office
room temperature until analysis. of Solid Wastes, Washington, DC.

©1996 CRC Press LLC


neric analytes of PCDDs and PCDFs that are greater than ten
2,3,4,7,8-PeCDF EPA Method 8290
times the upper method calibration limits must be analyzed by
CAS #57117-31-4
a protocol designed for such concentration levels, e.g., EPA
TITLE Polychlorinated Dibenzodioxins (PCDDs) and Poly- Method 8280.
chlorinated Dibenzofurans (PCDFs) by High-Resolution Gas SAMPLE PREPARATION
Chromatography/High-Resolution Mass Spectrometry Sludge/wet fuel oil — Extract aqueous sludge or wet fuel oil
(HRGC/HRMS). samples by refluxing a sample with toluene using a Dean-Stark
MATRIX This method is applicable with a variety of envi- water separator until all the water is removed. Filter the toluene
ronmental matrices including: water, soil, sediment, paper extract through a glass fiber filter, or equivalent, and concen-
pulp, fl ash, fish tissue, human adipose tissue, sludges, fuel oil, trate it to near dryness either on a rotary evaporator using an
chemical reactor residue, and still bottoms. inert gas. Transfer the concentrate to a separatory funnel using
hexane and wash it with 5% sodium chloride solution. Proceed
METHOD SUMMARY This method provides procedures for to clean up.
the detection and quantitative measurement of polychlorinated
dibenzo-p-dioxins (tetra- through octachlorinated homo- Soil/sediment — If the sample is wet, add anhydrous powdered
logues; PCDDs), and polychlorinated dibenzofurans (tetra- sodium sulfate to it until a free flowing mixture is obtained.
through octachlorinated homologues; PCDFs) in a variety of Place the soil/sodium sulfate mixture in the Soxhlet apparatus,
environmental matrices and at part-per-trillion (ppt) to part- add toluene, and reflux for 16 h. The solvent must cycle com-
per-quadrillion (ppq) concentrations. High-resolution gas pletely through the system five times per h. Cool and filter the
chromatography and high-resolution mass spectrometry extract through a glass fiber filter and concentrate to near dry-
(HRGC/HRMS) on purified sample extracts provides highly ness on a rotary evaporator. Transfer the residue to a separatory
specific identification of each analyte. Quantification is pro- funnel, using hexane. Proceed to clean up.
vided using calibration standards. Aqueous samples — Use a 1-L sample; the method may require
INTERFERENCES Solvents, reagents, glassware, and other acetone to be added to it. When the sample is judged to contain
sample processing hardware may yield discrete artifacts that 1% or more solids, it must be filtered through a glass fiber filter
may cause misinterpretation of the chromatographic data. that has been rinsed with toluene. If the suspended solids con-
Analysts should avoid using PVC gloves. Interferants coex- tent is too great to filter, centrifuge the sample, decant, and
tracted from the sample will vary considerably from matrix to then filter the aqueous phase. Combine the solids from the
matrix. PCDDs and PCDFs are often associated with other centrifuge bottle(s) with the particulates on the filter and with
interfering chlorinated substances such as polychlorinated the filter itself and proceed with Soxhlet extraction for soil/sed-
biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), iment. Extract the aqueous filtrate with methylene chloride in
polychlorinated naphthalenes, and polychlorinated alkyldiben- a separatory funnel, filter the extract through anhydrous
zofurans that may be found at concentrations several orders of sodium sulfate, and concentrate it using a K-D apparatus or a
magnitude higher than the PCDDs or PCDFs. rotary evaporator. Exchange the solvent with hexane and pro-
ceed to clean up.
A high-resolution capillary column is used in this method.
However, no single column is known to resolve all isomers. The Clean up — The sample extract is cleaned up utilizing a num-
60 m DB-5 GC column is capable of 2,3,7,8-TCDD isomer ber of different techniques. Partition cleanup is where the sam-
specificity. In order to determine the concentration of the ple extract is partitioned with concentrated sulfuric acid, 5%
2,3,7,8-TCDD (if detected on the DB-5 column), the sample aqueous sodium chloride, and 20% aqueous potassium
extract must be reanalyzed on a column capable of hydroxide. Silica/alumina column cleanup involves packing
2,3,7,8-TCDF isomer specificity (e.g., DB-225, SP-2330, SP- gravity columns with silica gel and alumina and sequentially
2331, or equivalent). eluting the residue from the partition cleanup. Carbon column
cleanup involves packing a column with a mixture of AX–21
INSTRUMENTATION High-Resolution Gas Chromato- and Celite 545 and sequentially eluting the sample concentrate
graph/High-Resolution Mass Spectrometer/Data System from the silica/alumina cleanup with hexane, cyclohex-
(HRGC/HRMS/DS) equipped with a GC injection port ane/methylene chloride (50:50), and methylene chloride/meth-
designed so that the separation of 2,3,7,8-TCDD from the other anol/toluene (75:20:5). Then the column is turned upside
TCDD isomers achieved in the gas chromatographic column down and the PCDD/PCDF fraction is eluted with toluene.
is not appreciably degraded.
The toluene fraction is concentrated and stored in the dark at
Column 1: 60 m DB-5 fused silica capillary column. room temperature until analysis.
Column 2: 30 m DB-225 fused silica capillary column, or
QUALITY CONTROL Demonstrate, through the analysis of
equivalent.
a reagent water blank, that interferences from the analytical
PRECISION & ACCURACY Precision, bias and concentra- system, glassware, and reagents are under control. For each
tion ranges for the compounds covered by this method have analytical batch (up to 20 samples), a reagent blank, matrix
not been determined yet. The sensitivity of Method 8290 is spike, and matrix spike duplicate/duplicate must be analyzed
dependent upon the level of interferences within a given (the frequency of the spikes may be different for different moni-
matrix. Samples containing concentrations of specific conge- toring programs). The blank and spiked samples must be carried

©1996 CRC Press LLC


through all stages of the sample preparation and measurement MATRIX Chemical wastes, fuel oils, still bottoms, sludges,
steps. water, soil, fl ash, reactor residues.
A GC column performance check is required at the beginning APPLICATION This method is used for the analysis of tetra-
of each 12-h period during which samples are analyzed. An , penta-, hexa-, hepta-, and octachlorinated dibenzo-p-dioxins
HRGC/HRMS method blank run is required between a cali- (PCDDs) and dibenzofurans (PCDFs). The sensitivity of the
bration run and the first sample run. The same method blank method is dependent on the level of interferents within the
extract may thus be analyzed more than once if the number of matrix. Only experienced analysts should be used.
samples within a batch requires more than 12 h of analyses. Special safety precautions must be observed and an EPA-
At the beginning of each 12-h period during which samples approved sample disposal plan must be used.
are to be analyzed, an aliquot of the 1) GC column performance INTERFERENCES Solvents, reagents, and glassware may
check solution and 2) a high-resolution concentration calibra- introduce artifacts. Other interferences may come from coex-
tion must be analyzed to demonstrate adequate GC resolution tracted compounds from samples; PCBs and polychlorinated
and sensitivity, response factor reproducibility, and mass range diphenyl ethers are common interferents.
calibration, and to establish the PCDD/PCDF retention time
INSTRUMENTATION GC/MS with a fused silica capillary
windows. A mass resolution check must also be performed to column. Also, solvent extraction and concentration glassware
demonstrate adequate mass resolution using an appropriate and either a gravity flow activated carbon AX–21/silica gel Type
reference compound (perfluorokerosene (PFK) is recom- 60 EM reagent column or a HPLC with a 10 mm by 7 cm
mended). If the required criteria are not met, remedial action silanized glass column with active carbon AX–21 and Spher-
must be taken before any samples are analyzed. isorb S10W silica for sample cleanup. One of three fused silica
Routine or continuing calibration (using a high resolution cal- capillary GC columns may be used: column 1: 50 m CP-Sil-88;
ibration solution) and the mass resolution check must also be Column 2: 30 m by 0.25 mm DB-5; colunm 3: 30 m SP-2250.
performed at the end of each 12 h period. Furthermore, a RANGE 50–6,000 picograms
HRGC/HRMS method blank analysis must be recorded follow-
MDL 1.64 ng/L (in reagent water); 0.33 g/kg (in Missouri
ing a calibration analysis and the first sample analysis.
soil); 0.16 g/kg (in fl ash); 0.92 g/kg (in industrial sludge);
To evaluate the performance of the analytical method, the QC 1.61 g/kg (in still bottom); 0.80 g/kg (in fuel oil); MDLs are
check samples must be handled in exactly the same manner as for carbon-13 labeled analyte.
actual samples. Therefore, 1.0 mL of the QC check sample PRECISION (as RSD): 6.1% with 5 ng/g in clay; 5.0% with
concentrate is spiked into each of four 1 L aliquots of reagent 25 ng/g soil; 4.8% with 125 ng/g in sludge.
water (which becomes the QC check sample), extracted, and
then analyzed by GC. The variety of semivolatile analytes which ACCURACY (as Mean % Recovery): 57.4% with 5 ng/g in
may be analyzed by GC is such that the concentration of the clay; 64.4% with 25 ng/g in soil; 84.8% with 125 ng/g in sludge;
QC check sample concentrate is different for the different ana- 105.8% with 46 ng/g in fl ash.
lytical techniques presented in the full method. SAMPLING METHOD Use 1 L (or quart) amber glass bot-
The analyst must demonstrate also that the compounds of tles with Teflon®-lined or solvent washed foil screw caps. Tape
caps to bottle after sampling.
interest are being quantitatively recovered by the cleanup tech-
nique before the cleanup is applied to actual samples. For sam- Compositing equipment must use glass containers and contain
ple extracts that are cleaned up, the associated quality control no Tygon or rubber tubing. Sample bottles must not be pre-
samples (e.g., spikes, blanks, and duplicates) must also be pro- washed with the sample before its collection. Aqueous samples
cessed through the same cleanup procedure. The analysis using cannot be aliquoted from sample containers — the entire sam-
each determinative method (GC, GC/MS, HPLC) specifies ple must be used and the container is washed out with the
instrument calibration procedures using stock standards. It is extracting solvent.
recommended that cleanup also be performed on a series of STABILITY Cool to 4C and store at this temperature. When
the same type of standards to validate chromatographic elution toluene is employed as the final solvent use a bonded phase GC
patterns for the compounds of interest and to verify the absence column for separation. Otherwise, solvent exchange into tride-
of interferences from reagents. cane is required for other liquid phases or the CP-Sil-88 GC
column.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
846). U.S. EPA. 1983. Method 8290, Rev. 0, Nov. 1990. Office MHT 30 days; samples must be completely analyzed within
of Solid Wastes, Washington, DC. 45 days of collection.
QUALITY CONTROL A method blank must be analyzed
each time a set of samples is extracted or there is a change in
1,2,3,7,8-PeCDF EPA Method 8280 reagents. A lab method blank must be run with each analytical
CAS #57117-41-6 batch of 20 or fewer samples. Field duplicates and field blanks
should be analyzed periodically. GC column performance must
TITLE Analysis of PCDDs and PCDFs be demonstrated initially and verified prior to analyzing any

©1996 CRC Press LLC


sample in a 12 h period. A series of calibration standards must from source to source, depending on the diversity of the site
be processed through the procedure to validate elution patterns being sampled.
and absence of interferents from reagents. Both the alumina
INSTRUMENTATION Major instrumentation includes a GC
column and carbon column performance must be routinely with a splitless or on-column injection port for capillary col-
checked for presence of the analyte. umn, a MS with 70 eV electron impact ionization, and a data
Performance evaluation samples and split samples with other system to collect and record MS data, and process it. A K-D
laboratories are also expected to be periodically analyzed. apparatus is used to concentrate extracts.

REFERENCE Method 8280, SW-846, 3rd ed., Nov.1986. GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
Pentachlorobenzene EPA Method 1625 method are usually dependent on the level of interferences
CAS #608-93-5 rather than instrumental limitations. The limits typify the min-
imum quantities that can be detected with no interferences
TITLE Semivolatile Organic Compounds by Isotope Dilu- present.
tion GC/MS The minimum level (in g/mL) was not listed. This is defined
MATRIX The compounds may be determined in waters, as a minimum level at which the analytical system shall give
soils, and municipal sludges by this method. recognizable mass spectra (background corrected) and accept-
able calibration points.
METHOD SUMMARY This method is used to determine
The MDL (in g/kg) in low solids was not listed and in high
176 semivolatile toxic organic pollutants associated with the
solids was not listed; these were determined in digested sludge
CWA (as amended 1987); the RCRA (as amended 1986); the
(low solids) and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
to extraction and analysis by capillary column gas chromatog- The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS). deviation (in g/L) was not listed.
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%,
a 1-L sample is extracted at pH 12–13, then at pH <2 with SAMPLE COLLECTION, PRESERVATION & HANDLING
methylene chloride using continuous extraction techniques. Collect samples in glass containers. Aqueous samples which
flow freely are collected in refrigerated bottles using automatic
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from
extracted at pH 12–13, then at pH <2 with methylene chloride the time of collection until extraction. If residual chlorine is
using continuous extraction techniques. If the solids content is present in aqueous samples, add 80 mg sodium thiosulfate/L
greater than 30%, the sample is extracted using ultrasonic of water. Begin sample extraction within 7 days of collection,
techniques. and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a SAMPLE PREPARATION Samples containing 1% solids or
volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid
centrated. Extracts are concentrated to 1 mL if GPC is not extraction techniques. Samples containing 1 to 30% solids are
performed, and to 0.5 mL if GPC is performed. diluted to the 1% level with reagent water and extracted using
continuous liquid-liquid extraction techniques. Samples con-
An internal standard is added to the extract, and a 1-mL aliquot taining greater than 30% solids are extracted using ultrasonic
of the extract is injected into the GC. The compounds are techniques.
separated by GC and detected by a MS. The labeled compounds
serve to correct the variability of the analytical technique. Base/neutral extraction — Adjust the pH of the waters in the
extractors to 12–13 with 6 N NaOH. Extract with methylene
INTERFERENCES Solvents, reagents, glassware, and other chloride for 24–48 h.
sample processing hardware may yield artifacts and/or elevated Acid extraction — Adjust the pH of the waters in the extractors
baselines causing misinterpretation of chromatograms and to 2 or less using 6 N sulfuric acid. Extract with methylene
spectra. Materials used in the analysis must be demonstrated chloride for 24–48 h.
to be free from interferences under the conditions of analysis Ultrasonic extraction of high solids samples — Add anhy-
by running method blanks initially and with each sample lot drous sodium sulfate to the sample and QC aliquot(s).
(sample started through the extraction process on a given 8-h Add acetone:methylene chloride (1:1) to the sample and
shift, to a maximum of 20). Specific selection of reagents and mix thoroughly
purification of solvents by distillation in all glass systems may
Concentrate extracts using a K-D apparatus.
be required. Glassware and, where possible, reagents are
cleaned by solvent rinse and baking at 450C for 1-h minimum. QUALITY CONTROL The analyst is permitted to modify
Interferences coextracted from samples will vary considerably this method to improve separations or lower the costs of

©1996 CRC Press LLC


measurements, provided all performance specifications are cleanup, the extract or diluted sample is analyzed by gas chro-
met. Analyses of blanks are required to demonstrate freedom matography with electron capture detection (GC/ECD).
from contamination. When results of spikes indicate atypical
The sensitivity level of this method usually depends on the level
method performance for samples, the samples are diluted to
bring method performance within acceptable limits. of interferences rather than on instrumental limitations. This
method may be used in conjunction with EPA Method 3620,
For low solids (aqueous samples), extract, concentrate, and Florisil Column Cleanup, EPA Method 3660, Sulfur Cleanup,
analyze two sets of four 1-L aliquots (8 aliquots total) of the and EPA Method 3640, Gel Permeation Chromatography, to
precision and recovery standard. For high solids samples, two aid in the elimination of interferences.
sets of four 30-g aliquots of the high solids reference matrix
are used. INTERFERENCES Solvents, reagents, glassware, and other
hardware used in sample processing may introduce artifacts
Spike all samples with labeled compounds to assess method which may result in elevated baselines, causing misinterpreta-
performance. Compute percent recovery of the labeled com- tion of gas chromatograms. Interferants coextracted from the
pounds using the internal standard method. Compare the samples will vary considerably from waste to waste. Glassware
labeled compound recovery for each compound with the cor- must be scrupulously clean. Phthalate esters, if present in a
responding labeled compound recovery. sample, will interfere only with the BHC isomers. The presence
Reagent water and high solids reference matrix blanks are ana- of elemental sulfur will result in large peaks, and can often
lyzed to demonstrate freedom from contamination. Extract mask the region of compounds eluting after 1,2,4,5-tetra-
and concentrate a 1-L reagent water blank or a high solids chlorobenzene. The tetrabutylammonium (TBA)-sulfite pro-
reference matrix blank with each sample’s lot (samples started cedure (EPA Method 3660) works well for the removal of
through the extraction process on the same 8-h shift, to a elemental sulfur. Waxes and lipids can be removed by gel per-
maximum of 20 samples). meation chromatography (EPA Method 3640).
Field replicates may be collected to determine the precision of INSTRUMENTATION A GC suitable for on-column injec-
the sampling technique, and spiked samples may be required tions and all required accessories, including and electron cap-
to determine the accuracy of the analysis when the internal ture detector (ECD), analytical columns, recorder, gases, and
standard method is used. syringes are needed. A data system for measuring peak heights
and/or peak areas is recommended. A Kuderna-Danish (K-D)
REFERENCE Semivolatile Organic Compounds by Isotope
apparatus will also be needed to concentrate extracts.
Dilution GC/MS. Office of Water Regulation and Standards,
U.S. EPA Industrial Technology Division, Washington, DC, Column 1: 30 m 0.53 mm I.D. fused-silica capillary column
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, chemically bonded with trifluoropropyl methyl silicone
U.S. EPA, Office of Water Regulations and Standards, 401 M (DB-210 or equivalent).
St., SW, Washington, DC, 20460. Phone: 202-382-7131). Column 2: 30 m 0.53 mm I.D. fused-silica capillary column
chemically bonded with polyethylene glycol (DB-WAX or
equivalent).
Pentachlorobenzene EPA Method 8121 PRECISION & ACCURACY This method has been tested in
CAS #608-93-5 a single lab by using organic-free reagent water, sandy loam
samples, and extracts which were spiked with the test com-
TITLE Chlorinated Hydrocarbons by GC: Capillary Column pounds at one concentration. Single-operator precision and
Technique method accuracy were found to be related to the concentration
MATRIX This method covers aqueous and solid matrices. of compound and the type of matrix. The accuracy and preci-
This includes a wide variety such as drinking water, ground- sion technique will be determined by the sample matrix, sam-
water, industrial wastewaters, surface waters, soils, solids, and ple preparation technique, optional cleanup techniques, and
sediments. calibration procedures used.

METHOD SUMMARY This method provides procedures for MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
the determination of 22 chlorinated hydrocarbons in water, Matrix Factor (b)
soil/sediment, and waste matrices. A measured volume or
Groundwater 10
weight of sample is extracted by using one of the appropriate
Low-concentration soil by ultrasonic extraction 670
sample extraction techniques specified in EPA Method 3510,
with GPC cleanup
EPA Method 3520, EPA Method 3540, or EPA Method 3550,
High-concentration soil and sludges 10,000
or diluted using EPA Method 3580. Aqueous samples are
by ultrasonic extraction
extracted at neutral pH with methylene chloride by using either
Waste not miscible with water 100,000
a separatory funnel (EPA Method 3510) or a continuous liquid-
liquid extractor (EPA Method 3520). Solid samples are (a) Sample EQLs are highly matrix-dependent. The EQLs listed
extracted with hexane/acetone (1:1) by using a Soxhlet extrac- herein are provided for guidance and may not always be achievable.
tor (EPA Method 3540) or with methylene chloride/acetone (b) EQL = [Method detection limit]  [Factor]. For nonaqueous
(1:1) by using an ultrasonic extractor (EPA Method 3550).After samples, the factor is on a wet-weight basis.

©1996 CRC Press LLC


PRECISION & ACCURACY MDL is the method detection 7 days and their extracts analyzed within 40 days. Concentrated
limit for organic-free reagent water. MDLwas determined from waste, soil, sediment, and sludge samples must be extracted
the analysis of eight replicate aliquots processed through the within 14 days and their extracts analyzed within 40 days.
entire analytical method (extraction, Florisil cartridge cleanup,
and GC/ECD analysis). SAMPLE PREPARATION Prepare stock standard solutions in
hexane. Calibration standards at a minimum of five concentra-
The MDL (in ng/L) was 38. tions should be prepared through dilution of the stock standards
The accuracy (as average % recovery using 5 determinations with hexane. The suggested internal standards are: 2,5-dibromo-
and no Florisil cleanup) from a spike concentration of 1.0 g/L toluene, 1,3,5-tribromobenzene, and , -dibromo-m-xylene.
and separatory funnel extraction was 89% with a final volume The analyst can use any of the three compounds provided that
of 10 mL. they are resolved from matrix interferences. Recommended sur-
rogate compounds are -2,6-trichlorotoluene, 1,4-dichloronaph-
The precision (as RSD% using 5 determinations and no Florisil thalene, and 2,3,4,5,6-pentachlorotoluene.
cleanup) from a spike concentration of 1.0 g/L and separatory
funnel extraction was 6.5% with a final volume of 10 mL. In general, water samples are extracted at a neutral pH with
methylene chloride using a separatory funnel (EPA Method
The accuracy (as average % recovery using 5 determinations 3510) or a continuous liquid-liquid extractor (EPA Method
and no Florisil cleanup), from a spike concentration of 330g/L 3520). Solid samples are extracted with hexane/acetone (1:1
and ultrasonic extraction of solid samples using 1:1 methylene v:v) using a Soxhlet extractor (EPA Method 3540) or with
chloride and acetone, was 81% with a final volume of 10 mL.
methylene chloride/acetone (1:1 v:v) using an ultrasonic
The precision (as RSD% using 5 determinations and no Florisil extractor (EPA Method 3550). Non-aqueous waste samples
cleanup), from a spike concentration of 330g/L and ultrasonic may be diluted using EPA Method 3580. Prior to Florisil
extraction of solid samples using 1:1 methylene chloride and cleanup or gas chromatographic analysis, the extraction solvent
acetone, was 3.5% with a final volume of 10 mL. must be exchanged to hexane. Sample extracts that will be
subjected to gel permeation chromatography do not need sol-
SAMPLE COLLECTION, PRESERVATION & HANDLING
Volatile organics — Standard 40-mL glass screw-cap VOA vials vent exchange.
with Teflon®-faced silicone septum may be used for both liquid Cleanup procedures may not be necessary for a relatively clean
and solid matrices. When collecting samples, liquids and solids matrix. If removal of interferences such as chlorinated phenols,
should be introduced into the vials gently to reduce agitation phthalate esters, etc., is required, proceed with the procedure
which might drive off volatile compounds. If there are any air outlined in EPA Method 3620.
bubbles present the sample must be retaken. The vials with
solids should be tapped slightly as they are filled to try and QUALITY CONTROL Analyze a quality control check stan-
eliminate as much free air space as possible. Two vials from dard to demonstrate that the operation of the GC is in control.
each sampling location should be sealed in separate plastic bags The frequency of the check standard analysis is equivalent to
to prevent cross-contamination between samples. 10% of the samples analyzed. If the recovery of any compound
found in the check standard is less than 80% of the certified
Semivolatile organics — Containers used to collect samples for value, the problem must be corrected and a new set of calibra-
the determination of semivolatile organic compounds should tion standards must be prepared and analyzed. Calculate sur-
be soap and water washed followed by methanol (or isopro- rogate standard recoveries for all samples, blanks, and spikes.
panol) rinsing. The sample containers should be of glass or
An internal standard peak area check must be performed on
Teflon® and have screw-top covers with Teflon® liners.
all samples. The internal standard must be evaluated for accep-
Preservation for volatile organics — No preservation is used tance by determining whether the measured area for the inter-
with concentrated waste samples. With liquid samples contain- nal standard deviates by more than 30% from the average area
ing no residual chlorine, 4 drops of concentrated hydrochloric for the internal standard in the calibration standards. When
acid are added and the samples are immediately cooled to 4 C. the internal standard peak area is outside that limit, all samples
When liquid samples contain residual chlorine, they are treated that fall outside the QC criteria must be reanalyzed. Any com-
as above and, in addition, 4 drops of 4% aqueous sodium pound confirmed by two columns may also be confirmed by
thiosulfate are added to remove the residual chlorine. Soil, GC/MS (EPA Method 8270). The GC/MS would normally
sediment, and sludge samples are only cooled to 4C. require a minimum concentration of 1 ng/L in the final
Preservation for semivolatile organics — No preservation is extract for each compound. Include a mid-concentration cal-
used with concentrated waste samples. With liquid samples ibration standard after each group of 20 samples in the analysis
containing no residual chlorine and with soil, sediment, and sequence. The response factors for the mid-concentration cal-
sludge samples, immediately cooling to 4C is the only preser- ibration must be within 15% of the average values for the
vation used. When residual chlorine is present then 3 mL of multiconcentration calibration.
10% aqueous sodium sulfate is added for each gallon of sample
REFERENCE Test Methods for Evaluating Solid Waste, Phys-
collected, followed by cooling to 4C.
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
Holding times — The holding time for all volatile organics of Solid Waste, Washington, DC, 1990. EPA Method 8121, Rev.
samples is 14 days. Liquid samples must be extracted within 0, Nov. 1990.

©1996 CRC Press LLC


This calculation is based on a 30 g sample and gel perme-
Pentachlorobenzene EPA Method 8270
ation chromatography cleanup.
CAS #608-93-5
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc. High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec- (a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate, This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral with a screw-top Teflon®-lined cover that has been prewashed
and 200 ng of acid surrogates (for a 1-L injection). Analysis with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column. (or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam- SAMPLE PRESERVATION
ples, and spikes must be evaluated for interferences. Contam- Liquid samples — If residual chlorine is present, add 3 mL of
ination by carryover can occur whenever high-concentration 10% sodium thiosulfate per gallon, cool to 4C and store in a
and low-concentration samples are sequentially analyzed. To solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out then eliminate the sodium thiosulfate addition.
between samples with solvent. Whenever an unusually concen-
trated sample is encountered, it should be followed by the Soils, sediments, or sludges — Cool samples to 4C and store
analysis of blank solvent to check for cross-contamination. in a solvent-free refrigerator.

INSTRUMENTATION A GC/MS and a data system are MHT Liquid samples must be extracted within 7 days and
required. The GC column used is a 30 m 0.25 mm I.D. (or the extracts analyzed within 40 days. Soils, sediments, or slud-
0.32 mm I.D.) 1um film thickness silicone-coated fused silica ges may be stored for a maximum of 14 days and the extracts
capillary column. A continuous liquid-liquid extractor analyzed within 40 days.
equipped with Teflon® or glass connection joints and stopcocks SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
PRECISION & ACCURACY The estimated quantitation water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
limit (EQL) of Method 8270B for determining an individual sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
compound is approximately 1 mg/kg (wet weight) for soil or solution into each sample. For the sample in each analytical
sediment samples, 1–200 mg/kg for wastes (dependent on batch selected for spiking, add 1.0 mL of a matrix spiking stan-
dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground-
gates and matrix spiking compounds added to the sample
water samples. EQLs will be proportionately higher for sample
extracts that require dilution to avoid saturation of the detector. should result in a final concentration of 100 ng/L of each
analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is 10. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
Overall precision in g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
(a) EQLs listed for soil/sediment are based on wet weight. Nor- concentrator.
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous or
will be higher based on the % dry weight of each sample. wet samples (gummy or clay type) that do not have a free-flowing

©1996 CRC Press LLC


sandy texture must be mixed with anhydrous sodium sulfate Pentachloroethane EPA Method 1625
until the sample is free flowing. Add 1 mL of surrogate stan- CAS #76-01-7
dards to all samples, spikes, standards, and blanks. For the
sample in each analytical batch selected for spiking, add 1.0 mL TITLE Semivolatile Organic Compounds by Isotope Dilu-
of a matrix spiking standard. For base/neutral acid analysis, the tion GC/MS
amount added of the surrogates and matrix spiking com-
pounds should result in a final concentration of 100 ng/ L of MATRIX The compounds may be determined in waters,
soils, and municipal sludges by this method.
each base/neutral analyte and 200 ng/L of each acid analyte
in the extract to be analyzed (assuming a 1- L injection). METHOD SUMMARY This method is used to determine
Immediately add a 100-mL mixture of 1:1 methylene chlo- 176 semivolatile toxic organic pollutants associated with the
ride:acetone and extract the sample ultrasonically for 3 min CWA (as amended 1987); the RCRA (as amended 1986); the
and then decant or filter the extracts. Repeat the extraction two CERCLA (as amended 1986); and other compounds amenable
or more times. Dry the extract using a column with anhydrous to extraction and analysis by capillary column gas chromatog-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. raphy-mass spectrometry (GC/MS).

QUALITY CONTROL A methylene chloride solution con- Stable isotopically-labeled analogs of the compounds of interest
are added to the sample. If the solids content is less than 1%,
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
a 1-L sample is extracted at pH 12–13, then at pH <2 with
used for tuning the GC/MS system each 12-h shift. A system
methylene chloride using continuous extraction techniques.
performance check also must be made during every 12-h shift.
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- If the solids content is 30% or less, the sample is diluted to 1%
rophenol, and benzidine is required to verify injection port solids with reagent water, homogenized ultrasonically, and
inertness and GC column performance. A calibration standard extracted at pH 12–13, then at pH <2 with methylene chloride
at mid-concentration, containing each compound of interest, using continuous extraction techniques. If the solids content is
including all required surrogates, must be performed every 12 h greater than 30%, the sample is extracted using ultrasonic
during analysis. After the system performance check is met, techniques.
calibration check compounds (CCCs) are used to check the Each extract is dried over sodium sulfate, concentrated to a
validity of the initial calibration. volume of 5 mL, cleaned up using GPC, if necessary, and con-
centrated. Extracts are concentrated to 1 mL if GPC is not
The internal standard responses and retention times in the
performed, and to 0.5 mL if GPC is performed.
calibration check standard must be evaluated immediately after
or during data acquisition. If the retention time for any internal An internal standard is added to the extract, and a 1-mL aliquot
standard changes by more than 30 seconds from the last check of the extract is injected into the GC. The compounds are
calibration (12 h), the chromatographic system must be separated by GC and detected by a MS. The labeled compounds
inspected for malfunctions and corrections must be made, as serve to correct the variability of the analytical technique.
required. If the electron ionization current plot (EICP) area for INTERFERENCES Solvents, reagents, glassware, and other
any of the internal standards changes by a factor of two from sample processing hardware may yield artifacts and/or elevated
the last daily calibration standard check, the mass spectrometer baselines causing misinterpretation of chromatograms and
must be inspected for malfunctions and corrections must be spectra. Materials used in the analysis must be demonstrated
made, as appropriate. to be free from interferences under the conditions of analysis
by running method blanks initially and with each sample lot
Demonstrate, through the analysis of a reagent water blank, (sample started through the extraction process on a given 8-h
that interferences from the analytical system, glassware, and shift, to a maximum of 20). Specific selection of reagents and
reagents are under control. The blank samples should be car- purification of solvents by distillation in all glass systems may
ried through all stages of the sample preparation and measure- be required. Glassware and, where possible, reagents are
ment steps. For each analytical batch (up to 20 samples), a cleaned by solvent rinse and baking at 450C for 1-h minimum.
reagent blank, matrix spike, and matrix spike duplicate/dupli- Interferences coextracted from samples will vary considerably
cate must be analyzed (the frequency of the spikes may be from source to source, depending on the diversity of the site
different for different monitoring programs). The blank and being sampled.
spiked samples must be carried through all stages of the sample INSTRUMENTATION Major instrumentation includes a GC
preparation and measurement steps. A QC reference sample with a splitless or on-column injection port for capillary col-
concentrate containing each analyte at a concentration of umn, a MS with 70 eV electron impact ionization, and a data
100 mg/L in methanol is required. system to collect and record MS data, and process it. A K-D
REFERENCE Test Methods for Evaluating Solid Waste (SW- apparatus is used to concentrate extracts.
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
of Solid Waste, Washington, DC. vinyl silicone bonded phased fused silica capillary column.

©1996 CRC Press LLC


PRECISION & ACCURACY The detection limits of the Spike all samples with labeled compounds to assess method
method are usually dependent on the level of interferences performance. Compute percent recovery of the labeled com-
rather than instrumental limitations. The limits typify the min- pounds using the internal standard method. Compare the
imum quantities that can be detected with no interferences labeled compound recovery for each compound with the cor-
present. responding labeled compound recovery.
The minimum level (in g/mL) was not listed. This is defined Reagent water and high solids reference matrix blanks are ana-
as a minimum level at which the analytical system shall give lyzed to demonstrate freedom from contamination. Extract
recognizable mass spectra (background corrected) and accept- and concentrate a 1-L reagent water blank or a high solids
able calibration points. reference matrix blank with each sample’s lot (samples started
The MDL (in g/kg) in low solids was not listed and in high through the extraction process on the same 8-h shift, to a
solids was not listed; these were determined in digested sludge maximum of 20 samples).
(low solids) and in filter cake or compost (high solids). Field replicates may be collected to determine the precision of
The labeled and native compound initial precision as standard the sampling technique, and spiked samples may be required
deviation (in g/L) was not listed. to determine the accuracy of the analysis when the internal
The labeled and native compound initial accuracy as average standard method is used.
recovery (in g/L) was not listed. REFERENCE Semivolatile Organic Compounds by Isotope
SAMPLE COLLECTION, PRESERVATION & HANDLING Dilution GC/MS. Office of Water Regulation and Standards,
Collect samples in glass containers. Aqueous samples which U.S. EPA Industrial Technology Division, Washington, DC,
flow freely are collected in refrigerated bottles using automatic EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
sampling equipment. Solid samples are collected as grab sam- U.S. EPA, Office of Water Regulations and Standards, 401 M
ples using widemouth jars. Maintain samples at 0 to 4C from St., SW, Washington, DC, 20460. Phone: 202-382-7131).
the time of collection until extraction. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
Pentachloroethane EPA Method 8240
and analyze all extracts within 40 days of extraction.
CAS #76-01-7
SAMPLE PREPARATION Samples containing 1% solids or
less are extracted directly using continuous liquid-liquid TITLE Volatile Organics By GC/MS: Packed Column Technique
extraction techniques. Samples containing 1 to 30% solids are
MATRIX Nearly all types of sample matarices, regardless of
diluted to the 1% level with reagent water and extracted using
water content, can be analyzed using this method. This includes
continuous liquid-liquid extraction techniques. Samples con-
groundwater, aqueous sludges, caustic liquors, acid liquors,
taining greater than 30% solids are extracted using ultrasonic
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
techniques.
metric emulsions, filter cakes, spent carbons, spent catalysts,
Base/neutral extraction — Adjust the pH of the waters in the soils, and sediments.
extractors to 12–13 with 6 N NaOH. Extract with methylene
chloride for 24–48 h. METHOD SUMMARY Method 8240B covers 80 volatile
Acid extraction — Adjust the pH of the waters in the extractors organic compounds that are introduced into a gas chromato-
to 2 or less using 6 N sulfuric acid. Extract with methylene graph by the purge-and-trap method or by direct injection (in
chloride for 24–48 h. limited applications). For the purge-and-trap method an inert
Ultrasonic extraction of high solids samples — Add anhy- gas (zero grade nitrogen or helium) is bubbled through a 5-mL
drous sodium sulfate to the sample and QC aliquot(s). solution at ambient temperature. Purged sample components
Add acetone:methylene chloride (1:1) to the sample and are trapped in a tube of sorbent materials. When purging is
mix thoroughly complete, the sorbent tube is heated and backflushed with inert
gas to desorb the trapped components onto a GC column.
Concentrate extracts using a K-D apparatus.
INTERFERENCES Impurities in the purge gas and from
QUALITY CONTROL The analyst is permitted to modify organic compounds outgassing from the plumbing ahead of
this method to improve separations or lower the costs of mea- the trap account for many contamination problems. Interfer-
surements, provided all performance specifications are met. ences purged or coextracted from the samples will vary con-
Analyses of blanks are required to demonstrate freedom from siderably from source to source. Cross-contamination can
contamination. When results of spikes indicate atypical occur whenever high-level and low-level samples are analyzed
method performance for samples, the samples are diluted to
sequentially. Whenever an unusually concentrated sample is
bring method performance within acceptable limits.
analyzed, it should be followed by the analysis of organic-free
For low solids (aqueous samples), extract, concentrate, and reagent water to check for cross-contamination. Samples also
analyze two sets of four 1-L aliquots (8 aliquots total) of the can be contaminated by diffusion of volatile organics (partic-
precision and recovery standard. For high solids samples, two ularly methylene chloride and fluorocarbons) through the sep-
sets of four 30-g aliquots of the high solids reference matrix tum seal into the sample during shipment and storage. A trip
are used. blank can serve as a check on such contamination. The lab

©1996 CRC Press LLC


where volatile analysis is performed and also the refrigerated SAMPLE PRESERVATION
storage area should be completely free of solvents. Liquid samples — Add 4 drops of concentrated HCL and
immediately cool samples to 4C and store in a solvent-free
INSTRUMENTATION A gas chromatograph/mass spec-
refrigerator.
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
I.D. glass column packed with 1% SP-1000 on Carbopack-B Soils or sediments, and sludges — Cool samples to 4C and
(60/80 mesh) is required.Also needed is a 5-mL purging device, store in a solvent-free refrigerator.
a sorbent trap, and a thermal desorption apparatus. MHT Maximum holding time is 14 days from the date of
PRECISION & ACCURACY This method is reported to have sample collection.
been tested by 15 laboratories using organic-free reagent water, SAMPLE PREPARATION
drinking water, surface water, and industrial wastewaters (not Liquid samples — Remove the plunger from a 5-mL syringe
specified) fortified at six concentrations over the range 5– and carefully pour the sample into the syringe barrel to just
600 g/L. short of overflowing. Replace the syringe plunger and compress
Sample estimated quantitation limits (EQLs) are highly the sample. Open the syringe valve and vent any residual air
while adjusting the sample volume to 5.0 mL. If there is only
matrix-dependent. The EQLs listed may not always be achiev-
one volatile organic analysis (VOA) vial, a second syringe
able. EQLs listed for soils or sediments are based on wet weight.
should be filled at this time to protect against possible loss of
Normally, data is reported on a dry-weight basis; therefore,
sample integrity. Add 10 L of surrogate spiking solution and
EQLs will be higher, based on the percent dry weight of each
10 L of internal standard spiking solution through the valve
sample. Note that EQLs are even more variable than MDLs and
bore of the 5-mL syringe, then close the valve. The surrogate
that they are highly variable depending on the matrix being and internal standards may be mixed and added as a single
analyzed. spiking solution.
EQL in groundwater in g/L was 10. Sediments, soils, and waste samples — All samples of this type
EQL in low soil or sediment in g/kg was 10. should be screened by GC analysis using a headspace method
Accuracy (a) in g/L was not listed.
(EPA Method 3810) or the hexadecane extraction and screen-
Precision (b) in g/L was not listed.
ing method (EPA Method 3820). Use the screening data to
(a) Average recovery found for measurements of samples con- determine whether to use the low-concentration method
taining a concentration of C, in g/L. (0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
(b) Overall precision found for measurements of samples with
Low-concentration method — The low-concentration method
average recovery X for samples containing a concentration
is based on purging a heated sediment or soil sample mixed
of C in g/L. with organic-free reagent water containing the surrogate and
X = Average recovery found for measurement of samples con- internal standards. Analyze all reagent blanks and standards
taining a concentration of C in g/L. under the same conditions as the samples.
MULTIPLICATION FACTORS FOR OTHER MATRICES Use a 5-g sample if the expected concentration is <0.1 mg/kg
Other Matrices Factor (a) or a 1-g sample for expected concentrations between 0.1 and
Waste miscible liquid waste 50 1 mg/kg. Mix the contents of the sample container with a nar-
High-concentration soil and sludge 125 row metal spatula. Weigh the amount of the sample into a tared
Non-water miscible waste 500 purge device. Add the spiked water to the purge device, which
contains the weighed amount of sample, and connect the
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous device to the purge-and-trap system.
samples, the factor is on a wet-weight basis.
High-concentration method — This method is based on
SAMPLING METHOD extracting the sediment or soil with methanol. A waste sample
Liquid samples — Use a 40-mL glass screw-cap VOA vial with is either extracted or diluted, depending on its solubility in
a Teflon®-faced silicone septum that has been prewashed, methanol. Wastes that are insoluble in methanol are diluted
rinsed with distilled deionized water, and oven dried. However, with reagent tetraglyme or possibly polyethylene glycol (PEG).
if residual chlorine is present, collect sample in a 40-oz. soil An aliquot of the extract is added to organic-free reagent water
VOA container which has been pre-preserved with 4 drops of containing surrogate and internal standards. This is purged at
10% sodium thiosulfate, mix gently, and then transfer the sam- ambient temperature. All samples with an expected concentra-
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli- tion of >1.0 mg/kg should be analyzed by this method.
cate and seal them in separate plastic bags.
Mix the contents of the sample container with a narrow metal
Soils or sediments, and sludges — Use an 8-oz. widemouth spatula. For sediments or soils and solid wastes that are insol-
glass bottle with a Teflon®-faced silicone septum that has been uble in methanol, weigh 4 g (wet weight) of sample into a tared
prewashed with detergent, rinsed with distilled deionized 20-mL vial. For waste that is soluble in methanol, tetraglyme,
water, and oven dried. Tap slightly to eliminate free air space. or PEG, weigh 1 g (wet weight) into a tared scintillation vial
Collect samples in duplicate and seal them in separate plastic bags. or culture tube or a 10-mL volumetric flask. Quickly add

©1996 CRC Press LLC


9.0 mL of appropriate solvent then add 1.0 mL of a surrogate INTERFERENCES Solvents, reagents, glassware, and other
spiking solution to the vial, cap it, and shake it for 2 min. sample processing hardware may yield discrete artifacts and/or
elevated baselines causing misinterpretation of gas chromato-
METHANOL EXTRACT REQUIRED FOR ANALYSIS
grams. Interferences coextracted from samples will vary con-
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS siderably from source to source, depending upon the waste
Approximate Volume of being sampled.
Concentration Range Methanol Extract (a)
INSTRUMENTATION An analytical system complete with
500–10,000 g/kg 100 L GC suitable for on-column injections and accessories, includ-
1,000–20,000 g/kg 50 L ing detectors, column supplies, recorder, gases and syringes is
5,000–100,000 g/kg 10 L required. A data system for measuring peak areas and/or peak
25,000–500,000 g/kg 100 L of 1/50 dilution (b) heights is recommended. The GC is equipped with an electron
Calculate appropriate dilution factor for concentrations capture detector (ECD). A K-D apparatus is needed for sample
exceeding this table. preparation.

(a) The volume of methanol added to 5 mL of water being purged Column 1: 1.8 m 2 mm I.D. glass column packed with 1%
should be kept constant. Therefore, add to the 5-mLsyringe whatever SP-1000 on Supelcoport (100/120 mesh) or equivalent.
volume of methanol is necessary to maintain a volume of 100 L Column 2: 1.8 m 2 mm I.D. glass column packed with 1.5%
added to the syringe. OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or
(b) Dilute an aliquot of the methanol extract and then take 100 L equivalent.
for analysis. PRECISION & ACCURACY The method was tested by 20
QUALITY CONTROL Demonstrate, through the analysis of laboratories using organic-free reagent water, drinking water,
a reagent water blank, that interferences from the analytical surface water, and three industrial wastewaters spiked at six
system, glassware, and reagents are under control. Blank sam- concentrations over the range 1.0 to 356 g/L. Single operator
ples should be carried through all stages of the sample prepa- precision, overall precision, and method accuracy were found
ration and measurement steps. For each analytical batch (up to be directly related to the concentration of the parameter and
to 20 samples), a reagent blank, matrix spike, and matrix spike essentially independent of the sample matrix.
duplicate must be analyzed (the frequency of the spikes may MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
be different for different monitoring programs). The blank and Matrix Factor (b)
spiked samples must be carried through all stages of the sample
preparation and measurement steps. QC samples mentioned Groundwater 10
in the section on Interferences will also be needed as appropri- Low-concentration soil by ultrasonic extraction 670
ate to those situations. with GPC cleanup
High-concentration soil and sludges 10,000
REFERENCE Test Methods for Evaluating Solid Waste (SW- by ultrasonic extraction
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office Waste not miscible with water 100,000
of Solid Wastes, Washington, DC.
(a) Sample EQLs are highly matrix-dependent. The EQLs listed
herein are provided for guidance and may not always be achievable.
(b) EQL = [Method detection limit]  [Factor]. For nonaqueous
Pentachlorohexane EPA Method 8120 samples, the factor is on a wet-weight basis.
CAS #96989-91-2
PRECISION & ACCURACY The estimates below are based
TITLE Chlorinated Hydrocarbons by Gas Chromatography upon the performance in a single lab.

MATRIX This method covers aqueous and solid matrices. The accuracy (in g/L) as expected recovery for one or more
This includes a wide variety such as drinking water, ground- measurements of a sample containing a concentration of C
water, industrial wastewaters, surface waters, soils, solids, and was No Data.
sediments. The precision (in g/L) as expected single analyst standard
deviation of measurements at an average concentration of
METHOD SUMMARY This method is used to determine the x” was No Data.
concentration of 14 chlorinated hydrocarbons. It provides gas The precision (in g/L) as expected interlaboratory standard
chromatographic conditions for the detection of ppb concen- deviation measurements at an average concentration found
trations of certain chlorinated hydrocarbons. Prior to use of of x” was No Data.
this method, appropriate sample extraction techniques must
be used. Both neat and diluted organic liquids (EPA Method C = True value for the concentration, in g/L.
3580, Waste Dilution) may be analyzed by direct injection. A x”= Average recovery found for measurements of samples con-
taining a concentration of C, in g/L.
2 to 5 g/mL aliquot of the extract is injected into a gas chro-
matograph (GC) using the solvent flush technique, and com- SAMPLE COLLECTION, PRESERVATION & HANDLING
pounds in the GC effluent are detected by an electron capture Extracts must be stored under refrigeration at 4C and analyzed
detector (ECD). within 40 days of extraction.

©1996 CRC Press LLC


SAMPLE PREPARATION In general, water samples are INSTRUMENTATION A GC/MS and a data system are
extracted at a neutral, or as is, pH with methylene chloride required. The GC column used is a 30 m 0.25 mm I.D. (or
using either EPA Method 3510 or EPA Method 3520. Solid 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
samples are extracted using either EPA Method 3540 or EPA capillary column. A continuous liquid-liquid extractor
Method 3550. Prior to gas chromatographic analysis, the equipped with Teflon® or glass connection joints and stopcocks
extraction solvent must be exchanged to hexane. requiring no lubrication, a K-D concentrating apparatus, water
QUALITY CONTROL The quality control check concentrate bath, and an ultrasonic disrupter with a minimum power of
(EPA Method 8000) should contain each parameter of interest 300 W and with pulsing capability are also required.
in acetone at the following concentrations: hexachloro-substi- PRECISION & ACCURACY The estimated quantitation
tuted hydrocarbon, 10 g/mL; and any other chlorinated limit (EQL) of Method 8270B for determining an individual
hydrocarbon, 100 g/mL. Calculate surrogate standard recov- compound is approximately 1 mg/kg (wet weight) for soil or
ery on all samples, blanks, and spikes. sediment samples, 1–200 mg/kg for wastes (dependent on
Prepare stock standard solutions in isooctane or hexane. Cali- matrix and method of preparation), and 10 g/L for ground-
bration standards at a minimum of five concentrations should water samples. EQLs will be proportionately higher for sample
be prepared through dilution of the stock standards with isooc- extracts that require dilution to avoid saturation of the detector.
tane or hexane. Internal standards and surrogate standards are The EQL(b) for groundwater in g/L is 20.
also needed. The EQL (a, b) for low concentrations in soil and sediment
REFERENCE Test Methods for Evaluating Solid Waste, Phys- in g/kg is not determined.
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Accuracy as g/L is not listed.
of Solid Waste, Washington, DC, 1990. EPA Method 8120 A Overall precision in g/L is not listed.
Rev. 1, Nov. 1990. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
Pentachloronitrobenzene EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #82-68-8 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate,
This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately
Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The
Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral
with a screw-top Teflon®-lined cover that has been prewashed
and 200 ng of acid surrogates (for a 1-L injection). Analysis
with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column.
(or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam-
SAMPLE PRESERVATION
ples, and spikes must be evaluated for interferences. Contam-
Liquid samples — If residual chlorine is present, add 3 mL of
ination by carryover can occur whenever high-concentration
10% sodium thiosulfate per gallon, cool to 4C and store in a
and low-concentration samples are sequentially analyzed. To
solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out
then eliminate the sodium thiosulfate addition.
between samples with solvent. Whenever an unusually concen-
trated sample is encountered, it should be followed by the Soils, sediments, or sludges — Cool samples to 4C and store
analysis of blank solvent to check for cross-contamination. in a solvent-free refrigerator.

©1996 CRC Press LLC


MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.
SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,
Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust
REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for
of Solid Waste, Washington, DC.
18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Pentachlorophenol EPA Method 1625
Soils, sediments, or sludges — Use 30 g of sample. Nonporous
CAS #87-86-5
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium
TITLE Semivolatile Organic Compounds by Isotope Dilu-
sulfate until the sample is free flowing. Add 1 mL of surrogate
tion GC/MS
standards to all samples, spikes, standards, and blanks. For the
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX The compounds may be determined in waters,
of a matrix spiking standard. For base/neutral acid analysis, the soils, and municipal sludges by this method.
amount added of the surrogates and matrix spiking com-
METHOD SUMMARY This method is used to determine
pounds should result in a final concentration of 100 ng/ L of
176 semivolatile toxic organic pollutants associated with the
each base/neutral analyte and 200 ng/L of each acid analyte
CWA (as amended 1987); the RCRA (as amended 1986); the
in the extract to be analyzed (assuming a 1- L injection). CERCLA (as amended 1986); and other compounds amenable
Immediately add a 100-mL mixture of 1:1 methylene chlo- to extraction and analysis by capillary column gas chromatog-
ride:acetone and extract the sample ultrasonically for 3 min raphy-mass spectrometry (GC/MS).
and then decant or filter the extracts. Repeat the extraction two
or more times. Dry the extract using a column with anhydrous Stable isotopically-labeled analogs of the compounds of interest
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. are added to the sample. If the solids content is less than 1%,
a 1-L sample is extracted at pH 12–13, then at pH <2 with
QUALITY CONTROL A methylene chloride solution con- methylene chloride using continuous extraction techniques.
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
used for tuning the GC/MS system each 12-h shift. A system If the solids content is 30% or less, the sample is diluted to 1%
performance check also must be made during every 12-h shift. solids with reagent water, homogenized ultrasonically, and
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- extracted at pH 12–13, then at pH <2 with methylene chloride
rophenol, and benzidine is required to verify injection port using continuous extraction techniques. If the solids content is
inertness and GC column performance. A calibration standard greater than 30%, the sample is extracted using ultrasonic
at mid-concentration, containing each compound of interest, techniques.
including all required surrogates, must be performed every 12 h Each extract is dried over sodium sulfate, concentrated to a
during analysis. After the system performance check is met, volume of 5 mL, cleaned up using GPC, if necessary, and con-
calibration check compounds (CCCs) are used to check the centrated. Extracts are concentrated to 1 mL if GPC is not
validity of the initial calibration. performed, and to 0.5 mL if GPC is performed.
The internal standard responses and retention times in the
An internal standard is added to the extract, and a 1-mL aliquot
calibration check standard must be evaluated immediately after of the extract is injected into the GC. The compounds are
or during data acquisition. If the retention time for any internal separated by GC and detected by a MS. The labeled compounds
standard changes by more than 30 seconds from the last check serve to correct the variability of the analytical technique.
calibration (12 h), the chromatographic system must be
inspected for malfunctions and corrections must be made, as INTERFERENCES Solvents, reagents, glassware, and other
required. If the electron ionization current plot (EICP) area for sample processing hardware may yield artifacts and/or elevated

©1996 CRC Press LLC


baselines causing misinterpretation of chromatograms and Acid extraction — Adjust the pH of the waters in the extractors
spectra. Materials used in the analysis must be demonstrated to 2 or less using 6 N sulfuric acid. Extract with methylene
to be free from interferences under the conditions of analysis chloride for 24–48 h.
by running method blanks initially and with each sample lot Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h drous sodium sulfate to the sample and QC aliquot(s).
shift, to a maximum of 20). Specific selection of reagents and Add acetone:methylene chloride (1:1) to the sample and
purification of solvents by distillation in all glass systems may mix thoroughly
be required. Glassware and, where possible, reagents are
Concentrate extracts using a K-D apparatus.
cleaned by solvent rinse and baking at 450C for 1-h minimum.
Interferences coextracted from samples will vary considerably QUALITY CONTROL The analyst is permitted to modify
from source to source, depending on the diversity of the site this method to improve separations or lower the costs of mea-
being sampled. surements, provided all performance specifications are met.
Analyses of blanks are required to demonstrate freedom from
INSTRUMENTATION Major instrumentation includes a GC contamination. When results of spikes indicate atypical
with a splitless or on-column injection port for capillary col- method performance for samples, the samples are diluted to
umn, a MS with 70 eV electron impact ionization, and a data bring method performance within acceptable limits.
system to collect and record MS data, and process it. A K-D
apparatus is used to concentrate extracts. For low solids (aqueous samples), extract, concentrate, and
analyze two sets of four 1-L aliquots (8 aliquots total) of the
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% precision and recovery standard. For high solids samples, two
vinyl silicone bonded phased fused silica capillary column. sets of four 30-g aliquots of the high solids reference matrix
PRECISION & ACCURACY The detection limits of the are used.
method are usually dependent on the level of interferences Spike all samples with labeled compounds to assess method
rather than instrumental limitations. The limits typify the min- performance. Compute percent recovery of the labeled com-
imum quantities that can be detected with no interferences pounds using the internal standard method. Compare the
present. labeled compound recovery for each compound with the cor-
The minimum level (in g/mL) was 50. This is defined as a responding labeled compound recovery.
minimum level at which the analytical system shall give recog- Reagent water and high solids reference matrix blanks are ana-
nizable mass spectra (background corrected) and acceptable lyzed to demonstrate freedom from contamination. Extract
calibration points. and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was 51 and in high solids reference matrix blank with each sample’s lot (samples started
was 207; these were determined in digested sludge (low solids) through the extraction process on the same 8-h shift, to a
and in filter cake or compost (high solids). maximum of 20 samples).

The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was 21. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was 76–140. standard method is used.

SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
U.S. EPA, Office of Water Regulations and Standards, 401 M
ples using widemouth jars. Maintain samples at 0 to 4C from
St., SW, Washington, DC, 20460. Phone: 202-382-7131).
the time of collection until extraction. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction. Pentachlorophenol EPA Method 625
SAMPLE PREPARATION Samples containing 1% solids or CAS #87-86-5
less are extracted directly using continuous liquid-liquid
TITLE Base/Neutrals and Acids, U.S. EPA Method 625
extraction techniques. Samples containing 1 to 30% solids are
diluted to the 1% level with reagent water and extracted using MATRIX This methods covers municipal and industrial
continuous liquid-liquid extraction techniques. Samples con- wastewaters.
taining greater than 30% solids are extracted using ultrasonic
METHOD SUMMARY Approximately 1 L of sample is seri-
techniques.
ally extracted with methylene chloride at a pH greater than 11
Base/neutral extraction — Adjust the pH of the waters in the and again at a pH less than 2 using a separatory funnel or a
extractors to 12–13 with 6 N NaOH. Extract with methylene continuous extractor. The methylene chloride extract is dried,
chloride for 24–48 h. concentrated to a volume of 1 mL, and analyzed by GC/MS.

©1996 CRC Press LLC


Qualitative identification of the parameters in the extract is the pH to <2 with sulfuric acid and serially extract in a sepa-
performed using the retention time and the relative abundance ratory funnel with methylene chloride or else in a continuous
of three characteristic masses (m/z). Qualitative analysis is per- extractor. Dry the extracts separately through a column of
formed using either external or internal standard techniques anhydrous sodium sulfate and then concentrate each of the
with a single characteristic m/z. extracts to 1.0 mL using a K-D apparatus.
INTERFERENCES Method interferences may be caused by SAMPLE COLLECTION, PRESERVATION & HANDLING
contaminants in solvents, reagents, glassware, and other sample Grab samples must be collected in glass containers. All samples
processing hardware. Glassware must be scrupulously cleaned. must be refrigerated at 4C from the time of collection until
Glassware should be heated in a muffle furnace at 400C for 5 extraction. If residual chlorine is present, add 80 mg of sodium
to 30 min. Some thermally stable materials, such as PCBs, may thiosulfate/L of sample and mix well. All samples must be
not be eliminated by this treatment. Solvent rinses with acetone extracted within 7 days of collection and completely analyzed
and pesticide quality hexane may be substituted for the muffle within 40 days of extraction.
furnace heating. Matrix interferences may be caused by con-
taminants that are coextracted from the sample. The base- QUALITY CONTROL Make an initial, one-time, demonstra-
neutral extraction may cause significantly reduced recovery of tion of the ability to generate acceptable accuracy and precision
phenols. The packed gas chromatographic columns recom- with this method. Before processing any samples, the analyst
mended for the basic fraction may not exhibit sufficient reso- must analyze a reagent water blank to demonstrate that inter-
lution for some analytes. ferences from the analytical system and glassware are under
control. Each time a set of samples is extracted or reagents are
INSTRUMENTATION A GC/MS system with an injection changed, a reagent water blank must be processed. Spike and
port designed for on-column injection when using packed col- analyze a minimum of 5% of all samples to monitor and eval-
umns and for splitless injection when using capillary columns. uate lab data quality. A QC check sample concentrate that
Column for base/neutrals: 1.8 m long  2 mm I.D. glass, contains each parameter of interest at a concentration of
packed with 3% SP-2550 on Supelcoport (100/120 mesh) 100 g/mL in acetone is required. PCBs and multicomponent
or equivalent. pesticides may be omitted from this test.
Column for acids: 1.8 m long 2 mm I.D. glass, packed with 1%
After analysis of five spiked wastewater samples, calculate the
SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
average percent recovery and the standard deviation of the
PRECISION & ACCURACY The MDL concentrations were percent recovery. Spike all samples with the surrogate standard
obtained using reagent water. The MDL actually achieved in a spiking solution and calculate the percent recovery of each
given analysis will vary depending on instrument sensitivity surrogate compound.
and matrix effects. This method was tested by 15 laboratories
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
using reagent water, drinking water, surface water, and indus-
trial wastewaters spiked at six concentrations over the range 5 26, 1984.
to 100 g/L. Single operator precision, overall precision, and
method accuracy were found to be directly related to the con-
centration of the parameter matrix. Pentachlorophenol EPA Method 8151
The MDL (in g/L) in reagent water was 3.6. CAS #87-86-5
The standard deviation (in g/L based on 4 recovery measure-
ments) was 48.9. TITLE Chlorinated Herbicides by GC Using Methylation or
The range (in g/L) for average recovery for 4 measurements Pentafluorobenzylation Derivatization: Capillary Column
was 38.1–151.8. Technique.
The range (in %) for percent recovery was 14–176. MATRIX This method covers aqueous and solid matrices.
Accuracy (in g/L) as expected recovery for one or more mea- This includes a wide variety such as drinking water, ground-
surements of a sample containing a true concentration of water, industrial wastewaters, surface waters, soils, solids, and
C was 0.93C + 1.99. sediments.
Precision (in g/L) as expected single analyst standard devia-
tion of measurements at an average concentration found at METHOD SUMMARY This is a GC method for determining
X was 0.24X + 3.03. 19 chlorinated acid herbicides in aqueous, soil, and waste
Overall precision (in g/L) as expected interlaboratory stan- matrices. Because these compounds are produced and used in
dard deviation of measurements in an average concentra- various forms (i.e., acid, salt, ester, etc.) a hydrolysis step is
tion found at X was 0.30X + 4.33. included to convert the herbicide to the acid form prior to
analysis. This method provides hydrolysis, extraction, deriva-
C = True value of the concentration in g/L. tization and GC conditions for the analysis of chlorinated acid
X = Average recovery found for measurements of samples con- herbicides in water, soil, and waste samples. Water samples are
taining a concentration at C in g/L. hydrolyzed in situ, extracted with diethyl ether, and then ester-
SAMPLE PREPARATION Adjust the pH to >11 with sodium ified with either diazomethane or pentafluorobenzyl bromide.
hydroxide and serially extract in a separatory funnel with meth- The derivatives are determined by gas chromatography with an
ylene chloride or else in a continuous extractor. Next, adjust electron capture detector (GC/ECD). The results are reported

©1996 CRC Press LLC


as acid equivalents. The sensitivity of this method depends on Mean percent recovery, calculated from 10 determinations of
the level of interferences in addition to instrumental limitations. spiked clay and clay/still bottom samples over the linear con-
centration range (in ng/g) of no data was none reported with
INTERFERENCES Method interferences may be caused by
a percent relative standard deviation of none. The RSD % was
contaminants in solvents, reagents, glassware, and other sample calculated on 10 samples high in the linear concentration range
processing hardware. Immediately prior to use, glassware and 10 low in the range. The linear concentration range was
should be rinsed with the next solvent to be used. Matrix inter- determined using standard solutions and corrected to 50 g soil
ferences may be caused by contaminants that are coextracted samples.
from the sample. Organic acids, especially chlorinated acids,
cause the most direct interference with the determination by SAMPLE COLLECTION, PRESERVATION & HANDLING
methylation. Phenols, including chlorophenols, may also inter- Containers used to collect samples for the determination of
fere with this procedure. The determination using pentafluo- semivolatile organic compounds should be soap and water
robenzylation is more sensitive, and more prone to washed followed by methanol (or isopropanol) rinsing. The
interferences from the presence of organic acids of phenols than sample containers should be of glass or Teflon® and have screw-
by methylation. Alkaline hydrolysis and subsequent extraction top covers with Teflon® liners.
of the basic solution removes many chlorinated hydrocarbons No preservation is used with concentrated waste samples. With
and phthalate esters that might otherwise interfere with the liquid samples containing no residual chlorine and with soil,
ECD analysis. The herbicides, being strong organic acids, react sediment, and sludge samples, immediately cooling to 4C is
readily with alkaline substances and may be lost during analy- the only preservation used. When residual chlorine is present
sis. Therefore, glassware must be acid-rinsed and then rinsed then 3 mL of 10% aqueous sodium sulfate is added for each
to constant pH with organic-free reagent water. gallon of sample collected, followed by cooling to 4C.
INSTRUMENTATION A GC suitable for Grob-type injec- The holding time for all volatile organics samples is 14 days.
tion using capillary columns. A data system for measuring peak Liquid samples must be extracted within 7 days and their
heights and/or peak areas is recommended.An electron capture extracts analyzed within 40 days. Concentrated waste, soil, sed-
detector (ECD) is used. Also a K-D apparatus, a diazomethane iment, and sludge samples must be extracted within 14 days
generator, a centrifuge and an ultrasonic disrupter will be and their extracts analyzed within 40 days.
required.
SAMPLE PREPARATION
Narrow Bore Columns: Preparation of soil, sediment, and other solid samples — Acid-
Primary Column 1: 30 m 0.25 mm, 5% phenyl/95% methyl ify 30 g (dry weight) solids with 0.1 M phosphate buffer (pH =
silicone (DB-5), 0.25 m film thickness. 2.5) and thoroughly mix the contents. Spike the sample with
Primary Column 1a (GC/MS): 30 m  0.32 mm, 5% phe- surrogate compound(s). The ultrasonic extraction of solids
nyl/95% methyl silicone (DB-5), 1-m film thickness. must be optimized for each type of sample. In order for the
Column 2: 30 m 0.25 mm DB-608 with a 25 m film thickness. ultrasonic extractor to efficiently extract solid samples, the
Confirmation Column: 30 m  0.25 mm, 14% cyanopropyl sample must be free flowing when the solvent is added. Acid-
phenyl silicone (DB-1701), 0.25 m film thickness. ified anhydrous sodium sulfate should be added to clay-type
soils, or any other solid that is not a free-flowing sandy texture,
Megabore Columns: until a free flowing mixture is obtained. Add methylene chlo-
Primary Column: 30 m 0.53 mm DB-608 with 0.83 m film ride and perform ultrasonic extraction. Combine organic
thickness. extracts from the repetitive extractings of the sample and cen-
Confirmation Column: 30 m  0.53 mm, 14% cyanopropyl trifuge. Add aqueous potassium hydroxide, water, and metha-
phenyl silicone (DB-1701), 1.0 m film thickness. nol to the extract and reflux the mixture on a water bath.
PRECISION & ACCURACY Method detection limits Extract the solution three times with methylene chloride and
(MDLs) are compound-dependent and vary with derivitization discard the methylene chloride phase. The basic solution con-
efficiency, derivative recovery, the matrix sampled, and herbi- tains the herbicide salts. Adjust the pH of the solution to <2
cide concentration. with cold sulfuric acid and extract three times with methylene
chloride. Combine the extracts and pour them through a pre-
The estimated MDL (in g/L) was 0.076 for aqueous samples rinsed drying column containing acidified anhydrous sodium
using GC/ECD. sulfate. Collect the dried extracts in a K-D flask and concentrate
The estimated MDL (in g/kg) was 0.16 for soil samples using them.
GC/ECD when corrected back to 50 g samples extracted and Preparation of aqueous samples — Measure 1 L of sample into
concentrated to 10 mL with 5-L injections. a 2 L separatory funnel and spike it with surrogate com-
pound( s). Add NaCl to the sample, then add 6 N NaOH to the
The estimated GC/MS identification limit (in ng) was 1.3 for
sample to a pH of 12 or more and let the sample sit at room
soil samples using GC/MS.
temperature for 1 h to hydrolyze esters. Extract the sample
Mean percent recovery, calculated from 7–8 determinations of three times with methylene chloride and discard the extracts.
spiked reagent water, after diazomethane derivatization, from Then add cold 12 N sulfuric acid to a pH less than or equal to
a spike concentration (in g/L) of 0.04 was 130 with a standard 2, and extract the sample three times with ethyl ether. Collect
deviation of the percent recovery of 31.2. the ether phase in a flask containing acidified anhydrous

©1996 CRC Press LLC


sodium sulfate and allow it to remain in contact with the INTERFERENCES Raw GC/MS data from all blanks, sam-
sodium sulfate for a minimum of 2 h. The drying step is very ples, and spikes must be evaluated for interferences. Contam-
critical to ensuring complete esterification; any moisture ination by carryover can occur whenever high-concentration
remaining in the ether will result in low herbicide recoveries. and low-concentration samples are sequentially analyzed. To
reduce carryover, the sample syringe must be rinsed out
Extract concentration and derivatization — The combined between samples with solvent. Whenever an unusually concen-
ether extract is concentrated to about 1 mL using a K-D appa- trated sample is encountered, it should be followed by the
ratus followed by using a micro Snyder column or nitrogen gas analysis of blank solvent to check for cross-contamination.
blowdown. If methyl esters are to be produced, then dilute the
concentrated ether extract with 1 mL of isooctane and 0.5 mL INSTRUMENTATION A GC/MS and a data system are
of methanol, dilute to a final volume of 4 mL, and esterify with required. The GC column used is a 30 m 0.25 mm I.D. (or
diazomethane. If pentafluorobenzene esters are to be produced, 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
then dilute concentrated ether extract with acetone to a final capillary column. A continuous liquid-liquid extractor
volume of 4 mL and esterify with pentafluorobenzyl bromide. equipped with Teflon® or glass connection joints and stopcocks
requiring no lubrication, a K-D concentrating apparatus, water
QUALITY CONTROL Select a representative spike concen- bath, and an ultrasonic disrupter with a minimum power of
tration for each compound (acid or ester) to be measured. 300 W and with pulsing capability are also required.
Using stock standard, prepare a quality control check sample
PRECISION & ACCURACY The estimated quantitation
concentrate, in acetone, that is 1000 times more concentrated
limit (EQL) of Method 8270B for determining an individual
than the selected concentrations. Use this quality control check
compound is approximately 1 mg/kg (wet weight) for soil or
sample concentrate to prepare quality control check samples. sediment samples, 1–200 mg/kg for wastes (dependent on
Calculate surrogate standard recovery on all standards, sam- matrix and method of preparation), and 10 g/L for ground-
ples, blanks, and spikes. GC/MS techniques should be judi- water samples. EQLs will be proportionately higher for sample
ciously employed to support qualitative identifications made extracts that require dilution to avoid saturation of the detector.
with this method. When available, chemical ionization mass
spectra may be employed to aid the qualitative identification The EQL(b) for groundwater in g/L is 50.
process. The EQL (a, b) for low concentrations in soil and sediment
in g/kg is 3300.
REFERENCE Test Methods for Evaluating Solid Waste, Phys- Accuracy as g/L is 0.93C + 1.99.
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Overall precision in g/L is 0.30X + 4.33.
of Solid Waste, Washington, DC, EPA Method 8151, Nov. 1990.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
Pentachlorophenol EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #87-86-5 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra-
X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared
taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate,
This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral with a screw-top Teflon®-lined cover that has been prewashed
and 200 ng of acid surrogates (for a 1-L injection). Analysis with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column. (or isopropanol).

©1996 CRC Press LLC


SAMPLE PRESERVATION including all required surrogates, must be performed every 12 h
Liquid samples — If residual chlorine is present, add 3 mL of during analysis. After the system performance check is met,
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check compounds (CCCs) are used to check the
solvent-free refrigerator until analysis; if chlorine is not present, validity of the initial calibration.
then eliminate the sodium thiosulfate addition.
The internal standard responses and retention times in the
Soils, sediments, or sludges — Cool samples to 4C and store calibration check standard must be evaluated immediately after
in a solvent-free refrigerator. or during data acquisition. If the retention time for any internal
MHT Liquid samples must be extracted within 7 days and standard changes by more than 30 seconds from the last check
the extracts analyzed within 40 days. Soils, sediments, or slud- calibration (12 h), the chromatographic system must be
ges may be stored for a maximum of 14 days and the extracts inspected for malfunctions and corrections must be made, as
analyzed within 40 days. required. If the electron ionization current plot (EICP) area for
any of the internal standards changes by a factor of two from
SAMPLE PREPARATION the last daily calibration standard check, the mass spectrometer
Liquid samples — Transfer 1 L quantitatively to a continuous must be inspected for malfunctions and corrections must be
extractor. If high concentrations are anticipated, a smaller vol- made, as appropriate.
ume may be used and then diluted with organic-free reagent
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) Demonstrate, through the analysis of a reagent water blank,
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking that interferences from the analytical system, glassware, and
solution into each sample. For the sample in each analytical reagents are under control. The blank samples should be car-
batch selected for spiking, add 1.0 mL of a matrix spiking stan- ried through all stages of the sample preparation and measure-
dard. For base/neutral acid analysis, the amount of the surro- ment steps. For each analytical batch (up to 20 samples), a
gates and matrix spiking compounds added to the sample reagent blank, matrix spike, and matrix spike duplicate/dupli-
should result in a final concentration of 100 ng/L of each cate must be analyzed (the frequency of the spikes may be
analyte in the extract to be analyzed (assuming a 1- L injec- different for different monitoring programs). The blank and
tion). Extract with methylene chloride for 18–24 h. Next, adjust spiked samples must be carried through all stages of the sample
the pH of the aqueous phase to pH >11 using 10 N sodium preparation and measurement steps. A QC reference sample
hydroxide and extract it with methylene chloride again for concentrate containing each analyte at a concentration of
18–24 h. Dry the extract through a column containing anhy- 100 mg/L in methanol is required.
drous sodium sulfate and concentrate it to 1 mL using a K-D REFERENCE Test Methods for Evaluating Solid Waste (SW-
concentrator. 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
Soils, sediments, or sludges — Use 30 g of sample. Nonporous of Solid Waste, Washington, DC.
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium
sulfate until the sample is free flowing. Add 1 mL of surrogate Pentachlorophenol EPA Method 8040
standards to all samples, spikes, standards, and blanks. For the CAS #87-86-5
sample in each analytical batch selected for spiking, add 1.0 mL
of a matrix spiking standard. For base/neutral acid analysis, the TITLE Phenols
amount added of the surrogates and matrix spiking com-
pounds should result in a final concentration of 100 ng/ L of MATRIX Groundwater, soils, sludges, water miscible liquid
each base/neutral analyte and 200 ng/L of each acid analyte wastes, and non-water miscible wastes.
in the extract to be analyzed (assuming a 1- L injection). APPLICATION This method is used for the analysis of 17
Immediately add a 100-mL mixture of 1:1 methylene chlo- phenols. Samples are extracted, concentrated, and analyzed
ride:acetone and extract the sample ultrasonically for 3 min using direct injection of both neat and diluted organic liquids.
and then decant or filter the extracts. Repeat the extraction two Pentafluorobenzylbromide (PFB) derivatives also may be made
or more times. Dry the extract using a column with anhydrous to increase sensitivity of the method.
sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
INTERFERENCES There can be carryover contamination
Note: N-nitrosodiphenylamine decomposes in the gas chro- with high- and low-level samples. Solvents, reagents, and glass-
matographic inlet and cannot be separated from dipheny- ware may introduce artifacts. Other interferences may come
lamine. from coextracted compounds from samples.
QUALITY CONTROL A methylene chloride solution con- INSTRUMENTATION GC capable of on-column injections
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is and a flame with detector (FID) or electron capture detector
used for tuning the GC/MS system each 12-h shift. A system (ECD). Column for underivatized phenol: 1.8 m by 2.0 mm
performance check also must be made during every 12-h shift. with 1% SP-1240DA on Supelcoport. Column for derivatized
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- phenols: 1.8 m by 2.0 mm with 5% OV-17 on Chromosorb W-
rophenol, and benzidine is required to verify injection port AW-DMCS.
inertness and GC column performance. A calibration standard
at mid-concentration, containing each compound of interest, RANGE 12–450 g/L

©1996 CRC Press LLC


MDL 7.4 g/L (FID) and 0.59 g/L (ECD) extracted at pH 12–13, then at pH <2 with methylene chloride
using continuous extraction techniques. If the solids content is
PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
greater than 30%, the sample is extracted using ultrasonic
Matrix Multiplication Factor techniques.
Groundwater 10 Each extract is dried over sodium sulfate, concentrated to a
Low-level soil by sonication with GPC cleanup 670 volume of 5 mL, cleaned up using GPC, if necessary, and con-
High-level soil and sludge by sonication 10,000 centrated. Extracts are concentrated to 1 mL if GPC is not
Non-water miscible waste 100,000 performed, and to 0.5 mL if GPC is performed.
PRECISION 0.23X + 0.57 g/L (overall precision using FID) An internal standard is added to the extract, and a 1-mL aliquot
ACCURACY 0.83C + 2.07 g/L (as recovery using FID) of the extract is injected into the GC. The compounds are
separated by GC and detected by a MS. The labeled compounds
SAMPLING METHOD Use 8-oz. widemouth glass bottles serve to correct the variability of the analytical technique.
with Teflon®-lined caps for concentrated waste samples, soils,
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles INTERFERENCES Solvents, reagents, glassware, and other
with Teflon®-lined caps for liquid (water) samples. sample processing hardware may yield artifacts and/or elevated
baselines causing misinterpretation of chromatograms and
STABILITY Cool soil, sediment, sludge, and liquid samples spectra. Materials used in the analysis must be demonstrated
to 4C. If residual chlorine is present in liquid samples add to be free from interferences under the conditions of analysis
3 mL of 10% sodium thiosulfate per gallon of sample and cool by running method blanks initially and with each sample lot
to 4C. (sample started through the extraction process on a given 8-h
MHT 14 days for concentrated waste, soil, sediment, or shift, to a maximum of 20). Specific selection of reagents and
sludge; 7 days for liquid samples; all extracts must be analyzed purification of solvents by distillation in all glass systems may
within 40 days. be required. Glassware and, where possible, reagents are
cleaned by solvent rinse and baking at 450C for 1-h minimum.
QUALITY CONTROL A quality control check sample con- Interferences coextracted from samples will vary considerably
centrate containing each analyte of interest is required. The QC from source to source, depending on the diversity of the site
check sample concentrate may be prepared from pure standard being sampled.
materials or purchased as certified solutions Use appropriate
trip, matrix, control site, method, reagent, and solvent blanks. INSTRUMENTATION Major instrumentation includes a GC
Internal, surrogate, and five concentration level calibration with a splitless or on-column injection port for capillary col-
standards are used. The QC check sample concentrate should umn, a MS with 70 eV electron impact ionization, and a data
contain this compound at 100 g/mL in 2-propanol. system to collect and record MS data, and process it. A K-D
apparatus is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC, GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
Method 8040A, Rev. 1, Nov. 1990. vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
Pentamethylbenzene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #700-12-9 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
The minimum level (in g/mL) was not listed. This is defined
tion GC/MS
as a minimum level at which the analytical system shall give
MATRIX The compounds may be determined in waters, recognizable mass spectra (background corrected) and accept-
soils, and municipal sludges by this method. able calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was not listed and in high
176 semivolatile toxic organic pollutants associated with the solids was not listed; these were determined in digested sludge
CWA (as amended 1987); the RCRA (as amended 1986); the (low solids) and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog-
deviation (in g/L) was not listed.
raphy-mass spectrometry (GC/MS).
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%,
SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with
Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques.
flow freely are collected in refrigerated bottles using automatic
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from

©1996 CRC Press LLC


the time of collection until extraction. If residual chlorine is
Perylene EPA Method 1625
present in aqueous samples, add 80 mg sodium thiosulfate/L
CAS #198-55-0
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
SAMPLE PREPARATION Samples containing 1% solids or tion GC/MS
less are extracted directly using continuous liquid-liquid
MATRIX The compounds may be determined in waters,
extraction techniques. Samples containing 1 to 30% solids are
soils, and municipal sludges by this method.
diluted to the 1% level with reagent water and extracted using
continuous liquid-liquid extraction techniques. Samples con- METHOD SUMMARY This method is used to determine
taining greater than 30% solids are extracted using ultrasonic 176 semivolatile toxic organic pollutants associated with the
techniques. CWA (as amended 1987); the RCRA (as amended 1986); the
CERCLA (as amended 1986); and other compounds amenable
Base/neutral extraction — Adjust the pH of the waters in the
to extraction and analysis by capillary column gas chromatog-
extractors to 12–13 with 6 N NaOH. Extract with methylene
raphy-mass spectrometry (GC/MS).
chloride for 24–48 h.
Acid extraction — Adjust the pH of the waters in the extractors Stable isotopically-labeled analogs of the compounds of interest
to 2 or less using 6 N sulfuric acid. Extract with methylene are added to the sample. If the solids content is less than 1%,
chloride for 24–48 h. a 1-L sample is extracted at pH 12–13, then at pH <2 with
Ultrasonic extraction of high solids samples — Add anhy- methylene chloride using continuous extraction techniques.
drous sodium sulfate to the sample and QC aliquot(s).
If the solids content is 30% or less, the sample is diluted to 1%
Add acetone:methylene chloride (1:1) to the sample and
solids with reagent water, homogenized ultrasonically, and
mix thoroughly
extracted at pH 12–13, then at pH <2 with methylene chloride
Concentrate extracts using a K-D apparatus. using continuous extraction techniques. If the solids content is
greater than 30%, the sample is extracted using ultrasonic
QUALITY CONTROL The analyst is permitted to modify
techniques.
this method to improve separations or lower the costs of mea-
surements, provided all performance specifications are met. Each extract is dried over sodium sulfate, concentrated to a
Analyses of blanks are required to demonstrate freedom from volume of 5 mL, cleaned up using GPC, if necessary, and con-
contamination. When results of spikes indicate atypical centrated. Extracts are concentrated to 1 mL if GPC is not
method performance for samples, the samples are diluted to performed, and to 0.5 mL if GPC is performed.
bring method performance within acceptable limits.
An internal standard is added to the extract, and a 1-mL aliquot
For low solids (aqueous samples), extract, concentrate, and of the extract is injected into the GC. The compounds are
analyze two sets of four 1-L aliquots (8 aliquots total) of the separated by GC and detected by a MS. The labeled compounds
precision and recovery standard. For high solids samples, two serve to correct the variability of the analytical technique.
sets of four 30-g aliquots of the high solids reference matrix
are used. INTERFERENCES Solvents, reagents, glassware, and other
sample processing hardware may yield artifacts and/or elevated
Spike all samples with labeled compounds to assess method baselines causing misinterpretation of chromatograms and
performance. Compute percent recovery of the labeled com- spectra. Materials used in the analysis must be demonstrated
pounds using the internal standard method. Compare the to be free from interferences under the conditions of analysis
labeled compound recovery for each compound with the cor- by running method blanks initially and with each sample lot
responding labeled compound recovery. (sample started through the extraction process on a given 8-h
shift, to a maximum of 20). Specific selection of reagents and
Reagent water and high solids reference matrix blanks are ana-
purification of solvents by distillation in all glass systems may
lyzed to demonstrate freedom from contamination. Extract
be required. Glassware and, where possible, reagents are
and concentrate a 1-L reagent water blank or a high solids
cleaned by solvent rinse and baking at 450C for 1-h minimum.
reference matrix blank with each sample’s lot (samples started
Interferences coextracted from samples will vary considerably
through the extraction process on the same 8-h shift, to a
from source to source, depending on the diversity of the site
maximum of 20 samples).
being sampled.
Field replicates may be collected to determine the precision of
INSTRUMENTATION Major instrumentation includes a GC
the sampling technique, and spiked samples may be required
with a splitless or on-column injection port for capillary col-
to determine the accuracy of the analysis when the internal
umn, a MS with 70 eV electron impact ionization, and a data
standard method is used.
system to collect and record MS data, and process it. A K-D
REFERENCE Semivolatile Organic Compounds by Isotope apparatus is used to concentrate extracts.
Dilution GC/MS. Office of Water Regulation and Standards,
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
U.S. EPA Industrial Technology Division, Washington, DC,
vinyl silicone bonded phased fused silica capillary column.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
U.S. EPA, Office of Water Regulations and Standards, 401 M PRECISION & ACCURACY The detection limits of the
St., SW, Washington, DC, 20460. Phone: 202-382-7131). method are usually dependent on the level of interferences

©1996 CRC Press LLC


rather than instrumental limitations. The limits typify the min- Spike all samples with labeled compounds to assess method
imum quantities that can be detected with no interferences performance. Compute percent recovery of the labeled com-
present. pounds using the internal standard method. Compare the
labeled compound recovery for each compound with the cor-
The minimum level (in g/mL) was not listed. This is defined responding labeled compound recovery.
as a minimum level at which the analytical system shall give
recognizable mass spectra (background corrected) and accept- Reagent water and high solids reference matrix blanks are ana-
able calibration points. lyzed to demonstrate freedom from contamination. Extract
and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was not listed and in high reference matrix blank with each sample’s lot (samples started
solids was not listed; these were determined in digested sludge through the extraction process on the same 8-h shift, to a
(low solids) and in filter cake or compost (high solids). maximum of 20 samples).
The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was not listed. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was not listed. standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from U.S. EPA, Office of Water Regulations and Standards, 401 M
the time of collection until extraction. If residual chlorine is St., SW, Washington, DC, 20460. Phone: 202-382-7131).
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction. pH EPA Method 9040
SAMPLE PREPARATION Samples containing 1% solids or
less are extracted directly using continuous liquid-liquid TITLE pH Electrometric Measurement
extraction techniques. Samples containing 1 to 30% solids are MATRIX This method is applicable to the measurement of
diluted to the 1% level with reagent water and extracted using pH of aqueous wastes and those multi-phase wastes where the
continuous liquid-liquid extraction techniques. Samples con- aqueous phase constitutes at least 20% of the total volume of
taining greater than 30% solids are extracted using ultrasonic the waste. The pH measurement requires minimum water con-
techniques. tent to cover the electrodes (about 25 mL).
Base/neutral extraction — Adjust the pH of the waters in the METHOD SUMMARY The pH of the sample is determined
extractors to 12–13 with 6 N NaOH. Extract with methylene electrometrically using either a glass electrode in combination
chloride for 24–48 h. with a reference electrode or with a combination electrode. The
Acid extraction — Adjust the pH of the waters in the extractors measuring device is calibrated using a series of standard solu-
to 2 or less using 6 N sulfuric acid. Extract with methylene tions of known pH. Samples are placed in a clean glass beaker
chloride for 24–48 h. using a sufficient volume to cover the sensing elements of the
Ultrasonic extraction of high solids samples — Add anhy- electrodes and to give adequate clearance for the magnetic
drous sodium sulfate to the sample and QC aliquot(s). stirring bar. The corrosivity of concentrated acids and bases
Add acetone:methylene chloride (1:1) to the sample and cannot be measured.
mix thoroughly INTERFERENCES The glass electrode is not generally sub-
Concentrate extracts using a K-D apparatus. ject to solution interferences from color, turbidity, collidal mat-
ter, oxidants, reductants, or high salinity. Sodium error at pH
QUALITY CONTROL The analyst is permitted to modify levels > 10 can be reduced or eliminated by using a low sodium
this method to improve separations or lower the costs of mea- error electrode. Coatings of oily material or particulate matter
surements, provided all performance specifications are met. can impair electrode response. Temperature effects on the elec-
Analyses of blanks are required to demonstrate freedom from trometric determination of pH arise from two sources. The first
contamination. When results of spikes indicate atypical is caused by the change in electrode output at various temper-
method performance for samples, the samples are diluted to atures. This interference can be controlled with instruments
bring method performance within acceptable limits. having temperature compensation. The second source of tem-
perature effects is the change of pH due to changes in the
For low solids (aqueous samples), extract, concentrate, and
sample as the temperature changes; this is sample-dependent
analyze two sets of four 1-L aliquots (8 aliquots total) of the and cannot be controlled.
precision and recovery standard. For high solids samples, two
sets of four 30-g aliquots of the high solids reference matrix INSTRUMENTATION A pH meter with glass electrode and
are used. a reference electrode is required.

©1996 CRC Press LLC


PRECISION & ACCURACY QUALITY CONTROL Calibrate at minimum of two points
that bracket expected pH of the samples and are approximately
Variation of accuracy as a function of pH units is listed below.
3 pH units or more apart. Sample should be within 2 C of
PRECISION & ACCURACY VERSUS pH buffers, if automatic temperature compensation is not provided.
Std. Dev. Accuracy as Accuracy as pH Units REFERENCE EPA Methods for the Chemical Analysis of
(pH Units) Bias (%) Bias (pH Units) Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
3.5 0.10 –0.29 –0.01
3.5 0.11 –0.00 Not listed.
7.1 0.20 +1.01 0.07 Phenacetin EPA Method 1625
7.2 0.18 –0.03 –0.002 CAS #62-44-2
8.0 0.13 –0.12 –0.01
8.0 0.12 +0.16 +0.01 TITLE Semivolatile Organic Compounds by Isotope Dilu-
SAMPLING METHOD Collect samples in 60 mL or larger, tion GC/MS
plastic or glass bottles. All bottles must be thoroughly cleaned MATRIX The compounds may be determined in waters,
and rinsed to remove soluble materials. soils, and municipal sludges by this method.
SAMPLE PRESERVATION No preservation is required. METHOD SUMMARY This method is used to determine
MHT Analyze samples immediately. 176 semivolatile toxic organic pollutants associated with the
CWA (as amended 1987); the RCRA (as amended 1986); the
SAMPLE PREPARATION No specific sample preparation is CERCLA (as amended 1986); and other compounds amenable
required when determining the pH of an aqueous sample. to extraction and analysis by capillary column gas chromatog-
QUALITY CONTROL No specific quality control procedures raphy-mass spectrometry (GC/MS).
were listed for this method. Electrodes must be rinsed thor-
Stable isotopically-labeled analogs of the compounds of interest
oughly between samples.
are added to the sample. If the solids content is less than 1%,
REFERENCE Test Methods for Evaluating Solid Waste (SW- a 1-L sample is extracted at pH 12–13, then at pH <2 with
846). U.S. EPA. 1983. Method 9040A, Rev. 1, Nov. 1990. Office methylene chloride using continuous extraction techniques.
of Solid Wastes, Washington, DC.
If the solids content is 30% or less, the sample is diluted to 1%
solids with reagent water, homogenized ultrasonically, and
extracted at pH 12–13, then at pH <2 with methylene chloride
pH (electrometric) EPA Method 150.1 using continuous extraction techniques. If the solids content is
greater than 30%, the sample is extracted using ultrasonic
TITLE Physical Properties techniques.
MATRIX Drinking, surface, and saline waters. Wastewater. Each extract is dried over sodium sulfate, concentrated to a
APPLICATION Date issued 1971. Editorial Rev. 1978. At a volume of 5 mL, cleaned up using GPC, if necessary, and con-
given temperature the intensity of the acidic or basic nature of centrated. Extracts are concentrated to 1 mL if GPC is not
a solution is indicated by pH (hydrogen ion activity). Alkalinity performed, and to 0.5 mL if GPC is performed.
and acidity are acid-and-base neutralizing abilities of water An internal standard is added to the extract, and a 1-mL aliquot
usually expressed as mg CaCO3/L. pH is determined electro- of the extract is injected into the GC. The compounds are
metrically using a glass electrode with a reference potential or separated by GC and detected by a MS. The labeled compounds
a combination electrode. serve to correct the variability of the analytical technique.
INTERFERENCES Coatings of oily or particulate matter, INTERFERENCES Solvents, reagents, glassware, and other
temperature effects, and sodium errors at pH levels >10 are sample processing hardware may yield artifacts and/or elevated
interferences. baselines causing misinterpretation of chromatograms and
INSTRUMENTATION pH meter, lab or field model. Mag- spectra. Materials used in the analysis must be demonstrated
netic stirrer and Teflon® stirring bar. to be free from interferences under the conditions of analysis
by running method blanks initially and with each sample lot
RANGE pH meter range (0–14). (sample started through the extraction process on a given 8-h
MDL Report pH to nearest 0.1 unit. shift, to a maximum of 20). Specific selection of reagents and
purification of solvents by distillation in all glass systems may
PRECISION Not listed. be required. Glassware and, where possible, reagents are
ACCURACY Limit of accuracy, 0.1 pH unit. cleaned by solvent rinse and baking at 450C for 1-h minimum.
Interferences coextracted from samples will vary considerably
SAMPLING METHOD Plastic or glass. (25 mL).
from source to source, depending on the diversity of the site
STABILITY No preservation required. Analyze immediately. being sampled.

©1996 CRC Press LLC


INSTRUMENTATION Major instrumentation includes a GC contamination. When results of spikes indicate atypical
with a splitless or on-column injection port for capillary col- method performance for samples, the samples are diluted to
umn, a MS with 70 eV electron impact ionization, and a data bring method performance within acceptable limits.
system to collect and record MS data, and process it. A K-D
For low solids (aqueous samples), extract, concentrate, and
apparatus is used to concentrate extracts.
analyze two sets of four 1-L aliquots (8 aliquots total) of the
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% precision and recovery standard. For high solids samples, two
vinyl silicone bonded phased fused silica capillary column. sets of four 30-g aliquots of the high solids reference matrix
are used.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences Spike all samples with labeled compounds to assess method
rather than instrumental limitations. The limits typify the min- performance. Compute percent recovery of the labeled com-
imum quantities that can be detected with no interferences pounds using the internal standard method. Compare the
present. labeled compound recovery for each compound with the cor-
responding labeled compound recovery.
The minimum level (in g/mL) was not listed. This is defined
as a minimum level at which the analytical system shall give Reagent water and high solids reference matrix blanks are ana-
recognizable mass spectra (background corrected) and accept- lyzed to demonstrate freedom from contamination. Extract
able calibration points. and concentrate a 1-L reagent water blank or a high solids
reference matrix blank with each sample’s lot (samples started
The MDL (in g/kg) in low solids was not listed and in high
through the extraction process on the same 8-h shift, to a
solids was not listed; these were determined in digested sludge
maximum of 20 samples).
(low solids) and in filter cake or compost (high solids).
Field replicates may be collected to determine the precision of
The labeled and native compound initial precision as standard the sampling technique, and spiked samples may be required
deviation (in g/L) was not listed. to determine the accuracy of the analysis when the internal
The labeled and native compound initial accuracy as average
standard method is used.
recovery (in g/L) was not listed.
REFERENCE Semivolatile Organic Compounds by Isotope
SAMPLE COLLECTION, PRESERVATION & HANDLING
Dilution GC/MS. Office of Water Regulation and Standards,
Collect samples in glass containers. Aqueous samples which
U.S. EPA Industrial Technology Division, Washington, DC,
flow freely are collected in refrigerated bottles using automatic
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
sampling equipment. Solid samples are collected as grab sam-
U.S. EPA, Office of Water Regulations and Standards, 401 M
ples using widemouth jars. Maintain samples at 0 to 4C from
St., SW, Washington, DC, 20460. Phone: 202-382-7131).
the time of collection until extraction. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction. Phenacetin EPA Method 8270
CAS #62-44-2
SAMPLE PREPARATION Samples containing 1% solids or
less are extracted directly using continuous liquid-liquid
TITLE Semivolatile Organic Compounds by GC/MS
extraction techniques. Samples containing 1 to 30% solids are
diluted to the 1% level with reagent water and extracted using MATRIX This method is used to determine the concentra-
continuous liquid-liquid extraction techniques. Samples con- tion of semivolatile organic compounds in extracts prepared
taining greater than 30% solids are extracted using ultrasonic from all types of solid waste matrices, soils, and groundwater.
techniques. Although surface waters are not specifically mentioned, this
method should be applicable to water samples from rivers,
Base/neutral extraction — Adjust the pH of the waters in the
lakes, etc.
extractors to 12–13 with 6 N NaOH. Extract with methylene
chloride for 24–48 h. METHOD SUMMARY This method covers 259 semivolatile
Acid extraction — Adjust the pH of the waters in the extractors organic compounds. In very limited applications direct injec-
to 2 or less using 6 N sulfuric acid. Extract with methylene tion of the sample into the GC/MS system may be appropriate,
chloride for 24–48 h. but this results in very high detection limits (approximately
Ultrasonic extraction of high solids samples — Add anhy- 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
drous sodium sulfate to the sample and QC aliquot(s). gate, and matrix spiking standards, is extracted in a continuous
Add acetone:methylene chloride (1:1) to the sample and extractor first under acid conditions and then under basic con-
mix thoroughly ditions. Typically 30 g of a solid sample, containing surrogate,
and matrix spiking standards, is extracted ultrasonically. After
Concentrate extracts using a K-D apparatus.
concentrating the extract to 1 mL it is spiked with 10 L of an
QUALITY CONTROL The analyst is permitted to modify internal standard solution just prior to analysis by GC/MS. The
this method to improve separations or lower the costs of mea- volume injected should contain about 100 ng of base/neutral
surements, provided all performance specifications are met. and 200 ng of acid surrogates (for a 1-L injection). Analysis
Analyses of blanks are required to demonstrate freedom from is performed by GC/MS using a capillary GC column.

©1996 CRC Press LLC


INTERFERENCES Raw GC/MS data from all blanks, sam- SAMPLE PRESERVATION
ples, and spikes must be evaluated for interferences. Contam- Liquid samples — If residual chlorine is present, add 3 mL of
ination by carryover can occur whenever high-concentration 10% sodium thiosulfate per gallon, cool to 4C and store in a
and low-concentration samples are sequentially analyzed. To solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out then eliminate the sodium thiosulfate addition.
between samples with solvent. Whenever an unusually concen-
Soils, sediments, or sludges — Cool samples to 4C and store
trated sample is encountered, it should be followed by the in a solvent-free refrigerator.
analysis of blank solvent to check for cross-contamination.
MHT Liquid samples must be extracted within 7 days and
INSTRUMENTATION A GC/MS and a data system are the extracts analyzed within 40 days. Soils, sediments, or slud-
required. The GC column used is a 30 m 0.25 mm I.D. (or ges may be stored for a maximum of 14 days and the extracts
0.32 mm I.D.) 1um film thickness silicone-coated fused silica analyzed within 40 days.
capillary column. A continuous liquid-liquid extractor
equipped with Teflon® or glass connection joints and stopcocks SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
PRECISION & ACCURACY The estimated quantitation sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
limit (EQL) of Method 8270B for determining an individual solution into each sample. For the sample in each analytical
compound is approximately 1 mg/kg (wet weight) for soil or batch selected for spiking, add 1.0 mL of a matrix spiking stan-
sediment samples, 1–200 mg/kg for wastes (dependent on dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground- gates and matrix spiking compounds added to the sample
water samples. EQLs will be proportionately higher for sample should result in a final concentration of 100 ng/L of each
extracts that require dilution to avoid saturation of the detector. analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is 20. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
Overall precision in g/L is not listed.
concentrator.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
Soils, sediments, or sludges — Use 30 g of sample. Nonporous
mally data is reported in a dry-weight basis; therefore, EQLs
or wet samples (gummy or clay type) that do not have a free-
will be higher based on the % dry weight of each sample.
flowing sandy texture must be mixed with anhydrous sodium
This calculation is based on a 30 g sample and gel perme-
sulfate until the sample is free flowing. Add 1 mL of surrogate
ation chromatography cleanup. standards to all samples, spikes, standards, and blanks. For the
(b) Sample EQLs are highly matrix-dependent. The EQLs are sample in each analytical batch selected for spiking, add 1.0 mL
provided for guidance and may not always be achievable. of a matrix spiking standard. For base/neutral acid analysis, the
C = True value for concentration, in g/L. amount added of the surrogates and matrix spiking com-
X = Average recovery found for measurements of samples con- pounds should result in a final concentration of 100 ng/ L of
taining a concentration of C, in g/L.
each base/neutral analyte and 200 ng/L of each acid analyte
ESTIMATED QUANTITATION LIMIT in the extract to be analyzed (assuming a 1- L injection).
Other Matrices Factor (a) Immediately add a 100-mL mixture of 1:1 methylene chlo-
ride:acetone and extract the sample ultrasonically for 3 min
High-concentration soil and sludges by sonicator 7.5 and then decant or filter the extracts. Repeat the extraction two
Non-water miscible waste 75 or more times. Dry the extract using a column with anhydrous
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
This estimated EQL is similar to an EPA “Practical Quantitation QUALITY CONTROL A methylene chloride solution con-
Limit.” taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD used for tuning the GC/MS system each 12-h shift. A system
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with performance check also must be made during every 12-h shift.
a screw-top Teflon®-lined cover that has been prewashed with A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
detergent and rinsed with distilled water and methanol (or rophenol, and benzidine is required to verify injection port
isopropanol). inertness and GC column performance. A calibration standard
at mid-concentration, containing each compound of interest,
Soils, sediments, or sludges — Use an 8-oz. widemouth glass including all required surrogates, must be performed every 12 h
with a screw-top Teflon®-lined cover that has been prewashed during analysis. After the system performance check is met,
with detergent and rinsed with distilled water and methanol calibration check compounds (CCCs) are used to check the
(or isopropanol). validity of the initial calibration.

©1996 CRC Press LLC


The internal standard responses and retention times in the An internal standard is added to the extract, and a 1-mL aliquot
calibration check standard must be evaluated immediately after of the extract is injected into the GC. The compounds are
or during data acquisition. If the retention time for any internal separated by GC and detected by a MS. The labeled compounds
standard changes by more than 30 seconds from the last check serve to correct the variability of the analytical technique.
calibration (12 h), the chromatographic system must be
INTERFERENCES Solvents, reagents, glassware, and other
inspected for malfunctions and corrections must be made, as
sample processing hardware may yield artifacts and/or elevated
required. If the electron ionization current plot (EICP) area for
baselines causing misinterpretation of chromatograms and
any of the internal standards changes by a factor of two from
the last daily calibration standard check, the mass spectrometer spectra. Materials used in the analysis must be demonstrated
must be inspected for malfunctions and corrections must be to be free from interferences under the conditions of analysis
made, as appropriate. by running method blanks initially and with each sample lot
(sample started through the extraction process on a given 8-h
Demonstrate, through the analysis of a reagent water blank, shift, to a maximum of 20). Specific selection of reagents and
that interferences from the analytical system, glassware, and purification of solvents by distillation in all glass systems may
reagents are under control. The blank samples should be car- be required. Glassware and, where possible, reagents are
ried through all stages of the sample preparation and measure- cleaned by solvent rinse and baking at 450C for 1-h minimum.
ment steps. For each analytical batch (up to 20 samples), a Interferences coextracted from samples will vary considerably
reagent blank, matrix spike, and matrix spike duplicate/dupli- from source to source, depending on the diversity of the site
cate must be analyzed (the frequency of the spikes may be being sampled.
different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample INSTRUMENTATION Major instrumentation includes a GC
preparation and measurement steps. A QC reference sample with a splitless or on-column injection port for capillary col-
concentrate containing each analyte at a concentration of umn, a MS with 70 eV electron impact ionization, and a data
100 mg/L in methanol is required. system to collect and record MS data, and process it. A K-D
apparatus is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
of Solid Waste, Washington, DC. vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
Phenanthrene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #85-01-8 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was 10. This is defined as a
tion GC/MS minimum level at which the analytical system shall give recog-
MATRIX The compounds may be determined in waters, nizable mass spectra (background corrected) and acceptable
soils, and municipal sludges by this method. calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was 42 and in high solids
176 semivolatile toxic organic pollutants associated with the was 22; these were determined in digested sludge (low solids)
CWA (as amended 1987); the RCRA (as amended 1986); the and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog-
deviation (in g/L) was 13.
raphy-mass spectrometry (GC/MS).
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was 93–119.
are added to the sample. If the solids content is less than 1%,
SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with
Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques.
flow freely are collected in refrigerated bottles using automatic
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from
extracted at pH 12–13, then at pH <2 with methylene chloride the time of collection until extraction. If residual chlorine is
using continuous extraction techniques. If the solids content is present in aqueous samples, add 80 mg sodium thiosulfate/L
greater than 30%, the sample is extracted using ultrasonic of water. Begin sample extraction within 7 days of collection,
techniques. and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a SAMPLE PREPARATION Samples containing 1% solids or
volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid extrac-
centrated. Extracts are concentrated to 1 mL if GPC is not tion techniques. Samples containing 1 to 30% solids are diluted
performed, and to 0.5 mL if GPC is performed. to the 1% level with reagent water and extracted using continuous

©1996 CRC Press LLC


liquid-liquid extraction techniques. Samples containing greater METHOD SUMMARY Approximately 1 L of sample is seri-
than 30% solids are extracted using ultrasonic techniques. ally extracted with methylene chloride at a pH greater than 11
and again at a pH less than 2 using a separatory funnel or a
Base/neutral extraction — Adjust the pH of the waters in the
continuous extractor. The methylene chloride extract is dried,
extractors to 12–13 with 6 N NaOH. Extract with methylene
concentrated to a volume of 1 mL, and analyzed by GC/MS.
chloride for 24–48 h.
Qualitative identification of the parameters in the extract is
Acid extraction — Adjust the pH of the waters in the extractors
performed using the retention time and the relative abundance
to 2 or less using 6 N sulfuric acid. Extract with methylene
of three characteristic masses (m/z). Qualitative analysis is per-
chloride for 24–48 h.
formed using either external or internal standard techniques
Ultrasonic extraction of high solids samples — Add anhy-
with a single characteristic m/z.
drous sodium sulfate to the sample and QC aliquot(s).
Add acetone:methylene chloride (1:1) to the sample and INTERFERENCES Method interferences may be caused by
mix thoroughly contaminants in solvents, reagents, glassware, and other sample
processing hardware. Glassware must be scrupulously cleaned.
Concentrate extracts using a K-D apparatus.
Glassware should be heated in a muffle furnace at 400C for 5
QUALITY CONTROL The analyst is permitted to modify to 30 min. Some thermally stable materials, such as PCBs, may
this method to improve separations or lower the costs of mea- not be eliminated by this treatment. Solvent rinses with acetone
surements, provided all performance specifications are met. and pesticide quality hexane may be substituted for the muffle
Analyses of blanks are required to demonstrate freedom from furnace heating. Matrix interferences may be caused by con-
contamination. When results of spikes indicate atypical taminants that are coextracted from the sample. The base-
method performance for samples, the samples are diluted to neutral extraction may cause significantly reduced recovery of
bring method performance within acceptable limits. phenols. The packed gas chromatographic columns recom-
mended for the basic fraction may not exhibit sufficient reso-
For low solids (aqueous samples), extract, concentrate, and
lution for some analytes.
analyze two sets of four 1-L aliquots (8 aliquots total) of the
precision and recovery standard. For high solids samples, two INSTRUMENTATION A GC/MS system with an injection
sets of four 30-g aliquots of the high solids reference matrix port designed for on-column injection when using packed col-
are used. umns and for splitless injection when using capillary columns.
Spike all samples with labeled compounds to assess method Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
performance. Compute percent recovery of the labeled com- packed with 3% SP-2550 on Supelcoport (100/120 mesh)
pounds using the internal standard method. Compare the or equivalent.
labeled compound recovery for each compound with the cor- Column for acids: 1.8 m long 2 mm I.D. glass, packed with 1%
responding labeled compound recovery. SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
Reagent water and high solids reference matrix blanks are ana- PRECISION & ACCURACY The MDL concentrations were
lyzed to demonstrate freedom from contamination. Extract obtained using reagent water. The MDL actually achieved in a
and concentrate a 1-L reagent water blank or a high solids given analysis will vary depending on instrument sensitivity
reference matrix blank with each sample’s lot (samples started and matrix effects. This method was tested by 15 laboratories
through the extraction process on the same 8-h shift, to a using reagent water, drinking water, surface water, and indus-
maximum of 20 samples). trial wastewaters spiked at six concentrations over the range 5
Field replicates may be collected to determine the precision of to 100 g/L. Single operator precision, overall precision, and
the sampling technique, and spiked samples may be required method accuracy were found to be directly related to the con-
to determine the accuracy of the analysis when the internal centration of the parameter matrix.
standard method is used. The MDL (in g/L) in reagent water was 5.4.
REFERENCE Semivolatile Organic Compounds by Isotope The standard deviation (in g/L based on 4 recovery measure-
Dilution GC/MS. Office of Water Regulation and Standards, ments) was 20.6.
U.S. EPA Industrial Technology Division, Washington, DC, The range (in g/L) for average recovery for 4 measurements
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, was 65.2–08.7.
The range (in %) for percent recovery was 54–120.
U.S. EPA, Office of Water Regulations and Standards, 401 M
St., SW, Washington, DC, 20460. Phone: 202-382-7131). Accuracy (in g/L) as expected recovery for one or more mea-
surements of a sample containing a true concentration of
C was 0.87C-0.06.
Precision (in g/L) as expected single analyst standard devia-
Phenanthrene EPA Method 625 tion of measurements at an average concentration found at
CAS #85-01-8 X was 0.12X + 0.57.
Overall precision (in g/L) as expected interlaboratory stan-
TITLE Base/Neutrals and Acids, U.S. EPA Method 625 dard deviation of measurements in an average concentra-
tion found at X was 0.15X + .025.
MATRIX This methods covers municipal and industrial
wastewaters. C = True value of the concentration in g/L.

©1996 CRC Press LLC


X = Average recovery found for measurements of samples con- ditions. Typically 30 g of a solid sample, containing surrogate,
taining a concentration at C in g/L. and matrix spiking standards, is extracted ultrasonically. After
concentrating the extract to 1 mL it is spiked with 10 L of an
SAMPLE PREPARATION Adjust the pH to >11 with sodium
internal standard solution just prior to analysis by GC/MS. The
hydroxide and serially extract in a separatory funnel with meth-
volume injected should contain about 100 ng of base/neutral
ylene chloride or else in a continuous extractor. Next, adjust
and 200 ng of acid surrogates (for a 1-L injection). Analysis
the pH to <2 with sulfuric acid and serially extract in a sepa- is performed by GC/MS using a capillary GC column.
ratory funnel with methylene chloride or else in a continuous
extractor. Dry the extracts separately through a column of INTERFERENCES Raw GC/MS data from all blanks, sam-
anhydrous sodium sulfate and then concentrate each of the ples, and spikes must be evaluated for interferences. Contam-
extracts to 1.0 mL using a K-D apparatus. ination by carryover can occur whenever high-concentration
and low-concentration samples are sequentially analyzed. To
SAMPLE COLLECTION, PRESERVATION & HANDLING reduce carryover, the sample syringe must be rinsed out
Grab samples must be collected in glass containers. All samples between samples with solvent. Whenever an unusually concen-
must be refrigerated at 4C from the time of collection until trated sample is encountered, it should be followed by the
extraction. If residual chlorine is present, add 80 mg of sodium analysis of blank solvent to check for cross-contamination.
thiosulfate/L of sample and mix well. All samples must be
extracted within 7 days of collection and completely analyzed INSTRUMENTATION A GC/MS and a data system are
within 40 days of extraction. required. The GC column used is a 30 m 0.25 mm I.D. (or
0.32 mm I.D.) 1um film thickness silicone-coated fused silica
QUALITY CONTROL Make an initial, one-time, demonstra- capillary column. A continuous liquid-liquid extractor
tion of the ability to generate acceptable accuracy and precision equipped with Teflon® or glass connection joints and stopcocks
with this method. Before processing any samples, the analyst requiring no lubrication, a K-D concentrating apparatus, water
must analyze a reagent water blank to demonstrate that inter- bath, and an ultrasonic disrupter with a minimum power of
ferences from the analytical system and glassware are under 300 W and with pulsing capability are also required.
control. Each time a set of samples is extracted or reagents are
changed, a reagent water blank must be processed. Spike and PRECISION & ACCURACY The estimated quantitation
analyze a minimum of 5% of all samples to monitor and eval- limit (EQL) of Method 8270B for determining an individual
uate lab data quality. A QC check sample concentrate that compound is approximately 1 mg/kg (wet weight) for soil or
contains each parameter of interest at a concentration of sediment samples, 1–200 mg/kg for wastes (dependent on
100 g/mL in acetone is required. PCBs and multicomponent matrix and method of preparation), and 10 g/L for ground-
pesticides may be omitted from this test. water samples. EQLs will be proportionately higher for sample
extracts that require dilution to avoid saturation of the detector.
After analysis of five spiked wastewater samples, calculate the
The EQL(b) for groundwater in g/L is 10.
average percent recovery and the standard deviation of the
The EQL (a, b) for low concentrations in soil and sediment
percent recovery. Spike all samples with the surrogate standard
in g/kg is 660.
spiking solution and calculate the percent recovery of each
Accuracy as g/L is 0.87C + 0.06.
surrogate compound.
Overall precision in g/L is 0.15X + 0.25.
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
26, 1984.
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
This calculation is based on a 30 g sample and gel perme-
Phenanthrene EPA Method 8270 ation chromatography cleanup.
CAS #85-01-8 (b) Sample EQLs are highly matrix-dependent. The EQLs are
provided for guidance and may not always be achievable.
TITLE Semivolatile Organic Compounds by GC/MS C = True value for concentration, in g/L.
X = Average recovery found for measurements of samples con-
MATRIX This method is used to determine the concentra- taining a concentration of C, in g/L.
tion of semivolatile organic compounds in extracts prepared
from all types of solid waste matrices, soils, and groundwater. ESTIMATED QUANTITATION LIMIT
Although surface waters are not specifically mentioned, this Other Matrices Factor (a)
method should be applicable to water samples from rivers,
High-concentration soil and sludges by sonicator 7.5
lakes, etc.
Non-water miscible waste 75
METHOD SUMMARY This method covers 259 semivolatile
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
organic compounds. In very limited applications direct injec-
This estimated EQL is similar to an EPA “Practical Quantitation
tion of the sample into the GC/MS system may be appropriate,
Limit.”
but this results in very high detection limits (approximately
10,000 g/L). Typically, a 1-L liquid sample, containing surro- SAMPLING METHOD
gate, and matrix spiking standards, is extracted in a continuous Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
extractor first under acid conditions and then under basic con- a screw-top Teflon®-lined cover that has been prewashed with

©1996 CRC Press LLC


detergent and rinsed with distilled water and methanol (or rophenol, and benzidine is required to verify injection port
isopropanol). inertness and GC column performance. A calibration standard
at mid-concentration, containing each compound of interest,
Soils, sediments, or sludges — Use an 8-oz. widemouth glass
including all required surrogates, must be performed every 12 h
with a screw-top Teflon®-lined cover that has been prewashed
during analysis. After the system performance check is met,
with detergent and rinsed with distilled water and methanol
calibration check compounds (CCCs) are used to check the
(or isopropanol).
validity of the initial calibration.
SAMPLE PRESERVATION
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check standard must be evaluated immediately after
solvent-free refrigerator until analysis; if chlorine is not present, or during data acquisition. If the retention time for any internal
then eliminate the sodium thiosulfate addition. standard changes by more than 30 seconds from the last check
calibration (12 h), the chromatographic system must be
Soils, sediments, or sludges — Cool samples to 4C and store inspected for malfunctions and corrections must be made, as
in a solvent-free refrigerator. required. If the electron ionization current plot (EICP) area for
MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.

SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,


Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust
the pH of the aqueous phase to pH >11 using 10 N sodium
hydroxide and extract it with methylene chloride again for
Phenanthrene EPA Method 8100
18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D CAS #85-01-8
concentrator.
TITLE Polynuclear Aromatic Hydrocarbons
Soils, sediments, or sludges — Use 30 g of sample. Nonporous
MATRIX Groundwater, soils, sludges, water miscible liquid
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium wastes, and non-water miscible wastes.
sulfate until the sample is free flowing. Add 1 mL of surrogate APPLICATION This method is used for the analysis of var-
standards to all samples, spikes, standards, and blanks. For the ious PAHs. Samples are extracted, concentrated, and analyzed
sample in each analytical batch selected for spiking, add 1.0 mL using direct injection of both neat and diluted organic liquids.
of a matrix spiking standard. For base/neutral acid analysis, the The method provides two optional GC columns that are better
amount added of the surrogates and matrix spiking com- than Column 1 and that may help resolve analytes from inter-
pounds should result in a final concentration of 100 ng/ L of ferences.
each base/neutral analyte and 200 ng/L of each acid analyte
in the extract to be analyzed (assuming a 1- L injection). INTERFERENCES Solvents, reagents, and glassware may
Immediately add a 100-mL mixture of 1:1 methylene chlo- introduce artifacts. Other interferences may come from coex-
ride:acetone and extract the sample ultrasonically for 3 min tracted compounds from samples.
and then decant or filter the extracts. Repeat the extraction two INSTRUMENTATION GC capable of on-column injections
or more times. Dry the extract using a column with anhydrous and a flame with detector (FID). Column 1: a 1.8 m by 2 mm
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. 3% OV-17 on Chromosorb W-AW-DCMS column. Column 2:
QUALITY CONTROL A methylene chloride solution con- a 30 m by 0.25 mm SE-54 fused silica capillary colunm. Col-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is umn 3: a 30 m by 0.32 mm SE-54 fused silica capillary column.
used for tuning the GC/MS system each 12-h shift. A system RANGE 0.1–425 g/L
performance check also must be made during every 12-h shift.
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- MDL Not reported.

©1996 CRC Press LLC


PQL FACTORS FOR MULTIPLYING  FID MDL VALUE PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
Not available. Matrix Multiplication Factor
PRECISION 0.47X–0.25 g/L (overall precision). Groundwater 10
ACCURACY 0.72C–0.95 g/L (as recovery). Low-level soil by sonication with GPC cleanup 670
High-level soil and sludge by sonication 10,000
SAMPLING METHOD Use 8-oz. widemouth glass bottles Non-water miscible waste 100,000
with Teflon®-lined caps for concentrated waste samples, soils,
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles PRECISION 0.47X–0.25 g/L (overall precision).
with Teflon®-lined caps for liquid (water) samples. ACCURACY 0.72C–0.95 g/L (as recovery).
STABILITY Cool soil, sediment, sludge, and liquid samples SAMPLING METHOD Use 8-oz. widemouth glass bottles
to 4C. If residual chlorine is present in liquid samples add with Teflon®-lined caps for concentrated waste samples, soils,
3 mL of 10% sodium thiosulfate per gallon of sample and cool sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
to 4C. with Teflon®-lined caps for liquid (water) samples.
MHT 14 days for concentrated waste, soil, sediment, or STABILITY Cool soil, sediment, sludge, and liquid samples
sludge; 7 days for liquid samples; all extracts must be analyzed to 4C. If residual chlorine is present in liquid samples add
within 40 days. 3 mL of 10% sodium thiosulfate per gallon of sample and cool
QUALITY CONTROL A quality control check sample con- to 4C.
centrate containing each analyte of interest is required. The QC MHT 14 days for concentrated waste, soil, sediment, or
check sample concentrate may be prepared from pure standard sludge; 7 days for liquid samples; all extracts must be analyzed
materials or purchased as certified solutions Use appropriate within 40 days.
trip, matrix, control site, method, reagent, and solvent blanks.
Internal, surrogate, and five concentration level calibration QUALITY CONTROL Internal, surrogate, and five concen-
standards are used. The quality control check sample concen- tration level calibration standards are used. The calibration
trate should contain phenanthrene at 100 g/mL in acetonitrile. standards must be used with the analytical method blank. A
quality control check sample concentrate containing phenan-
REFERENCE Test Methods for Evaluating Solid Waste
threne at 100 g/mL is required. The QC check sample con-
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
centrate may be prepared from pure standard materials or
Method 8100, Nov. 1986.
purchased as certified solutions. Use appropriate trip, matrix,
control site, method, reagent, and solvent blanks.
REFERENCE Test Methods for Evaluating Solid Waste
Phenanthrene EPA Method 8310
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
CAS #85-01-8
Method 8310, Rev. 0, Nov. 1986.
TITLE Polynuclear Aromatic Hydrocarbons
MATRIX Groundwater, soils, sludges, water miscible liquid
wastes, and non-water miscible wastes. Phenobarbital EPA Method 8270
CAS #50-06-6
APPLICATION This method is used for the analysis of 16
polynuclear aromatic hydrocarbons (PAHs). Samples are TITLE Semivolatile Organic Compounds by GC/MS
extracted, concentrated, and analyzed using HPLC with detec-
tion by UV and fluorescence detectors. MATRIX This method is used to determine the concentra-
tion of semivolatile organic compounds in extracts prepared
INTERFERENCES Solvents, reagents, and glassware may from all types of solid waste matrices, soils, and groundwater.
introduce artifacts. Other interferences may come from coex- Although surface waters are not specifically mentioned, this
tracted compounds from samples. method should be applicable to water samples from rivers,
INSTRUMENTATION HPLC with a gradient pumping sys- lakes, etc.
tem and a 250 mm by 2.6 mm reverse phase HC-ODS Sil-X METHOD SUMMARY This method covers 259 semivolatile
5-micron particle-size column. The fluorescence detector uses organic compounds. In very limited applications direct injec-
an excitation wavelength of 280 nm and emission greater than tion of the sample into the GC/MS system may be appropriate,
389 nm cutoff with dispersive optics. but this results in very high detection limits (approximately
RANGE 0.1–425 g/L 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous
MDL 0.64 g/L (fluorescence; reagent water). extractor first under acid conditions and then under basic con-
ditions. Typically 30 g of a solid sample, containing surrogate,
and matrix spiking standards, is extracted ultrasonically. After
concentrating the extract to 1 mL it is spiked with 10 L of an

©1996 CRC Press LLC


internal standard solution just prior to analysis by GC/MS. The Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral with a screw-top Teflon®-lined cover that has been prewashed
and 200 ng of acid surrogates (for a 1-L injection). Analysis with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column. (or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam- SAMPLE PRESERVATION
ples, and spikes must be evaluated for interferences. Contam- Liquid samples — If residual chlorine is present, add 3 mL of
ination by carryover can occur whenever high-concentration 10% sodium thiosulfate per gallon, cool to 4C and store in a
and low-concentration samples are sequentially analyzed. To solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out then eliminate the sodium thiosulfate addition.
between samples with solvent. Whenever an unusually concen- Soils, sediments, or sludges — Cool samples to 4C and store
trated sample is encountered, it should be followed by the in a solvent-free refrigerator.
analysis of blank solvent to check for cross-contamination.
MHT Liquid samples must be extracted within 7 days and
INSTRUMENTATION A GC/MS and a data system are the extracts analyzed within 40 days. Soils, sediments, or slud-
required. The GC column used is a 30 m 0.25 mm I.D. (or ges may be stored for a maximum of 14 days and the extracts
0.32 mm I.D.) 1um film thickness silicone-coated fused silica analyzed within 40 days.
capillary column. A continuous liquid-liquid extractor
equipped with Teflon® or glass connection joints and stopcocks SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
PRECISION & ACCURACY The estimated quantitation sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
limit (EQL) of Method 8270B for determining an individual solution into each sample. For the sample in each analytical
compound is approximately 1 mg/kg (wet weight) for soil or batch selected for spiking, add 1.0 mL of a matrix spiking stan-
sediment samples, 1–200 mg/kg for wastes (dependent on dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground- gates and matrix spiking compounds added to the sample
water samples. EQLs will be proportionately higher for sample should result in a final concentration of 100 ng/L of each
extracts that require dilution to avoid saturation of the detector. analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is 10. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
Overall precision in g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous
will be higher based on the % dry weight of each sample. or wet samples (gummy or clay type) that do not have a free-
This calculation is based on a 30 g sample and gel perme- flowing sandy texture must be mixed with anhydrous sodium
ation chromatography cleanup. sulfate until the sample is free flowing. Add 1 mL of surrogate
(b) Sample EQLs are highly matrix-dependent. The EQLs are standards to all samples, spikes, standards, and blanks. For the
provided for guidance and may not always be achievable. sample in each analytical batch selected for spiking, add 1.0 mL
C = True value for concentration, in g/L. of a matrix spiking standard. For base/neutral acid analysis, the
X = Average recovery found for measurements of samples con- amount added of the surrogates and matrix spiking com-
taining a concentration of C, in g/L. pounds should result in a final concentration of 100 ng/ L of
each base/neutral analyte and 200 ng/L of each acid analyte
ESTIMATED QUANTITATION LIMIT in the extract to be analyzed (assuming a 1- L injection).
Other Matrices Factor (a) Immediately add a 100-mL mixture of 1:1 methylene chlo-
High-concentration soil and sludges by sonicator 7.5 ride:acetone and extract the sample ultrasonically for 3 min
Non-water miscible waste 75 and then decant or filter the extracts. Repeat the extraction two
or more times. Dry the extract using a column with anhydrous
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
This estimated EQL is similar to an EPA “Practical Quantitation
QUALITY CONTROL A methylene chloride solution con-
Limit.”
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD used for tuning the GC/MS system each 12-h shift. A system
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with performance check also must be made during every 12-h shift.
a screw-top Teflon®-lined cover that has been prewashed with A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
detergent and rinsed with distilled water and methanol (or rophenol, and benzidine is required to verify injection port
isopropanol). inertness and GC column performance. A calibration standard

©1996 CRC Press LLC


at mid-concentration, containing each compound of interest, greater than 30%, the sample is extracted using ultrasonic
including all required surrogates, must be performed every 12 h techniques.
during analysis. After the system performance check is met,
Each extract is dried over sodium sulfate, concentrated to a
calibration check compounds (CCCs) are used to check the volume of 5 mL, cleaned up using GPC, if necessary, and con-
validity of the initial calibration. centrated. Extracts are concentrated to 1 mL if GPC is not
The internal standard responses and retention times in the performed, and to 0.5 mL if GPC is performed.
calibration check standard must be evaluated immediately after An internal standard is added to the extract, and a 1-mL aliquot
or during data acquisition. If the retention time for any internal of the extract is injected into the GC. The compounds are
standard changes by more than 30 seconds from the last check separated by GC and detected by a MS. The labeled compounds
calibration (12 h), the chromatographic system must be serve to correct the variability of the analytical technique.
inspected for malfunctions and corrections must be made, as
required. If the electron ionization current plot (EICP) area for INTERFERENCES Solvents, reagents, glassware, and other
any of the internal standards changes by a factor of two from sample processing hardware may yield artifacts and/or elevated
the last daily calibration standard check, the mass spectrometer baselines causing misinterpretation of chromatograms and
must be inspected for malfunctions and corrections must be spectra. Materials used in the analysis must be demonstrated
to be free from interferences under the conditions of analysis
made, as appropriate.
by running method blanks initially and with each sample lot
Demonstrate, through the analysis of a reagent water blank, (sample started through the extraction process on a given 8-h
that interferences from the analytical system, glassware, and shift, to a maximum of 20). Specific selection of reagents and
reagents are under control. The blank samples should be car- purification of solvents by distillation in all glass systems may
ried through all stages of the sample preparation and measure- be required. Glassware and, where possible, reagents are
ment steps. For each analytical batch (up to 20 samples), a cleaned by solvent rinse and baking at 450C for 1-h minimum.
reagent blank, matrix spike, and matrix spike duplicate/dupli- Interferences coextracted from samples will vary considerably
cate must be analyzed (the frequency of the spikes may be from source to source, depending on the diversity of the site
different for different monitoring programs). The blank and being sampled.
spiked samples must be carried through all stages of the sample INSTRUMENTATION Major instrumentation includes a GC
preparation and measurement steps. A QC reference sample with a splitless or on-column injection port for capillary col-
concentrate containing each analyte at a concentration of umn, a MS with 70 eV electron impact ionization, and a data
100 mg/L in methanol is required. system to collect and record MS data, and process it. A K-D
REFERENCE Test Methods for Evaluating Solid Waste (SW- apparatus is used to concentrate extracts.
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
of Solid Waste, Washington, DC. vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
Phenol EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #108-95-2 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
The minimum level (in g/mL) was 10. This is defined as a
tion GC/MS
minimum level at which the analytical system shall give recog-
MATRIX The compounds may be determined in waters, nizable mass spectra (background corrected) and acceptable
soils, and municipal sludges by this method. calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was 2501 and in high solids
176 semivolatile toxic organic pollutants associated with the was 757; these were determined in digested sludge (low solids)
CWA (as amended 1987); the RCRA (as amended 1986); the and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable Note: Background levels of this compound were present in the
to extraction and analysis by capillary column gas chromatog- sludge tested, resulting in higher than expected MDLs. The
raphy-mass spectrometry (GC/MS). MDL for this compound is expected to be approximately
Stable isotopically-labeled analogs of the compounds of interest 50 g/kg with no interferences present.
are added to the sample. If the solids content is less than 1%, The labeled and native compound initial precision as standard
a 1-L sample is extracted at pH 12–13, then at pH <2 with deviation (in g/L) was 36.
methylene chloride using continuous extraction techniques. The labeled and native compound initial accuracy as average
If the solids content is 30% or less, the sample is diluted to 1% recovery (in g/L) was 77–127.
solids with reagent water, homogenized ultrasonically, and SAMPLE COLLECTION, PRESERVATION & HANDLING
extracted at pH 12–13, then at pH <2 with methylene chloride Collect samples in glass containers. Aqueous samples which
using continuous extraction techniques. If the solids content is flow freely are collected in refrigerated bottles using automatic

©1996 CRC Press LLC


sampling equipment. Solid samples are collected as grab sam- U.S. EPA, Office of Water Regulations and Standards, 401 M
ples using widemouth jars. Maintain samples at 0 to 4C from St., SW, Washington, DC, 20460. Phone: 202-382-7131).
the time of collection until extraction. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
Phenol EPA Method 625
and analyze all extracts within 40 days of extraction.
CAS #108-95-2
SAMPLE PREPARATION Samples containing 1% solids or
less are extracted directly using continuous liquid-liquid TITLE Base/Neutrals and Acids, U.S. EPA Method 625
extraction techniques. Samples containing 1 to 30% solids are
diluted to the 1% level with reagent water and extracted using MATRIX This methods covers municipal and industrial
continuous liquid-liquid extraction techniques. Samples con- wastewaters.
taining greater than 30% solids are extracted using ultrasonic METHOD SUMMARY Approximately 1 L of sample is seri-
techniques. ally extracted with methylene chloride at a pH greater than 11
Base/neutral extraction — Adjust the pH of the waters in the and again at a pH less than 2 using a separatory funnel or a
extractors to 12–13 with 6 N NaOH. Extract with methylene continuous extractor. The methylene chloride extract is dried,
chloride for 24–48 h. concentrated to a volume of 1 mL, and analyzed by GC/MS.
Acid extraction — Adjust the pH of the waters in the extractors Qualitative identification of the parameters in the extract is
to 2 or less using 6 N sulfuric acid. Extract with methylene performed using the retention time and the relative abundance
chloride for 24–48 h. of three characteristic masses (m/z). Qualitative analysis is per-
Ultrasonic extraction of high solids samples — Add anhy- formed using either external or internal standard techniques
drous sodium sulfate to the sample and QC aliquot(s). with a single characteristic m/z.
Add acetone:methylene chloride (1:1) to the sample and INTERFERENCES Method interferences may be caused by
mix thoroughly contaminants in solvents, reagents, glassware, and other sample
Concentrate extracts using a K-D apparatus. processing hardware. Glassware must be scrupulously cleaned.
Glassware should be heated in a muffle furnace at 400C for 5
QUALITY CONTROL The analyst is permitted to modify to 30 min. Some thermally stable materials, such as PCBs, may
this method to improve separations or lower the costs of mea- not be eliminated by this treatment. Solvent rinses with acetone
surements, provided all performance specifications are met. and pesticide quality hexane may be substituted for the muffle
Analyses of blanks are required to demonstrate freedom from furnace heating. Matrix interferences may be caused by con-
contamination. When results of spikes indicate atypical taminants that are coextracted from the sample. The base-
method performance for samples, the samples are diluted to neutral extraction may cause significantly reduced recovery of
bring method performance within acceptable limits. phenols. The packed gas chromatographic columns recom-
For low solids (aqueous samples), extract, concentrate, and mended for the basic fraction may not exhibit sufficient reso-
analyze two sets of four 1-L aliquots (8 aliquots total) of the lution for some analytes.
precision and recovery standard. For high solids samples, two INSTRUMENTATION A GC/MS system with an injection
sets of four 30-g aliquots of the high solids reference matrix port designed for on-column injection when using packed col-
are used. umns and for splitless injection when using capillary columns.
Spike all samples with labeled compounds to assess method Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
performance. Compute percent recovery of the labeled com- packed with 3% SP-2550 on Supelcoport (100/120 mesh)
pounds using the internal standard method. Compare the or equivalent.
labeled compound recovery for each compound with the cor- Column for acids: 1.8 m long 2 mm I.D. glass, packed with 1%
responding labeled compound recovery. SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
Reagent water and high solids reference matrix blanks are ana- PRECISION & ACCURACY The MDL concentrations were
lyzed to demonstrate freedom from contamination. Extract obtained using reagent water. The MDL actually achieved in a
and concentrate a 1-L reagent water blank or a high solids given analysis will vary depending on instrument sensitivity
reference matrix blank with each sample’s lot (samples started and matrix effects. This method was tested by 15 laboratories
through the extraction process on the same 8-h shift, to a using reagent water, drinking water, surface water, and indus-
maximum of 20 samples).
trial wastewaters spiked at six concentrations over the range 5
Field replicates may be collected to determine the precision of to 100 g/L. Single operator precision, overall precision, and
the sampling technique, and spiked samples may be required method accuracy were found to be directly related to the con-
to determine the accuracy of the analysis when the internal centration of the parameter matrix.
standard method is used.
The MDL (in g/L) in reagent water was 1.5.
REFERENCE Semivolatile Organic Compounds by Isotope The standard deviation (in g/L based on 4 recovery measure-
Dilution GC/MS. Office of Water Regulation and Standards, ments) was 22.6.
U.S. EPA Industrial Technology Division, Washington, DC, The range (in g/L) for average recovery for 4 measurements
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, was 16.6–100.0.

©1996 CRC Press LLC


The range (in %) for percent recovery was 5–112. from all types of solid waste matrices, soils, and groundwater.
Accuracy (in g/L) as expected recovery for one or more mea- Although surface waters are not specifically mentioned, this
surements of a sample containing a true concentration of method should be applicable to water samples from rivers,
C was 0.43C + 1.26. lakes, etc.
Precision (in g/L) as expected single analyst standard devia-
METHOD SUMMARY This method covers 259 semivolatile
tion of measurements at an average concentration found at
organic compounds. In very limited applications direct injec-
X was 0.28X + 0.73.
tion of the sample into the GC/MS system may be appropriate,
Overall precision (in g/L) as expected interlaboratory stan-
but this results in very high detection limits (approximately
dard deviation of measurements in an average concentra-
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
tion found at X was 0.35X + 0.58.
gate, and matrix spiking standards, is extracted in a continuous
C = True value of the concentration in g/L. extractor first under acid conditions and then under basic con-
X = Average recovery found for measurements of samples con- ditions. Typically 30 g of a solid sample, containing surrogate,
taining a concentration at C in g/L. and matrix spiking standards, is extracted ultrasonically. After
concentrating the extract to 1 mL it is spiked with 10 L of an
SAMPLE PREPARATION Adjust the pH to >11 with sodium
internal standard solution just prior to analysis by GC/MS. The
hydroxide and serially extract in a separatory funnel with meth-
volume injected should contain about 100 ng of base/neutral
ylene chloride or else in a continuous extractor. Next, adjust
and 200 ng of acid surrogates (for a 1-L injection). Analysis
the pH to <2 with sulfuric acid and serially extract in a sepa-
is performed by GC/MS using a capillary GC column.
ratory funnel with methylene chloride or else in a continuous
extractor. Dry the extracts separately through a column of INTERFERENCES Raw GC/MS data from all blanks, sam-
anhydrous sodium sulfate and then concentrate each of the ples, and spikes must be evaluated for interferences. Contam-
extracts to 1.0 mL using a K-D apparatus. ination by carryover can occur whenever high-concentration
and low-concentration samples are sequentially analyzed. To
SAMPLE COLLECTION, PRESERVATION & HANDLING
reduce carryover, the sample syringe must be rinsed out
Grab samples must be collected in glass containers. All samples
between samples with solvent. Whenever an unusually concen-
must be refrigerated at 4C from the time of collection until
trated sample is encountered, it should be followed by the
extraction. If residual chlorine is present, add 80 mg of sodium
analysis of blank solvent to check for cross-contamination.
thiosulfate/L of sample and mix well. All samples must be
extracted within 7 days of collection and completely analyzed INSTRUMENTATION A GC/MS and a data system are
within 40 days of extraction. required. The GC column used is a 30 m 0.25 mm I.D. (or
0.32 mm I.D.) 1um film thickness silicone-coated fused silica
QUALITY CONTROL Make an initial, one-time, demonstra-
capillary column. A continuous liquid-liquid extractor
tion of the ability to generate acceptable accuracy and precision
equipped with Teflon® or glass connection joints and stopcocks
with this method. Before processing any samples, the analyst
requiring no lubrication, a K-D concentrating apparatus, water
must analyze a reagent water blank to demonstrate that inter-
bath, and an ultrasonic disrupter with a minimum power of
ferences from the analytical system and glassware are under
300 W and with pulsing capability are also required.
control. Each time a set of samples is extracted or reagents are
changed, a reagent water blank must be processed. Spike and PRECISION & ACCURACY The estimated quantitation
analyze a minimum of 5% of all samples to monitor and eval- limit (EQL) of Method 8270B for determining an individual
uate lab data quality. A QC check sample concentrate that compound is approximately 1 mg/kg (wet weight) for soil or
contains each parameter of interest at a concentration of sediment samples, 1–200 mg/kg for wastes (dependent on
100 g/mL in acetone is required. PCBs and multicomponent matrix and method of preparation), and 10 g/L for ground-
pesticides may be omitted from this test. water samples. EQLs will be proportionately higher for sample
extracts that require dilution to avoid saturation of the detector.
After analysis of five spiked wastewater samples, calculate the
average percent recovery and the standard deviation of the The EQL(b) for groundwater in g/L is 10.
percent recovery. Spike all samples with the surrogate standard The EQL (a, b) for low concentrations in soil and sediment
spiking solution and calculate the percent recovery of each in g/kg is 660.
surrogate compound. Accuracy as g/L is 0.43C + 1.26.
Overall precision in g/L is 0.35X + 0.58.
REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
26, 1984. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
This calculation is based on a 30 g sample and gel perme-
Phenol EPA Method 8270
ation chromatography cleanup.
CAS #108-95-2
(b) Sample EQLs are highly matrix-dependent. The EQLs are
provided for guidance and may not always be achievable.
TITLE Semivolatile Organic Compounds by GC/MS
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.

©1996 CRC Press LLC


ESTIMATED QUANTITATION LIMIT in the extract to be analyzed (assuming a 1- L injection).
Other Matrices Factor (a) Immediately add a 100-mL mixture of 1:1 methylene chlo-
ride:acetone and extract the sample ultrasonically for 3 min
High-concentration soil and sludges by sonicator 7.5 and then decant or filter the extracts. Repeat the extraction two
Non-water miscible waste 75 or more times. Dry the extract using a column with anhydrous
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
This estimated EQL is similar to an EPA “Practical Quantitation QUALITY CONTROL A methylene chloride solution con-
Limit.”
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD used for tuning the GC/MS system each 12-h shift. A system
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with performance check also must be made during every 12-h shift.
a screw-top Teflon®-lined cover that has been prewashed with A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
detergent and rinsed with distilled water and methanol (or rophenol, and benzidine is required to verify injection port
isopropanol). inertness and GC column performance. A calibration standard
at mid-concentration, containing each compound of interest,
Soils, sediments, or sludges — Use an 8-oz. widemouth glass
with a screw-top Teflon®-lined cover that has been prewashed including all required surrogates, must be performed every 12 h
with detergent and rinsed with distilled water and methanol during analysis. After the system performance check is met,
(or isopropanol). calibration check compounds (CCCs) are used to check the
validity of the initial calibration.
SAMPLE PRESERVATION
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check standard must be evaluated immediately after
solvent-free refrigerator until analysis; if chlorine is not present, or during data acquisition. If the retention time for any internal
then eliminate the sodium thiosulfate addition. standard changes by more than 30 seconds from the last check
calibration (12 h), the chromatographic system must be
Soils, sediments, or sludges — Cool samples to 4C and store inspected for malfunctions and corrections must be made, as
in a solvent-free refrigerator. required. If the electron ionization current plot (EICP) area for
MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.

SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,


Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust
the pH of the aqueous phase to pH >11 using 10 N sodium REFERENCE Test Methods for Evaluating Solid Waste (SW-
hydroxide and extract it with methylene chloride again for 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
18–24 h. Dry the extract through a column containing anhy- of Solid Waste, Washington, DC.
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous Phenol EPA Method 8040
or wet samples (gummy or clay type) that do not have a free- CAS #108-95-2
flowing sandy texture must be mixed with anhydrous sodium
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Phenols
standards to all samples, spikes, standards, and blanks. For the MATRIX Groundwater, soils, sludges, water miscible liquid
sample in each analytical batch selected for spiking, add 1.0 mL wastes, and non-water miscible wastes.
of a matrix spiking standard. For base/neutral acid analysis, the
amount added of the surrogates and matrix spiking com- APPLICATION This method is used for the analysis of 17
pounds should result in a final concentration of 100 ng/ L of phenols. Samples are extracted, concentrated, and analyzed
each base/neutral analyte and 200 ng/L of each acid analyte using direct injection of both neat and diluted organic liquids.

©1996 CRC Press LLC


Pentafluorobenzylbromide (PFB) derivatives also may be made MATRIX The compounds may be determined in waters,
to increase sensitivity of the method. soils, and municipal sludges by this method.
INTERFERENCES There can be carryover contamination METHOD SUMMARY This method is used to determine
with high- and low-level samples. Solvents, reagents, and glass- 176 semivolatile toxic organic pollutants associated with the
ware may introduce artifacts. Other interferences may come CWA (as amended 1987); the RCRA (as amended 1986); the
from coextracted compounds from samples. CERCLA (as amended 1986); and other compounds amenable
to extraction and analysis by capillary column gas chromatog-
INSTRUMENTATION GC capable of on-column injections raphy-mass spectrometry (GC/MS).
and a flame with detector (FID) or electron capture detector
(ECD). Column for underivatized phenol: 1.8 m by 2.0 mm Stable isotopically-labeled analogs of the compounds of interest
with 1% SP-1240DA on Supelcoport. Column for derivatized are added to the sample. If the solids content is less than 1%,
phenols: 1.8 m by 2.0 mm with 5% OV-17 on Chromosorb W- a 1-L sample is extracted at pH 12–13, then at pH <2 with
AW-DMCS. methylene chloride using continuous extraction techniques.

RANGE 12–450 g/L If the solids content is 30% or less, the sample is diluted to 1%
solids with reagent water, homogenized ultrasonically, and
MDL 0.14 g/L (FID) and 2.2 g/L (ECD) extracted at pH 12–13, then at pH <2 with methylene chloride
PQL FACTORS FOR MULTIPLYING  FID MDL VALUE using continuous extraction techniques. If the solids content is
Matrix Multiplication Factor greater than 30%, the sample is extracted using ultrasonic
techniques.
Groundwater 10
Each extract is dried over sodium sulfate, concentrated to a
Low-level soil by sonication with GPC cleanup 670
volume of 5 mL, cleaned up using GPC, if necessary, and con-
High-level soil and sludge by sonication 10,000
centrated. Extracts are concentrated to 1 mL if GPC is not
Non-water miscible waste 100,000
performed, and to 0.5 mL if GPC is performed.
PRECISION 0.17X + 0.77 g/L (overall precision using FID)
An internal standard is added to the extract, and a 1-mL aliquot
ACCURACY 0.43C + 0.11 g/L (as recovery using FID) of the extract is injected into the GC. The compounds are
separated by GC and detected by a MS. The labeled compounds
SAMPLING METHOD Use 8-oz. widemouth glass bottles
serve to correct the variability of the analytical technique.
with Teflon®-lined caps for concentrated waste samples, soils,
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles INTERFERENCES Solvents, reagents, glassware, and other
with Teflon®-lined caps for liquid (water) samples. sample processing hardware may yield artifacts and/or elevated
baselines causing misinterpretation of chromatograms and
STABILITY Cool soil, sediment, sludge, and liquid samples
spectra. Materials used in the analysis must be demonstrated
to 4C. If residual chlorine is present in liquid samples add to be free from interferences under the conditions of analysis
3 mL of 10% sodium thiosulfate per gallon of sample and cool by running method blanks initially and with each sample lot
to 4C. (sample started through the extraction process on a given 8-h
MHT 14 days for concentrated waste, soil, sediment, or shift, to a maximum of 20). Specific selection of reagents and
sludge; 7 days for liquid samples; all extracts must be analyzed purification of solvents by distillation in all glass systems may
within 40 days. be required. Glassware and, where possible, reagents are
cleaned by solvent rinse and baking at 450C for 1-h minimum.
QUALITY CONTROL A quality control check sample con- Interferences coextracted from samples will vary considerably
centrate containing each analyte of interest is required. The QC from source to source, depending on the diversity of the site
check sample concentrate may be prepared from pure standard being sampled.
materials or purchased as certified solutions Use appropriate
trip, matrix, control site, method, reagent, and solvent blanks. INSTRUMENTATION Major instrumentation includes a GC
Internal, surrogate, and five concentration level calibration with a splitless or on-column injection port for capillary col-
standards are used. The QC check sample concentrate should umn, a MS with 70 eV electron impact ionization, and a data
system to collect and record MS data, and process it. A K-D
contain this compound at 100 g/mL in 2-propanol.
apparatus is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
vinyl silicone bonded phased fused silica capillary column.
Method 8040A, Rev. 1, Nov. 1990.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
rather than instrumental limitations. The limits typify the min-
Phenothiazine EPA Method 1625
imum quantities that can be detected with no interferences
CAS #92-84-2
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was not listed. This is defined
tion GC/MS as a minimum level at which the analytical system shall give

©1996 CRC Press LLC


recognizable mass spectra (background corrected) and accept- Reagent water and high solids reference matrix blanks are ana-
able calibration points. lyzed to demonstrate freedom from contamination. Extract
and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was not listed and in high reference matrix blank with each sample’s lot (samples started
solids was not listed; these were determined in digested sludge through the extraction process on the same 8-h shift, to a
(low solids) and in filter cake or compost (high solids). maximum of 20 samples).
The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was not listed. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was not listed. standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from U.S. EPA, Office of Water Regulations and Standards, 401 M
the time of collection until extraction. If residual chlorine is St., SW, Washington, DC, 20460. Phone: 202-382-7131).
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction.
1,4-Phenylenediamine EPA Method 8270
SAMPLE PREPARATION Samples containing 1% solids or CAS #106-50-3
less are extracted directly using continuous liquid-liquid
extraction techniques. Samples containing 1 to 30% solids are TITLE Semivolatile Organic Compounds by GC/MS
diluted to the 1% level with reagent water and extracted using MATRIX This method is used to determine the concentra-
continuous liquid-liquid extraction techniques. Samples con- tion of semivolatile organic compounds in extracts prepared
taining greater than 30% solids are extracted using ultrasonic from all types of solid waste matrices, soils, and groundwater.
techniques. Although surface waters are not specifically mentioned, this
Base/neutral extraction — Adjust the pH of the waters in the method should be applicable to water samples from rivers,
lakes, etc.
extractors to 12–13 with 6 N NaOH. Extract with methylene
chloride for 24–48 h. METHOD SUMMARY This method covers 259 semivolatile
Acid extraction — Adjust the pH of the waters in the extractors organic compounds. In very limited applications direct injec-
to 2 or less using 6 N sulfuric acid. Extract with methylene tion of the sample into the GC/MS system may be appropriate,
chloride for 24–48 h. but this results in very high detection limits (approximately
Ultrasonic extraction of high solids samples — Add anhy- 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
drous sodium sulfate to the sample and QC aliquot(s). gate, and matrix spiking standards, is extracted in a continuous
Add acetone:methylene chloride (1:1) to the sample and extractor first under acid conditions and then under basic con-
mix thoroughly ditions. Typically 30 g of a solid sample, containing surrogate,
and matrix spiking standards, is extracted ultrasonically. After
Concentrate extracts using a K-D apparatus. concentrating the extract to 1 mL it is spiked with 10 L of an
QUALITY CONTROL The analyst is permitted to modify internal standard solution just prior to analysis by GC/MS. The
this method to improve separations or lower the costs of mea- volume injected should contain about 100 ng of base/neutral
surements, provided all performance specifications are met. and 200 ng of acid surrogates (for a 1-L injection). Analysis
is performed by GC/MS using a capillary GC column.
Analyses of blanks are required to demonstrate freedom from
contamination. When results of spikes indicate atypical INTERFERENCES Raw GC/MS data from all blanks, sam-
method performance for samples, the samples are diluted to ples, and spikes must be evaluated for interferences. Contam-
bring method performance within acceptable limits. ination by carryover can occur whenever high-concentration
and low-concentration samples are sequentially analyzed. To
For low solids (aqueous samples), extract, concentrate, and reduce carryover, the sample syringe must be rinsed out
analyze two sets of four 1-L aliquots (8 aliquots total) of the between samples with solvent. Whenever an unusually concen-
precision and recovery standard. For high solids samples, two trated sample is encountered, it should be followed by the
sets of four 30-g aliquots of the high solids reference matrix analysis of blank solvent to check for cross-contamination.
are used.
INSTRUMENTATION A GC/MS and a data system are
Spike all samples with labeled compounds to assess method required. The GC column used is a 30 m 0.25 mm I.D. (or
performance. Compute percent recovery of the labeled com- 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
pounds using the internal standard method. Compare the capillary column. A continuous liquid-liquid extractor
labeled compound recovery for each compound with the cor- equipped with Teflon® or glass connection joints and stopcocks
responding labeled compound recovery. requiring no lubrication, a K-D concentrating apparatus, water

©1996 CRC Press LLC


bath, and an ultrasonic disrupter with a minimum power of SAMPLE PREPARATION
300 W and with pulsing capability are also required. Liquid samples — Transfer 1 L quantitatively to a continuous
extractor. If high concentrations are anticipated, a smaller vol-
PRECISION & ACCURACY The estimated quantitation ume may be used and then diluted with organic-free reagent
limit (EQL) of Method 8270B for determining an individual water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
compound is approximately 1 mg/kg (wet weight) for soil or sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
sediment samples, 1–200 mg/kg for wastes (dependent on solution into each sample. For the sample in each analytical
matrix and method of preparation), and 10 g/L for ground- batch selected for spiking, add 1.0 mL of a matrix spiking stan-
water samples. EQLs will be proportionately higher for sample dard. For base/neutral acid analysis, the amount of the surro-
extracts that require dilution to avoid saturation of the detector. gates and matrix spiking compounds added to the sample
should result in a final concentration of 100 ng/L of each
The EQL(b) for groundwater in g/L is 10.
The EQL (a, b) for low concentrations in soil and sediment analyte in the extract to be analyzed (assuming a 1- L injec-
tion). Extract with methylene chloride for 18–24 h. Next, adjust
in g/kg is not determined.
the pH of the aqueous phase to pH >11 using 10 N sodium
Accuracy as g/L is not listed.
hydroxide and extract it with methylene chloride again for
Overall precision in g/L is not listed.
18–24 h. Dry the extract through a column containing anhy-
(a) EQLs listed for soil/sediment are based on wet weight. Nor- drous sodium sulfate and concentrate it to 1 mL using a K-D
mally data is reported in a dry-weight basis; therefore, EQLs concentrator.
will be higher based on the % dry weight of each sample. Soils, sediments, or sludges — Use 30 g of sample. Nonporous
This calculation is based on a 30 g sample and gel perme- or wet samples (gummy or clay type) that do not have a free-
ation chromatography cleanup. flowing sandy texture must be mixed with anhydrous sodium
(b) Sample EQLs are highly matrix-dependent. The EQLs are sulfate until the sample is free flowing. Add 1 mL of surrogate
provided for guidance and may not always be achievable. standards to all samples, spikes, standards, and blanks. For the
C = True value for concentration, in g/L. sample in each analytical batch selected for spiking, add 1.0 mL
X = Average recovery found for measurements of samples con- of a matrix spiking standard. For base/neutral acid analysis, the
taining a concentration of C, in g/L. amount added of the surrogates and matrix spiking com-
pounds should result in a final concentration of 100 ng/ L of
ESTIMATED QUANTITATION LIMIT
each base/neutral analyte and 200 ng/L of each acid analyte
Other Matrices Factor (a) in the extract to be analyzed (assuming a 1- L injection).
High-concentration soil and sludges by sonicator 7.5 Immediately add a 100-mL mixture of 1:1 methylene chlo-
Non-water miscible waste 75 ride:acetone and extract the sample ultrasonically for 3 min
and then decant or filter the extracts. Repeat the extraction two
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor]. or more times. Dry the extract using a column with anhydrous
This estimated EQL is similar to an EPA “Practical Quantitation sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
Limit.”
QUALITY CONTROL A methylene chloride solution con-
SAMPLING METHOD taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with used for tuning the GC/MS system each 12-h shift. A system
a screw-top Teflon®-lined cover that has been prewashed with performance check also must be made during every 12-h shift.
detergent and rinsed with distilled water and methanol (or A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
isopropanol). rophenol, and benzidine is required to verify injection port
inertness and GC column performance. A calibration standard
Soils, sediments, or sludges — Use an 8-oz. widemouth glass
at mid-concentration, containing each compound of interest,
with a screw-top Teflon®-lined cover that has been prewashed
including all required surrogates, must be performed every 12 h
with detergent and rinsed with distilled water and methanol during analysis. After the system performance check is met,
(or isopropanol). calibration check compounds (CCCs) are used to check the
SAMPLE PRESERVATION validity of the initial calibration.
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check standard must be evaluated immediately after
solvent-free refrigerator until analysis; if chlorine is not present, or during data acquisition. If the retention time for any internal
then eliminate the sodium thiosulfate addition. standard changes by more than 30 seconds from the last check
Soils, sediments, or sludges — Cool samples to 4C and store calibration (12 h), the chromatographic system must be
inspected for malfunctions and corrections must be made, as
in a solvent-free refrigerator.
required. If the electron ionization current plot (EICP) area for
MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.

©1996 CRC Press LLC


Demonstrate, through the analysis of a reagent water blank, shift, to a maximum of 20). Specific selection of reagents and
that interferences from the analytical system, glassware, and purification of solvents by distillation in all glass systems may
reagents are under control. The blank samples should be car- be required. Glassware and, where possible, reagents are
ried through all stages of the sample preparation and measure- cleaned by solvent rinse and baking at 450C for 1-h minimum.
ment steps. For each analytical batch (up to 20 samples), a Interferences coextracted from samples will vary considerably
reagent blank, matrix spike, and matrix spike duplicate/dupli- from source to source, depending on the diversity of the site
cate must be analyzed (the frequency of the spikes may be being sampled.
different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample INSTRUMENTATION Major instrumentation includes a GC
preparation and measurement steps. A QC reference sample with a splitless or on-column injection port for capillary col-
concentrate containing each analyte at a concentration of umn, a MS with 70 eV electron impact ionization, and a data
100 mg/L in methanol is required. system to collect and record MS data, and process it. A K-D
apparatus is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
of Solid Waste, Washington, DC. vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
1-Phenylnaphthalene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #605-02-7 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was not listed. This is defined
tion GC/MS
as a minimum level at which the analytical system shall give
MATRIX The compounds may be determined in waters, recognizable mass spectra (background corrected) and accept-
soils, and municipal sludges by this method. able calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was not listed and in high
176 semivolatile toxic organic pollutants associated with the solids was not listed; these were determined in digested sludge
CWA (as amended 1987); the RCRA (as amended 1986); the (low solids) and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
to extraction and analysis by capillary column gas chromatog- The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS). deviation (in g/L) was not listed.
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%,
a 1-L sample is extracted at pH 12–13, then at pH <2 with SAMPLE COLLECTION, PRESERVATION & HANDLING
methylene chloride using continuous extraction techniques. Collect samples in glass containers. Aqueous samples which
flow freely are collected in refrigerated bottles using automatic
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from
extracted at pH 12–13, then at pH <2 with methylene chloride the time of collection until extraction. If residual chlorine is
using continuous extraction techniques. If the solids content is present in aqueous samples, add 80 mg sodium thiosulfate/L
greater than 30%, the sample is extracted using ultrasonic of water. Begin sample extraction within 7 days of collection,
techniques. and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a SAMPLE PREPARATION Samples containing 1% solids or
volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid
centrated. Extracts are concentrated to 1 mL if GPC is not extraction techniques. Samples containing 1 to 30% solids are
performed, and to 0.5 mL if GPC is performed. diluted to the 1% level with reagent water and extracted using
An internal standard is added to the extract, and a 1-mL aliquot continuous liquid-liquid extraction techniques. Samples con-
of the extract is injected into the GC. The compounds are taining greater than 30% solids are extracted using ultrasonic
separated by GC and detected by a MS. The labeled compounds techniques.
serve to correct the variability of the analytical technique.
Base/neutral extraction — Adjust the pH of the waters in the
INTERFERENCES Solvents, reagents, glassware, and other extractors to 12–13 with 6 N NaOH. Extract with methylene
sample processing hardware may yield artifacts and/or elevated chloride for 24–48 h.
baselines causing misinterpretation of chromatograms and Acid extraction — Adjust the pH of the waters in the extractors
spectra. Materials used in the analysis must be demonstrated to 2 or less using 6 N sulfuric acid. Extract with methylene
to be free from interferences under the conditions of analysis chloride for 24–48 h.
by running method blanks initially and with each sample lot Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h drous sodium sulfate to the sample and QC aliquot(s).

©1996 CRC Press LLC


Add acetone:methylene chloride (1:1) to the sample and a 1-L sample is extracted at pH 12–13, then at pH <2 with
mix thoroughly methylene chloride using continuous extraction techniques.
Concentrate extracts using a K-D apparatus. If the solids content is 30% or less, the sample is diluted to 1%
solids with reagent water, homogenized ultrasonically, and
QUALITY CONTROL The analyst is permitted to modify
extracted at pH 12–13, then at pH <2 with methylene chloride
this method to improve separations or lower the costs of mea-
using continuous extraction techniques. If the solids content is
surements, provided all performance specifications are met.
greater than 30%, the sample is extracted using ultrasonic
Analyses of blanks are required to demonstrate freedom from
techniques.
contamination. When results of spikes indicate atypical
method performance for samples, the samples are diluted to Each extract is dried over sodium sulfate, concentrated to a
bring method performance within acceptable limits. volume of 5 mL, cleaned up using GPC, if necessary, and con-
For low solids (aqueous samples), extract, concentrate, and centrated. Extracts are concentrated to 1 mL if GPC is not
analyze two sets of four 1-L aliquots (8 aliquots total) of the performed, and to 0.5 mL if GPC is performed.
precision and recovery standard. For high solids samples, two An internal standard is added to the extract, and a 1-mL aliquot
sets of four 30-g aliquots of the high solids reference matrix of the extract is injected into the GC. The compounds are
are used. separated by GC and detected by a MS. The labeled compounds
Spike all samples with labeled compounds to assess method serve to correct the variability of the analytical technique.
performance. Compute percent recovery of the labeled com- INTERFERENCES Solvents, reagents, glassware, and other
pounds using the internal standard method. Compare the sample processing hardware may yield artifacts and/or elevated
labeled compound recovery for each compound with the cor- baselines causing misinterpretation of chromatograms and
responding labeled compound recovery. spectra. Materials used in the analysis must be demonstrated
Reagent water and high solids reference matrix blanks are ana- to be free from interferences under the conditions of analysis
lyzed to demonstrate freedom from contamination. Extract by running method blanks initially and with each sample lot
and concentrate a 1-L reagent water blank or a high solids (sample started through the extraction process on a given 8-h
reference matrix blank with each sample’s lot (samples started shift, to a maximum of 20). Specific selection of reagents and
through the extraction process on the same 8-h shift, to a purification of solvents by distillation in all glass systems may
maximum of 20 samples). be required. Glassware and, where possible, reagents are
cleaned by solvent rinse and baking at 450C for 1-h minimum.
Field replicates may be collected to determine the precision of Interferences coextracted from samples will vary considerably
the sampling technique, and spiked samples may be required from source to source, depending on the diversity of the site
to determine the accuracy of the analysis when the internal being sampled.
standard method is used.
INSTRUMENTATION Major instrumentation includes a GC
REFERENCE Semivolatile Organic Compounds by Isotope with a splitless or on-column injection port for capillary col-
Dilution GC/MS. Office of Water Regulation and Standards, umn, a MS with 70 eV electron impact ionization, and a data
U.S. EPA Industrial Technology Division, Washington, DC, system to collect and record MS data, and process it. A K-D
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, apparatus is used to concentrate extracts.
U.S. EPA, Office of Water Regulations and Standards, 401 M
St., SW, Washington, DC, 20460. Phone: 202-382-7131). GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
2-Phenylnaphthalene EPA Method 1625 method are usually dependent on the level of interferences
CAS #612-94-2 rather than instrumental limitations. The limits typify the min-
imum quantities that can be detected with no interferences
TITLE Semivolatile Organic Compounds by Isotope Dilu- present.
tion GC/MS
The minimum level (in g/mL) was not listed. This is defined
MATRIX The compounds may be determined in waters, as a minimum level at which the analytical system shall give
soils, and municipal sludges by this method. recognizable mass spectra (background corrected) and accept-
able calibration points.
METHOD SUMMARY This method is used to determine
176 semivolatile toxic organic pollutants associated with the The MDL (in g/kg) in low solids was not listed and in high
CWA (as amended 1987); the RCRA (as amended 1986); the solids was not listed; these were determined in digested sludge
CERCLA (as amended 1986); and other compounds amenable (low solids) and in filter cake or compost (high solids).
to extraction and analysis by capillary column gas chromatog-
The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS).
deviation (in g/L) was not listed.
Stable isotopically-labeled analogs of the compounds of interest The labeled and native compound initial accuracy as average
are added to the sample. If the solids content is less than 1%, recovery (in g/L) was not listed.

©1996 CRC Press LLC


SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from U.S. EPA, Office of Water Regulations and Standards, 401 M
the time of collection until extraction. If residual chlorine is St., SW, Washington, DC, 20460. Phone: 202-382-7131).
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction. Phorate EPA Method 8141
SAMPLE PREPARATION Samples containing 1% solids or CAS #298-02-2
less are extracted directly using continuous liquid-liquid
extraction techniques. Samples containing 1 to 30% solids are TITLE Organophosphorus Compounds by Gas Chromatog-
diluted to the 1% level with reagent water and extracted using raphy: Capillary Column Technique
continuous liquid-liquid extraction techniques. Samples con- MATRIX This method covers aqueous and solid matrices.
taining greater than 30% solids are extracted using ultrasonic This includes a wide variety such as drinking water, ground-
techniques. water, industrial wastewaters, surface waters, soils, solids, and
Base/neutral extraction — Adjust the pH of the waters in the sediments.
extractors to 12–13 with 6 N NaOH. Extract with methylene METHOD SUMMARY This is a GC method used to deter-
chloride for 24–48 h. mine the concentration of 28 organophosphorus pesticides.
Acid extraction — Adjust the pH of the waters in the extractors
to 2 or less using 6 N sulfuric acid. Extract with methylene The use of Gel Permeation Cleanup (EPA Method 3640) for
chloride for 24–48 h. sample cleanup has been demonstrated to yield recoveries of
Ultrasonic extraction of high solids samples — Add anhy- less than 85% for many method analytes and is therefore not
drous sodium sulfate to the sample and QC aliquot(s). recommended for use with this method.
Add acetone:methylene chloride (1:1) to the sample and This method provides GC conditions for the detection of ppb
mix thoroughly concentrations of organophosphorus compounds. Prior to the
Concentrate extracts using a K-D apparatus. use of this method, appropriate sample preparation techniques
must be used. Water samples are extracted at a neutral pH with
QUALITY CONTROL The analyst is permitted to modify methylene chloride as a solvent by using a separatory funnel
this method to improve separations or lower the costs of mea- (EPA Method 3510) or a continuous liquid-liquid extractor
surements, provided all performance specifications are met. (EPA Method 3520). Soxhlet extraction (EPA Method 3540) or
Analyses of blanks are required to demonstrate freedom from ultrasonic extraction (EPA Method 3550) using methylene
contamination. When results of spikes indicate atypical chloride/acetone (1:1) are used for solid samples. Both neat
method performance for samples, the samples are diluted to and diluted organic liquids (EPA Method 3580) may be ana-
bring method performance within acceptable limits. lyzed by direct injection. Spiked samples are used to verify the
For low solids (aqueous samples), extract, concentrate, and applicability of the chosen extraction technique to each new
analyze two sets of four 1-L aliquots (8 aliquots total) of the sample type. A GC with a flame photometric (FPD) or nitro-
gen-phosphorus detector (NPD) is used for this multiresidue
precision and recovery standard. For high solids samples, two
procedure.
sets of four 30-g aliquots of the high solids reference matrix
are used. INTERFERENCES The use of Florisil cleanup materials (EPA
Method 3620) for some of the compounds in this method has
Spike all samples with labeled compounds to assess method
been demonstrated to yield recoveries less than 85% and is
performance. Compute percent recovery of the labeled com-
therefore not recommended for all compounds. Use of phos-
pounds using the internal standard method. Compare the
phorus or halogen specific detectors, however, often obviates
labeled compound recovery for each compound with the cor-
the necessity for cleanup for relatively clean sample matrices.
responding labeled compound recovery.
If particular circumstances demand the use of an alternative
Reagent water and high solids reference matrix blanks are ana- cleanup procedure, the analyst must determine the elution pro-
lyzed to demonstrate freedom from contamination. Extract file and demonstrate that the recovery of each analyte is no less
and concentrate a 1-L reagent water blank or a high solids than 85%.
reference matrix blank with each sample’s lot (samples started
Use of a flame photometric detector (FPD) in the phosphorus
through the extraction process on the same 8-h shift, to a
mode will minimize interferences from materials that do not
maximum of 20 samples).
contain phosphorus. Elemental sulfur, however, may interfere
Field replicates may be collected to determine the precision of with the determination of certain organophosphorus com-
the sampling technique, and spiked samples may be required pounds by flame photometric gas chromatography. Sulfur
to determine the accuracy of the analysis when the internal cleanup using EPA Method 3660 may alleviate this interference.
standard method is used. A nitrogen phosphorus detector (NPD) is also recommended.

©1996 CRC Press LLC


A few analytes coelute on certain columns. Therefore, select a Accuracy (as % recovery) with continuous liquid-liquid extrac-
second column for confirmation where coelution of the ana- tion ranged from 84 (with low spikes) to 74 (with high
lytes of interest does not occur. spikes).
Accuracy (as % recovery) with Soxhlet extraction of soils
Method interferences may be caused by contaminants in sol- ranged from 75 (with low spikes to 78 (with high spikes).
vents, reagents, glassware, and other sample processing hard- Accuracy (as % recovery) with ultrasonic extraction of soils
ware that lead to discrete artifacts or elevated baselines in gas ranged from not recovered (with low spikes) to 64 (with
chromatograms. All these materials must be routinely demon- high spikes).
strated to be free from interferences under the conditions of
the analysis by analyzing reagent blanks. SAMPLE COLLECTION, PRESERVATION & HANDLING
Containers used to collect samples for the determination of
INSTRUMENTATION A GC with a NPD or a FPD will be semivolatile organic compounds should be soap and water
needed. A data system or integrator is recommended for mea- washed followed by methanol (or isopropanol) rinsing. The
suring peak areas and/or peak heights. A Kuderna-Danish sample containers should be of glass or Teflon® and have screw-
(K-D) apparatus will be needed for extract concentration. top covers with Teflon® liners.

Column 1: 15 m  0.53 mm megabore capillary column, No preservation is used with concentrated waste samples. With
1.0 m film thickness, DB-210. liquid samples containing no residual chlorine and with soil,
Column 2: 15 m  0.53 mm megabore capillary column, sediment, and sludge samples, immediately cooling to 4C is
1.5 m film thickness, SPB-608. the only preservation used. When residual chlorine is present
Column 3: 15 m  0.53 mm megabore capillary column, then 3 mL of 10% aqueous sodium sulfate is added for each
1.0 m film thickness, DB-5. gallon of sample collected, followed by cooling to 4C.

Three megabore capillary columns are included for analysis of Liquid samples must be extracted within 7 days and their
organophosphates by this method. Column 1 (DB-210 or extracts analyzed within 40 days. Concentrated waste, soil, sed-
equivalent) and Column 2 (SPB-608 or equivalent) are recom- iment, and sludge samples must be extracted within 14 days
and their extracts analyzed within 40 days.
mended if a large number of organophosphorus analytes are
to be determined. If the superior resolution offered by Column SAMPLE PREPARATION In general, water samples are
1 and Column 2 is not required, Column 3 (DB-5 or equiva- extracted at a neutral pH with methylene chloride, using either
lent) may be used. For megabore capillary columns, automatic EPA Method 3510 or EPA Method 3520. Solid samples are
injections of 1 L are recommended. extracted using either EPA Method 3540 or EPA Method 3550
with methylene chloride/acetone (1:1) as the extraction solvent.
PRECISION & ACCURACY The MDL actually achieved in
a given analysis will vary, as it is dependent on instrument Prior to GC analysis, the extraction solvent may be exchanged
sensitivity and matrix effects. Single operator accuracy and to hexane. Single lab data indicates that samples should not be
precision studies have been conducted with spiked water and transferred with 100% hexane during sample workup as the
more water soluble organophosphorus compounds may be lost.
soil samples.
If cleanup is performed on the samples, the analyst should
MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
analyze the samples by GC. This will confirm elution patterns
Matrix Factor (b) and the absence of interferences from the reagents. If peak
Groundwater 10 detection and identification is prevented by the presence of
(EPA Method 3510 or EPA Method 3520) interferences, further cleanup is required.
Low-concentration soil by Soxhlet and no cleanup 10 (c) QUALITY CONTROL The analyst should monitor the per-
Low-concentration soil by ultrasonic extraction 6.7 (c) formance of the extraction, cleanup (when used), and analyt-
with GPC cleanup ical system and the effectiveness of the method in dealing with
High-concentration soil and sludges 500 (c) each sample matrix by spiking each sample, standard, and
by ultrasonic extraction blank with one or two surrogates (e.g., organophosphorus
Non-water miscible waste (EPA Method 3580) 1000 (c) compounds not expected to be present in the sample). Deu-
(a) SampleEQLs are highly matrix-dependent. TheEQLslisted here terated analogs of analytes should not be used as surrogates for
are provided for guidance and may not always be achievable. gas chromatographic analysis due to coelution problems.
(b) EQL = [Method detection limit] [Factor]. For non-aqueous A minimum of five concentrations for each analyte of interest
samples the factor is on a wet-weight basis. should be prepared through dilution of the stock standards
(c) Multiply this factory times the soil MDL. with isooctane. One of the concentrations should be at a con-
centration near, but above, the MDL.
The MDL (in g/L) when reagent water was extracted using a
separatory funnel was 0.04. Include a mid-level check standard after each group of 10 sam-
The MDL (in g/kg) when soil was extracted using Soxhlet ples in the analysis sequence. GC/MS techniques should be
extraction (EPA Method 3540) was 2.0. judiciously employed to support qualitative identifications
Accuracy (as % recovery) with separatory funnel extraction made with this method. Follow the GC/MS operating require-
ranged from 94 (with low spikes) to 73 (with high spikes). ments specified in EPA Method 8270.

©1996 CRC Press LLC


When available, chemical ionization mass spectra may be capillary column. A continuous liquid-liquid extractor
employed to aid in the qualitative identification process. To equipped with Teflon® or glass connection joints and stopcocks
confirm an identification of a compound, the background- requiring no lubrication, a K-D concentrating apparatus, water
corrected mass spectrum of the compound must be obtained bath, and an ultrasonic disrupter with a minimum power of
from the sample extract and must be compared with a mass 300 W and with pulsing capability are also required.
spectrum from a stock or calibration standard analyzed under
the same chromatographic conditions. The molecular ion and PRECISION & ACCURACY The estimated quantitation
all other ions present above 20% relative abundance in the mass limit (EQL) of Method 8270B for determining an individual
spectrum of the standard must be present in the mass spectrum compound is approximately 1 mg/kg (wet weight) for soil or
of the sample with agreement to 20%. The retention time of sediment samples, 1–200 mg/kg for wastes (dependent on
the compound in the sample must be within six seconds of the matrix and method of preparation), and 10 g/L for ground-
retention time for the same compound in the standard solution. water samples. EQLs will be proportionately higher for sample
Should the MS procedure fail to provide satisfactory results, extracts that require dilution to avoid saturation of the detector.
additional steps may be taken before reanalysis. These steps The EQL(b) for groundwater in g/L is 10.
may include the use of alternate packed or capillary GC col- The EQL (a, b) for low concentrations in soil and sediment
umns or additional sample cleanup. in g/kg is not determined.
REFERENCE Test Methods for Evaluating Solid Waste, Phys- Accuracy as g/L is not listed.
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office Overall precision in g/L is not listed.
of Solid Waste, Washington, DC, EPA Method 8141 July 1992. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
Phorate EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #298-02-2 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
but this results in very high detection limits (approximately This estimated EQL is similar to an EPA “Practical Quantitation
10,000 g/L). Typically, a 1-L liquid sample, containing surro- Limit.”
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral Soils, sediments, or sludges — Use an 8-oz. widemouth glass
and 200 ng of acid surrogates (for a 1-L injection). Analysis with a screw-top Teflon®-lined cover that has been prewashed
is performed by GC/MS using a capillary GC column. with detergent and rinsed with distilled water and methanol
INTERFERENCES Raw GC/MS data from all blanks, sam- (or isopropanol).
ples, and spikes must be evaluated for interferences. Contam- SAMPLE PRESERVATION
ination by carryover can occur whenever high-concentration Liquid samples — If residual chlorine is present, add 3 mL of
and low-concentration samples are sequentially analyzed. To 10% sodium thiosulfate per gallon, cool to 4C and store in a
reduce carryover, the sample syringe must be rinsed out solvent-free refrigerator until analysis; if chlorine is not present,
between samples with solvent. Whenever an unusually concen- then eliminate the sodium thiosulfate addition.
trated sample is encountered, it should be followed by the
analysis of blank solvent to check for cross-contamination. Soils, sediments, or sludges — Cool samples to 4C and store
in a solvent-free refrigerator.
INSTRUMENTATION A GC/MS and a data system are
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and the
0.32 mm I.D.) 1um film thickness silicone-coated fused silica extracts analyzed within 40 days. Soils, sediments, or sludges may

©1996 CRC Press LLC


be stored for a maximum of 14 days and the extracts analyzed must be inspected for malfunctions and corrections must be
within 40 days. made, as appropriate.
SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,
Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust
REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium
hydroxide and extract it with methylene chloride again for 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
18–24 h. Dry the extract through a column containing anhy- of Solid Waste, Washington, DC.
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous Phorate EPA Method 8140
or wet samples (gummy or clay type) that do not have a free- CAS #298-02-2
flowing sandy texture must be mixed with anhydrous sodium
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Organophosphorus Pesticides
standards to all samples, spikes, standards, and blanks. For the MATRIX Groundwater, soils, sludges, water miscible liquid
sample in each analytical batch selected for spiking, add 1.0 mL wastes, and non-water miscible wastes.
of a matrix spiking standard. For base/neutral acid analysis, the
amount added of the surrogates and matrix spiking com- APPLICATION This method is used for the analysis of 21
pounds should result in a final concentration of 100 ng/ L of organophosphorus pesticides. Samples are extracted, concen-
each base/neutral analyte and 200 ng/L of each acid analyte trated, and analyzed using direct injection of both neat and
in the extract to be analyzed (assuming a 1- L injection). diluted organic liquid into a gas chromatograph (GC).
Immediately add a 100-mL mixture of 1:1 methylene chlo- INTERFERENCES Solvents, reagents, and glassware may
ride:acetone and extract the sample ultrasonically for 3 min introduce artifacts. Other interferences may come from coex-
and then decant or filter the extracts. Repeat the extraction two tracted compounds from samples. The use of Florisil cleanup
or more times. Dry the extract using a column with anhydrous materials may produce low recoveries. Elemental sulfur may
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. interfere with some compounds when using a flame photomet-
QUALITY CONTROL A methylene chloride solution con- ric detector. Sulfur cleanup (Method 3660) may alleviate sulfur
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is interference.
used for tuning the GC/MS system each 12-h shift. A system INSTRUMENTATION GC capable of on-column injections
performance check also must be made during every 12-h shift. and a flame photometric detector (FPD) or a thermionic detec-
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- tor. Column 1: 1.8 m by 2 mm with 5% SP-2401 on Supelco-
rophenol, and benzidine is required to verify injection port port. Column 2: 1.8 m by 2 mm with 3% SP-2401 on
inertness and GC column performance. A calibration standard Supelcoport. Column 3: 50 cm by in Teflon® with 15% SE-
at mid-concentration, containing each compound of interest, 54 on Gas Chrom Q. The preferred column is Column Number 1.
including all required surrogates, must be performed every 12 h
during analysis. After the system performance check is met, RANGE 4.9–47 g/L
calibration check compounds (CCCs) are used to check the MDL 0.15 g/L (in reagent water).
validity of the initial calibration.
PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after Matrix Multiplication Factor
or during data acquisition. If the retention time for any internal Groundwater 10
standard changes by more than 30 seconds from the last check Low-level soil by sonication with GPC cleanup 670
calibration (12 h), the chromatographic system must be High-level soil and sludge by sonication 10,000
inspected for malfunctions and corrections must be made, as Non-water miscible waste 100,000
required. If the electron ionization current plot (EICP) area for
PRECISION 8.9% (single operator standard deviation)
any of the internal standards changes by a factor of two from
the last daily calibration standard check, the mass spectrometer ACCURACY 62.7% (single operator average recovery)

©1996 CRC Press LLC


SAMPLING METHOD Use 8-oz. widemouth glass bottles INSTRUMENTATION A GC/MS and a data system are
with Teflon®-lined caps for concentrated waste samples, soils, required. The GC column used is a 30 m 0.25 mm I.D. (or
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
with Teflon®-lined caps for liquid (water) samples. capillary column. A continuous liquid-liquid extractor
equipped with Teflon® or glass connection joints and stopcocks
STABILITY Cool soil, sediment, sludge, and liquid samples
requiring no lubrication, a K-D concentrating apparatus, water
to 4C. If residual chlorine is present in liquid samples add
bath, and an ultrasonic disrupter with a minimum power of
3 mL of 10% sodium thiosulfate per gallon of sample and cool
300 W and with pulsing capability are also required.
to 4C.
PRECISION & ACCURACY The estimated quantitation
MHT 14 days for concentrated waste, soil, sediment, or
limit (EQL) of Method 8270B for determining an individual
sludge; 7 days for liquid samples; all extracts must be analyzed
compound is approximately 1 mg/kg (wet weight) for soil or
within 40 days.
sediment samples, 1–200 mg/kg for wastes (dependent on
QUALITY CONTROL A quality control check sample con- matrix and method of preparation), and 10 g/L for ground-
centrate containing this compound in acetone at a concentra- water samples. EQLs will be proportionately higher for sample
tion 1,000 times more concentrated than the selected spike extracts that require dilution to avoid saturation of the detector.
concentration is required. The QC check sample concentrate
may be prepared from pure standard materials or purchased The EQL(b) for groundwater in g/L is 100.
The EQL (a, b) for low concentrations in soil and sediment
as certified solutions. Use appropriate trip, matrix, control site,
in g/kg is not determined.
method, reagent, and solvent blanks. Internal, surrogate, and
Accuracy as g/L is not listed.
five concentration level calibration standards are used.
Overall precision in g/L is not listed.
REFERENCE Method 8140, SW-846, 3rd ed., Sept. 1986.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
Phosalone EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #2310-17-0 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
MATRIX This method is used to determine the concentra- C = True value for concentration, in g/L.
X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared
taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQLforlow soil/sediment] [Factor].
but this results in very high detection limits (approximately This estimated EQL is similar to an EPA “Practical Quantitation
10,000 g/L). Typically, a 1-L liquid sample, containing surro- Limit.”
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral Soils, sediments, or sludges — Use an 8-oz. widemouth glass
and 200 ng of acid surrogates (for a 1-L injection). Analysis with a screw-top Teflon®-lined cover that has been prewashed
is performed by GC/MS using a capillary GC column. with detergent and rinsed with distilled water and methanol
(or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam-
ples, and spikes must be evaluated for interferences. Contam- SAMPLE PRESERVATION
ination by carryover can occur whenever high-concentration Liquid samples — If residual chlorine is present, add 3 mL of
and low-concentration samples are sequentially analyzed. To 10% sodium thiosulfate per gallon, cool to 4C and store in a
reduce carryover, the sample syringe must be rinsed out solvent-free refrigerator until analysis; if chlorine is not present,
between samples with solvent. Whenever an unusually concen- then eliminate the sodium thiosulfate addition.
trated sample is encountered, it should be followed by the Soils, sediments, or sludges — Cool samples to 4C and store
analysis of blank solvent to check for cross-contamination. in a solvent-free refrigerator.

©1996 CRC Press LLC


MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.
SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,
Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for of Solid Waste, Washington, DC.
18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Phosmet EPA Method 8270
Soils, sediments, or sludges — Use 30 g of sample. Nonporous CAS #732-11-6
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium TITLE Semivolatile Organic Compounds by GC/MS
sulfate until the sample is free flowing. Add 1 mL of surrogate
standards to all samples, spikes, standards, and blanks. For the MATRIX This method is used to determine the concentra-
sample in each analytical batch selected for spiking, add 1.0 mL tion of semivolatile organic compounds in extracts prepared
of a matrix spiking standard. For base/neutral acid analysis, the from all types of solid waste matrices, soils, and groundwater.
amount added of the surrogates and matrix spiking com- Although surface waters are not specifically mentioned, this
pounds should result in a final concentration of 100 ng/ L of method should be applicable to water samples from rivers,
each base/neutral analyte and 200 ng/L of each acid analyte lakes, etc.
in the extract to be analyzed (assuming a 1- L injection). METHOD SUMMARY This method covers 259 semivolatile
Immediately add a 100-mL mixture of 1:1 methylene chlo- organic compounds. In very limited applications direct injec-
ride:acetone and extract the sample ultrasonically for 3 min tion of the sample into the GC/MS system may be appropriate,
and then decant or filter the extracts. Repeat the extraction two but this results in very high detection limits (approximately
or more times. Dry the extract using a column with anhydrous 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. gate, and matrix spiking standards, is extracted in a continuous
QUALITY CONTROL A methylene chloride solution con- extractor first under acid conditions and then under basic con-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is ditions. Typically 30 g of a solid sample, containing surrogate,
used for tuning the GC/MS system each 12-h shift. A system and matrix spiking standards, is extracted ultrasonically. After
performance check also must be made during every 12-h shift. concentrating the extract to 1 mL it is spiked with 10 L of an
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- internal standard solution just prior to analysis by GC/MS. The
rophenol, and benzidine is required to verify injection port volume injected should contain about 100 ng of base/neutral
inertness and GC column performance. A calibration standard and 200 ng of acid surrogates (for a 1-L injection). Analysis
at mid-concentration, containing each compound of interest, is performed by GC/MS using a capillary GC column.
including all required surrogates, must be performed every 12 h INTERFERENCES Raw GC/MS data from all blanks, sam-
during analysis. After the system performance check is met, ples, and spikes must be evaluated for interferences. Contam-
calibration check compounds (CCCs) are used to check the ination by carryover can occur whenever high-concentration
validity of the initial calibration. and low-concentration samples are sequentially analyzed. To
The internal standard responses and retention times in the reduce carryover, the sample syringe must be rinsed out
calibration check standard must be evaluated immediately after between samples with solvent. Whenever an unusually concen-
or during data acquisition. If the retention time for any internal trated sample is encountered, it should be followed by the
analysis of blank solvent to check for cross-contamination.
standard changes by more than 30 seconds from the last check
calibration (12 h), the chromatographic system must be INSTRUMENTATION A GC/MS and a data system are
inspected for malfunctions and corrections must be made, as required. The GC column used is a 30 m 0.25 mm I.D. (or
required. If the electron ionization current plot (EICP) area for 0.32 mm I.D.) 1um film thickness silicone-coated fused silica

©1996 CRC Press LLC


capillary column. A continuous liquid-liquid extractor ges may be stored for a maximum of 14 days and the extracts
equipped with Teflon® or glass connection joints and stopcocks analyzed within 40 days.
requiring no lubrication, a K-D concentrating apparatus, water
SAMPLE PREPARATION
bath, and an ultrasonic disrupter with a minimum power of Liquid samples — Transfer 1 L quantitatively to a continuous
300 W and with pulsing capability are also required. extractor. If high concentrations are anticipated, a smaller vol-
PRECISION & ACCURACY The estimated quantitation ume may be used and then diluted with organic-free reagent
limit (EQL) of Method 8270B for determining an individual water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
compound is approximately 1 mg/kg (wet weight) for soil or sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
sediment samples, 1–200 mg/kg for wastes (dependent on solution into each sample. For the sample in each analytical
batch selected for spiking, add 1.0 mL of a matrix spiking stan-
matrix and method of preparation), and 10 g/L for ground-
dard. For base/neutral acid analysis, the amount of the surro-
water samples. EQLs will be proportionately higher for sample
gates and matrix spiking compounds added to the sample
extracts that require dilution to avoid saturation of the detector.
should result in a final concentration of 100 ng/L of each
The EQL(b) for groundwater in g/L is 40. analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL (a, b) for low concentrations in soil and sediment tion). Extract with methylene chloride for 18–24 h. Next, adjust
in g/kg is not determined. the pH of the aqueous phase to pH >11 using 10 N sodium
Accuracy as g/L is not listed. hydroxide and extract it with methylene chloride again for
Overall precision in g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
concentrator.
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample. Soils, sediments, or sludges — Use 30 g of sample. Nonporous
This calculation is based on a 30 g sample and gel perme- or wet samples (gummy or clay type) that do not have a free-
ation chromatography cleanup. flowing sandy texture must be mixed with anhydrous sodium
(b) Sample EQLs are highly matrix-dependent. The EQLs are sulfate until the sample is free flowing. Add 1 mL of surrogate
provided for guidance and may not always be achievable. standards to all samples, spikes, standards, and blanks. For the
C = True value for concentration, in g/L. sample in each analytical batch selected for spiking, add 1.0 mL
X = Average recovery found for measurements of samples con- of a matrix spiking standard. For base/neutral acid analysis, the
taining a concentration of C, in g/L. amount added of the surrogates and matrix spiking com-
pounds should result in a final concentration of 100 ng/ L of
ESTIMATED QUANTITATION LIMIT each base/neutral analyte and 200 ng/L of each acid analyte
Other Matrices Factor (a) in the extract to be analyzed (assuming a 1- L injection).
High-concentration soil and sludges by sonicator 7.5 Immediately add a 100-mL mixture of 1:1 methylene chlo-
Non-water miscible waste 75 ride:acetone and extract the sample ultrasonically for 3 min
and then decant or filter the extracts. Repeat the extraction two
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. or more times. Dry the extract using a column with anhydrous
This estimated EQL is similar to an EPA “Practical Quantitation sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
Limit.”
QUALITY CONTROL A methylene chloride solution con-
SAMPLING METHOD taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with used for tuning the GC/MS system each 12-h shift. A system
a screw-top Teflon®-lined cover that has been prewashed with performance check also must be made during every 12-h shift.
detergent and rinsed with distilled water and methanol (or A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
isopropanol). rophenol, and benzidine is required to verify injection port
inertness and GC column performance. A calibration standard
Soils, sediments, or sludges — Use an 8-oz. widemouth glass
at mid-concentration, containing each compound of interest,
with a screw-top Teflon®-lined cover that has been prewashed including all required surrogates, must be performed every 12 h
with detergent and rinsed with distilled water and methanol during analysis. After the system performance check is met,
(or isopropanol). calibration check compounds (CCCs) are used to check the
SAMPLE PRESERVATION validity of the initial calibration.
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check standard must be evaluated immediately after
solvent-free refrigerator until analysis; if chlorine is not present, or during data acquisition. If the retention time for any internal
then eliminate the sodium thiosulfate addition. standard changes by more than 30 seconds from the last check
Soils, sediments, or sludges — Cool samples to 4C and store calibration (12 h), the chromatographic system must be
in a solvent-free refrigerator. inspected for malfunctions and corrections must be made, as
required. If the electron ionization current plot (EICP) area for
MHT Liquid samples must be extracted within 7 days and any of the internal standards changes by a factor of two from
the extracts analyzed within 40 days. Soils, sediments, or slud- the last daily calibration standard check, the mass spectrometer

©1996 CRC Press LLC


must be inspected for malfunctions and corrections must be requiring no lubrication, a K-D concentrating apparatus, water
made, as appropriate. bath, and an ultrasonic disrupter with a minimum power of
Demonstrate, through the analysis of a reagent water blank, 300 W and with pulsing capability are also required.
that interferences from the analytical system, glassware, and PRECISION & ACCURACY The estimated quantitation
reagents are under control. The blank samples should be car- limit (EQL) of Method 8270B for determining an individual
ried through all stages of the sample preparation and measure- compound is approximately 1 mg/kg (wet weight) for soil or
ment steps. For each analytical batch (up to 20 samples), a sediment samples, 1–200 mg/kg for wastes (dependent on
reagent blank, matrix spike, and matrix spike duplicate/dupli- matrix and method of preparation), and 10 g/L for ground-
cate must be analyzed (the frequency of the spikes may be water samples. EQLs will be proportionately higher for sample
different for different monitoring programs). The blank and
extracts that require dilution to avoid saturation of the detector.
spiked samples must be carried through all stages of the sample
preparation and measurement steps. A QC reference sample The EQL(b) for groundwater in g/L is 100.
concentrate containing each analyte at a concentration of The EQL (a, b) for low concentrations in soil and sediment
100 mg/L in methanol is required. in g/kg is not determined.
Accuracy as g/L is not listed.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
Overall precision in g/L is not listed.
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
of Solid Waste, Washington, DC. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
Phosphamidon EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #13171-21-6 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate,
This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately
Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral Soils, sediments, or sludges — Use an 8-oz. widemouth glass
and 200 ng of acid surrogates (for a 1-L injection). Analysis with a screw-top Teflon®-lined cover that has been prewashed
is performed by GC/MS using a capillary GC column. with detergent and rinsed with distilled water and methanol
(or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam-
ples, and spikes must be evaluated for interferences. Contam- SAMPLE PRESERVATION
ination by carryover can occur whenever high-concentration Liquid samples — If residual chlorine is present, add 3 mL of
and low-concentration samples are sequentially analyzed. To 10% sodium thiosulfate per gallon, cool to 4C and store in a
reduce carryover, the sample syringe must be rinsed out solvent-free refrigerator until analysis; if chlorine is not present,
between samples with solvent. Whenever an unusually concen- then eliminate the sodium thiosulfate addition.
trated sample is encountered, it should be followed by the
analysis of blank solvent to check for cross-contamination. Soils, sediments, or sludges — Cool samples to 4C and store
in a solvent-free refrigerator.
INSTRUMENTATION A GC/MS and a data system are
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and
0.32 mm I.D.) 1um film thickness silicone-coated fused silica the extracts analyzed within 40 days. Soils, sediments, or slud-
capillary column. A continuous liquid-liquid extractor ges may be stored for a maximum of 14 days and the extracts
equipped with Teflon® or glass connection joints and stopcocks analyzed within 40 days.

©1996 CRC Press LLC


SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,
Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for of Solid Waste, Washington, DC.
18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Phosphorus EPA Method 6010
Soils, sediments, or sludges — Use 30 g of sample. Nonporous CAS #7723-14-0
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium TITLE Inductively Coupled Plasma-Atomic Emission Spec-
sulfate until the sample is free flowing. Add 1 mL of surrogate troscopy
standards to all samples, spikes, standards, and blanks. For the
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX This method is applicable to the determination of
of a matrix spiking standard. For base/neutral acid analysis, the trace elements, including metals, in groundwater, soils, sludges,
amount added of the surrogates and matrix spiking com- sediments, and other solid wastes. All matrices require diges-
pounds should result in a final concentration of 100 ng/ L of tion prior to analysis. The method of standard addition must
each base/neutral analyte and 200 ng/L of each acid analyte be used for the analysis of all sample digests unless either serial
dilution or matrix spike addition demonstrates it is not
in the extract to be analyzed (assuming a 1- L injection).
required.
Immediately add a 100-mL mixture of 1:1 methylene chlo-
ride:acetone and extract the sample ultrasonically for 3 min METHOD SUMMARY Method 6010 covers 25 elements
and then decant or filter the extracts. Repeat the extraction two using ICP analysis. It measures element-emitted light by optical
or more times. Dry the extract using a column with anhydrous spectrometry. Samples, following an appropriate acid diges-
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. tion, are nebulized and the resulting aerosol is transported to
the plasma torch. Element-specific atomic line emission spectra
QUALITY CONTROL A methylene chloride solution con-
are produced by a radio-frequency inductively coupled plasma.
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
used for tuning the GC/MS system each 12-h shift. A system INTERFERENCES Interferences may be categorized as spec-
performance check also must be made during every 12-h shift. tral or non-spectral. Spectral interferences are caused by over-
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- lap of a spectral line from another element, unresolved overlap
rophenol, and benzidine is required to verify injection port of molecular band spectra, background contribution from con-
inertness and GC column performance. A calibration standard tinuous or recombination phenomenon, and stray light from
at mid-concentration, containing each compound of interest, the line emission of high concentration elements. Non-spectral
including all required surrogates, must be performed every 12 h interferences include physical and chemical interferences. Phys-
during analysis. After the system performance check is met, ical interferences are effects associated with the sample nebu-
calibration check compounds (CCCs) are used to check the lization and transport processes. Changes in viscosity and
validity of the initial calibration. surface tension can cause significant inaccuracies. Chemical
interferences include molecular compound formation, ioniza-
The internal standard responses and retention times in the tion effects, and solute vaporization effects. Normally these
calibration check standard must be evaluated immediately after effects are not significant and can be minimized by careful
or during data acquisition. If the retention time for any internal selection of operating conditions. Chemical interferences are
standard changes by more than 30 seconds from the last check highly dependent on matrix type and the specific analyte element.
calibration (12 h), the chromatographic system must be
inspected for malfunctions and corrections must be made, as INSTRUMENTATION An inductively coupled argon plasma
required. If the electron ionization current plot (EICP) area for emission spectrometer (ICP) capable of background correction
any of the internal standards changes by a factor of two from is required.
the last daily calibration standard check, the mass spectrometer PRECISION & ACCURACY Detection limits, sensitivity, and
must be inspected for malfunctions and corrections must be optimum ranges of the metals will vary with the matrices and
made, as appropriate. model of the spectrometer. In a single lab evaluation, seven

©1996 CRC Press LLC


wastes were analyzed for 22 elements. The mean percent rela- acid and reflux for 30 min. Repeat last step and then allow the
tive standard deviation from triplicate analyses for all elements solution to evaporate to 5 mL without boiling. Cool and add
and wastes was 9 2%. The mean percent recovery of spiked 2 mL of water and 3 mL of 30% hydrogen peroxide. Cover and
elements for all wastes was 93 6%. Spike levels ranged from place the beaker on the hot plate. Heat and add 30% hydrogen
100 g/L to 100 mg/L. The wastes included sludges and indus- peroxide in 1-mL aliquots with warming until the effervescence
trial wastewaters. is minimal but do not add more than a total of 10 mL of 30%
hydrogen peroxide. If the sample is being prepared for the
Estimated instrument detection limit in g/L is 51. analysis of Ag, Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg,
Spiked concentration in g/L is not listed.
Mn, Mo, Na, Ni, Os, Pb, Se, Tl, V, and Zn, then add 5 mL of
Mean reported value in g/L is not listed.
concentrated hydrochloric acid and 10 mL of water and return
Precision as RSD % is not listed.
the covered beaker to a hot plate for 15 min of additional
SAMPLING METHOD Samples should be collected in boro- refluxing without boiling. Dilute the sample to a 100 mL vol-
silicate glass, linear polyethylene, polypropylene, or Teflon® ume with water after cooling and filter or centrifuge to remove
bottles that have been prewashed with detergent and tap water, particulates.
and rinsed with 1:1 nitric acid and tap water or 1:1 hydrochloric
QUALITY CONTROL Laboratory control samples must be
acid and tap water. Collect at least 2 g of solids and 200 mL of
analyzed for each analytical method. A method blank should
aqueous samples.
be analyzed with each batch of samples. The effect of the matrix
SAMPLE PRESERVATION Add nitric acid to make the sam- on method performance must be demonstrated: when appro-
ples pH <2. priate, there should be at least one matrix spike and either one
matrix duplicate or one matrix spike duplicate per analytical
MHT The maximum holding time for properly preserved
batch. The bias and precision of the method, as well as the
samples is 6 months.
method detection limit for each specific matrix type, must be
SAMPLE PREPARATION Preliminary treatment of most measured.
matrices is necessary because of the complexity and variability
Dilute and reanalyze samples that are more concentrated than
of sample matrices. Water samples that have been prefiltered
the linear calibration limit. Employ a minimum of one reagent
and acidified will not need acid digestion. Methods for acid
blank per sample batch to determine if contamination or any
digestion of waters for total recoverable or dissolved metals,
memory effects are occurring. Whenever a new or unusual
acid digestions of aqueous samples and extracts for total metals,
sample matrix is encountered, perform either a serial dilution
and acid digestion of sediments, sludges, and soils are summa-
test or a matrix spike addition test to ensure that neither pos-
rized below.
itive or negative interferences are operating on any of the ana-
Total recoverable or dissolved metals in water — To prepare lyte elements. Check the instrument standardization by
surface and groundwater samples for determination of total verifying calibration every 10 samples using a calibration blank
recoverable and dissolved metals, a 100-mL aliquot of well- and a check standard.
mixed sample is acidified with concentrated nitric acid and
REFERENCE Test Methods for Evaluating Solid Waste (SW-
concentrated hydrochloric acid, then heated until the volume
846). U.S. EPA. 1983. Method 6010, Rev. 0, Sept. 1986. Office
is reduced to 15–20 mL.Adjust the final volume to 100 mLwith
of Solid Wastes, Washington, DC.
reagent water.
Total metals in aqueous samples, soil and sediment extracts —
To prepare aqueous samples, soil and sediment extracts, and
Phosphorus EPA Method 365.1
wastes that contain suspended solids, a 100-mL aliquot is made
CAS #7723-14-0
acidic with concentrated nitric acid and the solution is evapo-
rated to about 5 mL on a hot plate. Continue heating and
TITLE Inorganics, Non-Metallics
adding additional acid until sample digestion is complete,
which is usually indicated when the digestate is light in color MATRIX Drinking, surface and saline waters. Wastewater.
or does not change in appearance. Evaporate the solution to
APPLICATION Date issued 1971. Editorial Rev. 1974 and
about 3 mL and cool it and add a small quantity of 1:1 hydro-
1978. (Colorimetric, automated, ascorbic acid). Applies to
chloric acid (10 mL/100 mL of final solution). Cover the beaker
specified forms of phosphorus (P), based on reactions for the
and reflux for 15 min. Wash down the beaker walls and filters
orthophosphate ion. Most analyses are run for phosphorus and
or centrifuge the sample to remove silicates and other insoluble
dissolved P, orthophosphate, and dissolved orthophosphate.
material. Filter the sample and adjust the final volume to
100 mL with reagent water and the final acid concentration to INTERFERENCES High iron concentrations cause precipi-
10%. tation of and loss of phosphorus. Sample turbidity must be
removed by filtration prior to analysis for orthophosphate. Salt
Sediments, sludges, and soils — To prepare sediments, sludges
error for samples 5 to 20% salt, <1%. Arsenic concentrations
and soil samples, transfer 1–2 g to a conical beaker and add
> phosphorus concentration, may interfere.
10 mL of 1:1 nitric acid, mix the slurry, and cover it with a
watch glass. Heat the sample and reflux for 10–15 min without INSTRUMENTATION Technicon auto analyzer. 650–660 or
boiling. Allow it to cool, then add 5 mL of concentrated nitric 880 nm filter.

©1996 CRC Press LLC


RANGE 0.001–1.0 mg P/L range. colored complex by ascorbic acid. Color is proportional to
phosphorus concentration. Measure color on auto analyzer.
MDL Not listed.
REFERENCE Methods for the Chemical Analysis of Water
PRECISION 0.066 mg P/L at 0.30 mg P/L (as orthophos-
and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
phate).
ACCURACY As bias, –0.04 mg P/L at 0.30 mg P/L (as ortho-
phosphate).
Phosphorus EPA Method 365.3
SAMPLING METHOD Plastic or glass. (50 mL). CAS #7723-14-0
STABILITY Cool, 4C. H2SO4 to pH <2. TITLE Inorganics, Non-Metallics
MHT 28 days. MATRIX Drinking, surface and saline waters. Wastewater.
QUALITY CONTROL This method is based on reactions APPLICATION Date issued 1978. (Colorimetric, ascorbic
specific for the orthophosphate ion in which an antimony- acid, two reagent).
phospho-molybdate complex is reduced to an intensely blue
colored complex by ascorbic acid. Color is proportional to Applies to specified forms of phosphorus (P), based on reac-
phosphorus concentration. Measure color on auto analyzer tions for the orthophosphate ion. Most commonly measured
forms are; phosphorus and dissolved P, orthophosphate and
REFERENCE EPA Methods for the Chemical Analysis of dissolved orthophosphate.
Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
INTERFERENCES Arsenate interference is eliminated by
reducing arsenic acid to arsenious acid using sodium bisulfite.
High concentrations of iron cause low phosphorus recovery.
Phosphorus EPA Method 365.2 The bisulfite treatment also eliminates this interference.
CAS #7723-14-0
INSTRUMENTATION Spectro(or filter)photometer. 660 or
TITLE Inorganics, Non-Metallics 880 nm. Light path of 1 cm or longer.

MATRIX Drinking, surface and saline waters. Wastewater. RANGE 0.01–1.2 mg P/L.

APPLICATION Date issued 1971. (Colorimetric, ascorbic MDL Not listed.


acid, single reagent). Applies to specified forms of phosphorus PRECISION Not listed.
(P), based on reactions for orthophosphate ion. Most com-
ACCURACY Recoveries = 99 and 100% at 7.6 and 0.55 mg
monly measured forms are; phosphorus and dissolved P, ortho-
P/L (waste and sewage)
phosphate and dissolved orthophosphate.
SAMPLING METHOD Plastic or glass (50 mL).
INTERFERENCES High iron concentrations cause precipi-
tation of and loss of phosphorus. Salt error for samples 5 to STABILITY Cool, 4C. H2SO4 to pH <2.
20% salt, <1%. Arsenic concentration> phosphorus concen- MHT 28 days.
tration, may interfere. (Only orthophosphate turns blue color
in this test. Other (P) forms are converted to orthophosphate). QUALITY CONTROL This Method is based on reactions
specific for the orthophosphate ion in which an antimony-
INSTRUMENTATION Spectro(or filter)photometer. 650 or phospho-molybdate complex is reduced to an intensely blue
880 nm. Light path of 1 cm or longer. colored complex by ascorbic acid. Color is proportional to
RANGE 0.01–0.5 mg P/L. phosphorus concentration. Measure color in auto analyzer.

MDL Not listed. REFERENCE EPA Methods for the Chemical Analysis of
Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
PRECISION SD = 0.018 mg P/L at 0.335 mg P/L (as ortho-
phosphate)
ACCURACY As bias, –0.009 mg P/L L 0.335 mg P/L (as Phosphorus EPA Method 365.4
orthophosphate). CAS #7723-14-0
SAMPLING METHOD Plastic or glass (50 mL).
TITLE Inorganics, Non-Metallics
STABILITY Cool, 4C. H2SO4 to pH <2.
MATRIX Drinking, surface, and wastewaters.
MHT 28 days.
APPLICATION Date issued 1974. (Colorimetric, automated,
QUALITY CONTROL This method is based on reactions block digestor AAII). Sample is heated in presence of sulfuric
specific for the orthophosphate ion in which an antimony- acid, potassium sulfate and mercuric sulfate for 2 1/2 h. Residue
phospho-molybdate complex is reduced to an intensely blue is cooled, diluted to 25 mL and placed on auto analyzer for

©1996 CRC Press LLC


phosphorus determination. Temperature of block digester dur- INTERFERENCES Raw GC/MS data from all blanks, sam-
ing 2 1/2 h digestion is 380 deg C. ples, and spikes must be evaluated for interferences. Contam-
ination by carryover can occur whenever high-concentration
INTERFERENCES Only add 4–8 Teflon® boiling chips dur- and low-concentration samples are sequentially analyzed. To
ing digestion. Too many boiling chips will cause sample to boil reduce carryover, the sample syringe must be rinsed out
over. between samples with solvent. Whenever an unusually concen-
INSTRUMENTATION block digestor BD-40. Technicon trated sample is encountered, it should be followed by the
analysis of blank solvent to check for cross-contamination.
auto analyzer and method no. 327-74W.
INSTRUMENTATION A GC/MS and a data system are
RANGE 0.01–20 mg P/L.
required. The GC column used is a 30 m 0.25 mm I.D. (or
MDL Not listed. 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
capillary column. A continuous liquid-liquid extractor
PRECISION SD = 0.06 at 2.0 mg P/L (sewage sample)
equipped with Teflon® or glass connection joints and stopcocks
ACCURACY Recoveries = 95 and 98% at 1.84 and 1.89 mg requiring no lubrication, a K-D concentrating apparatus, water
P/L (sewage samples) bath, and an ultrasonic disrupter with a minimum power of
300 W and with pulsing capability are also required.
SAMPLING METHOD Plastic or glass (50 mL).
PRECISION & ACCURACY The estimated quantitation
STABILITY Cool, 4C. H2SO4 to pH <2. limit (EQL) of Method 8270B for determining an individual
MHT 28 days. compound is approximately 1 mg/kg (wet weight) for soil or
sediment samples, 1–200 mg/kg for wastes (dependent on
QUALITY CONTROL This Method covers the determina- matrix and method of preparation), and 10 g/L for ground-
tion of total phosphorus. Prepare standard curve plotting peak water samples. EQLs will be proportionately higher for sample
heights of standards against concentration values. Compare extracts that require dilution to avoid saturation of the detector.
sample peak heights with standard curve to compute concen-
The EQL(b) for groundwater in g/L is 100.
tration. (If TKN is determined, the sample should be diluted The EQL (a, b) for low concentrations in soil and sediment
with ammonia-free water). in g/kg is not determined.
REFERENCE Methods for the Chemical Analysis of Water Accuracy as g/L is not listed.
and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979. Overall precision in g/L is not listed.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
Phthalic anhydride EPA Method 8270 will be higher based on the % dry weight of each sample.
This calculation is based on a 30 g sample and gel perme-
CAS #85-44-9
ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS
provided for guidance and may not always be achievable.
MATRIX This method is used to determine the concentra- C = True value for concentration, in g/L.
tion of semivolatile organic compounds in extracts prepared X = Average recovery found for measurements of samples con-
from all types of solid waste matrices, soils, and groundwater. taining a concentration of C, in g/L.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers,
Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
but this results in very high detection limits (approximately This estimated EQL is similar to an EPA “Practical Quantitation
Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral with a screw-top Teflon®-lined cover that has been prewashed
and 200 ng of acid surrogates (for a 1-L injection). Analysis with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column. (or isopropanol).

©1996 CRC Press LLC


SAMPLE PRESERVATION The internal standard responses and retention times in the
Liquid samples — If residual chlorine is present, add 3 mL of calibration check standard must be evaluated immediately after
10% sodium thiosulfate per gallon, cool to 4C and store in a or during data acquisition. If the retention time for any internal
solvent-free refrigerator until analysis; if chlorine is not present, standard changes by more than 30 seconds from the last check
then eliminate the sodium thiosulfate addition. calibration (12 h), the chromatographic system must be
inspected for malfunctions and corrections must be made, as
Soils, sediments, or sludges — Cool samples to 4C and store
required. If the electron ionization current plot (EICP) area for
in a solvent-free refrigerator.
any of the internal standards changes by a factor of two from
MHT Liquid samples must be extracted within 7 days and the last daily calibration standard check, the mass spectrometer
the extracts analyzed within 40 days. Soils, sediments, or slud- must be inspected for malfunctions and corrections must be
ges may be stored for a maximum of 14 days and the extracts made, as appropriate.
analyzed within 40 days.
Demonstrate, through the analysis of a reagent water blank,
SAMPLE PREPARATION that interferences from the analytical system, glassware, and
Liquid samples — Transfer 1 L quantitatively to a continuous reagents are under control. The blank samples should be car-
extractor. If high concentrations are anticipated, a smaller vol- ried through all stages of the sample preparation and measure-
ume may be used and then diluted with organic-free reagent ment steps. For each analytical batch (up to 20 samples), a
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) reagent blank, matrix spike, and matrix spike duplicate/dupli-
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking cate must be analyzed (the frequency of the spikes may be
solution into each sample. For the sample in each analytical different for different monitoring programs). The blank and
batch selected for spiking, add 1.0 mL of a matrix spiking stan- spiked samples must be carried through all stages of the sample
dard. For base/neutral acid analysis, the amount of the surro- preparation and measurement steps. A QC reference sample
gates and matrix spiking compounds added to the sample concentrate containing each analyte at a concentration of
should result in a final concentration of 100 ng/L of each 100 mg/L in methanol is required.
analyte in the extract to be analyzed (assuming a 1- L injec-
tion). Extract with methylene chloride for 18–24 h. Next, adjust REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for of Solid Waste, Washington, DC.
18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator. Picloram EPA Method 8151
Soils, sediments, or sludges — Use 30 g of sample. Nonporous CAS #1918-02-1
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium TITLE Chlorinated Herbicides by GC Using Methylation or
sulfate until the sample is free flowing. Add 1 mL of surrogate Pentafluorobenzylation Derivatization: Capillary Column
standards to all samples, spikes, standards, and blanks. For the Technique.
sample in each analytical batch selected for spiking, add 1.0 mL MATRIX This method covers aqueous and solid matrices.
of a matrix spiking standard. For base/neutral acid analysis, the This includes a wide variety such as drinking water, ground-
amount added of the surrogates and matrix spiking com- water, industrial wastewaters, surface waters, soils, solids, and
pounds should result in a final concentration of 100 ng/ L of sediments.
each base/neutral analyte and 200 ng/L of each acid analyte
in the extract to be analyzed (assuming a 1- L injection). METHOD SUMMARY This is a GC method for determining
Immediately add a 100-mL mixture of 1:1 methylene chlo- 19 chlorinated acid herbicides in aqueous, soil, and waste
ride:acetone and extract the sample ultrasonically for 3 min matrices. Because these compounds are produced and used in
and then decant or filter the extracts. Repeat the extraction two various forms (i.e., acid, salt, ester, etc.) a hydrolysis step is
or more times. Dry the extract using a column with anhydrous included to convert the herbicide to the acid form prior to
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. analysis. This method provides hydrolysis, extraction, deriva-
tization and GC conditions for the analysis of chlorinated acid
QUALITY CONTROL A methylene chloride solution con- herbicides in water, soil, and waste samples. Water samples are
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is hydrolyzed in situ, extracted with diethyl ether, and then ester-
used for tuning the GC/MS system each 12-h shift. A system ified with either diazomethane or pentafluorobenzyl bromide.
performance check also must be made during every 12-h shift. The derivatives are determined by gas chromatography with an
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- electron capture detector (GC/ECD). The results are reported
rophenol, and benzidine is required to verify injection port as acid equivalents. The sensitivity of this method depends on
inertness and GC column performance. A calibration standard the level of interferences in addition to instrumental limitations.
at mid-concentration, containing each compound of interest,
including all required surrogates, must be performed every 12 h INTERFERENCES Method interferences may be caused by
during analysis. After the system performance check is met, contaminants in solvents, reagents, glassware, and other sample
calibration check compounds (CCCs) are used to check the processing hardware. Immediately prior to use, glassware should
validity of the initial calibration. be rinsed with the next solvent to be used. Matrix interferences

©1996 CRC Press LLC


may be caused by contaminants that are coextracted from the determined using standard solutions and corrected to 50 g soil
sample. Organic acids, especially chlorinated acids, cause the samples.
most direct interference with the determination by methyla-
SAMPLE COLLECTION, PRESERVATION & HANDLING
tion. Phenols, including chlorophenols, may also interfere with
Containers used to collect samples for the determination of
this procedure. The determination using pentafluorobenzyla-
semivolatile organic compounds should be soap and water
tion is more sensitive, and more prone to interferences from
washed followed by methanol (or isopropanol) rinsing. The
the presence of organic acids of phenols than by methylation.
sample containers should be of glass or Teflon® and have screw-
Alkaline hydrolysis and subsequent extraction of the basic solu-
tion removes many chlorinated hydrocarbons and phthalate top covers with Teflon® liners.
esters that might otherwise interfere with the ECD analysis. No preservation is used with concentrated waste samples. With
The herbicides, being strong organic acids, react readily with liquid samples containing no residual chlorine and with soil,
alkaline substances and may be lost during analysis. Therefore, sediment, and sludge samples, immediately cooling to 4C is
glassware must be acid-rinsed and then rinsed to constant pH the only preservation used. When residual chlorine is present
with organic-free reagent water. then 3 mL of 10% aqueous sodium sulfate is added for each
INSTRUMENTATION A GC suitable for Grob-type injec- gallon of sample collected, followed by cooling to 4C.
tion using capillary columns. A data system for measuring peak The holding time for all volatile organics samples is 14 days.
heights and/or peak areas is recommended.An electron capture Liquid samples must be extracted within 7 days and their
detector (ECD) is used. Also a K-D apparatus, a diazomethane extracts analyzed within 40 days. Concentrated waste, soil, sed-
generator, a centrifuge and an ultrasonic disrupter will be iment, and sludge samples must be extracted within 14 days
required. and their extracts analyzed within 40 days.
Narrow Bore Columns: SAMPLE PREPARATION
Primary Column 1: 30 m 0.25 mm, 5% phenyl/95% methyl Preparation of soil, sediment, and other solid samples — Acid-
silicone (DB-5), 0.25 m film thickness. ify 30 g (dry weight) solids with 0.1 M phosphate buffer (pH =
Primary Column 1a (GC/MS): 30 m  0.32 mm, 5% phe- 2.5) and thoroughly mix the contents. Spike the sample with
nyl/95% methyl silicone (DB-5), 1-m film thickness. surrogate compound(s). The ultrasonic extraction of solids
Column 2: 30 m 0.25 mm DB-608 with a 25 m film thickness. must be optimized for each type of sample. In order for the
Confirmation Column: 30 m  0.25 mm, 14% cyanopropyl ultrasonic extractor to efficiently extract solid samples, the
phenyl silicone (DB-1701), 0.25 m film thickness. sample must be free flowing when the solvent is added. Acid-
Megabore Columns: ified anhydrous sodium sulfate should be added to clay-type
Primary Column: 30 m 0.53 mm DB-608 with 0.83 m film soils, or any other solid that is not a free-flowing sandy texture,
thickness. until a free flowing mixture is obtained. Add methylene chlo-
Confirmation Column: 30 m  0.53 mm, 14% cyanopropyl ride and perform ultrasonic extraction. Combine organic
phenyl silicone (DB-1701), 1.0 m film thickness. extracts from the repetitive extractings of the sample and cen-
trifuge. Add aqueous potassium hydroxide, water, and metha-
PRECISION & ACCURACY Method detection limits
nol to the extract and reflux the mixture on a water bath.
(MDLs) are compound-dependent and vary with derivitization
Extract the solution three times with methylene chloride and
efficiency, derivative recovery, the matrix sampled, and herbi-
discard the methylene chloride phase. The basic solution con-
cide concentration.
tains the herbicide salts. Adjust the pH of the solution to <2
The estimated MDL (in g/L) was 0.14 for aqueous samples with cold sulfuric acid and extract three times with methylene
using GC/ECD. chloride. Combine the extracts and pour them through a pre-
The estimated MDL (in g/kg) was not reported for soil sam- rinsed drying column containing acidified anhydrous sodium
ples using GC/ECD when corrected back to 50 g samples sulfate. Collect the dried extracts in a K-D flask and concentrate
extracted and concentrated to 10 mL with 5-L injections. them.

The estimated GC/MS identification limit (in ng) was not Preparation of aqueous samples — Measure 1 L of sample into
reported for soil samples using GC/MS. a 2 L separatory funnel and spike it with surrogate com-
pound( s). Add NaCl to the sample, then add 6 N NaOH to the
Mean percent recovery, calculated from 7–8 determinations of sample to a pH of 12 or more and let the sample sit at room
spiked reagent water, after diazomethane derivatization, from temperature for 1 h to hydrolyze esters. Extract the sample
a spike concentration (in g/L) of 0.6 was 91 with a standard three times with methylene chloride and discard the extracts.
deviation of the percent recovery of 15.5. Then add cold 12 N sulfuric acid to a pH less than or equal to
Mean percent recovery, calculated from 10 determinations of 2, and extract the sample three times with ethyl ether. Collect
spiked clay and clay/still bottom samples over the linear con- the ether phase in a flask containing acidified anhydrous
centration range (in ng/g) of no data was none reported with sodium sulfate and allow it to remain in contact with the
a percent relative standard deviation of none. The RSD % was sodium sulfate for a minimum of 2 h. The drying step is very
calculated on 10 samples high in the linear concentration range critical to ensuring complete esterification; any moisture
and 10 low in the range. The linear concentration range was remaining in the ether will result in low herbicide recoveries.

©1996 CRC Press LLC


Extract concentration and derivatization — The combined separated by GC and detected by a MS. The labeled compounds
ether extract is concentrated to about 1 mL using a K-D appa- serve to correct the variability of the analytical technique.
ratus followed by using a micro Snyder column or nitrogen gas
INTERFERENCES Solvents, reagents, glassware, and other
blowdown. If methyl esters are to be produced, then dilute the
sample processing hardware may yield artifacts and/or elevated
concentrated ether extract with 1 mL of isooctane and 0.5 mL
baselines causing misinterpretation of chromatograms and
of methanol, dilute to a final volume of 4 mL, and esterify with
spectra. Materials used in the analysis must be demonstrated
diazomethane. If pentafluorobenzene esters are to be produced,
to be free from interferences under the conditions of analysis
then dilute concentrated ether extract with acetone to a final
by running method blanks initially and with each sample lot
volume of 4 mL and esterify with pentafluorobenzyl bromide.
(sample started through the extraction process on a given 8-h
QUALITY CONTROL Select a representative spike concen- shift, to a maximum of 20). Specific selection of reagents and
tration for each compound (acid or ester) to be measured. purification of solvents by distillation in all glass systems may
Using stock standard, prepare a quality control check sample be required. Glassware and, where possible, reagents are
concentrate, in acetone, that is 1000 times more concentrated cleaned by solvent rinse and baking at 450C for 1-h minimum.
than the selected concentrations. Use this quality control check Interferences coextracted from samples will vary considerably
sample concentrate to prepare quality control check samples. from source to source, depending on the diversity of the site
Calculate surrogate standard recovery on all standards, sam- being sampled.
ples, blanks, and spikes. GC/MS techniques should be judi-
INSTRUMENTATION Major instrumentation includes a GC
ciously employed to support qualitative identifications made
with a splitless or on-column injection port for capillary col-
with this method. When available, chemical ionization mass
umn, a MS with 70 eV electron impact ionization, and a data
spectra may be employed to aid the qualitative identification
system to collect and record MS data, and process it. A K-D
process.
apparatus is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste, Phys-
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
vinyl silicone bonded phased fused silica capillary column.
of Solid Waste, Washington, DC, EPA Method 8151, Nov. 1990.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
rather than instrumental limitations. The limits typify the min-
2-Picoline EPA Method 1625
imum quantities that can be detected with no interferences
CAS #109-06-8
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was 50. This is defined as a
tion GC/MS minimum level at which the analytical system shall give recog-
nizable mass spectra (background corrected) and acceptable
MATRIX The compounds may be determined in waters,
calibration points.
soils, and municipal sludges by this method.
The MDL (in g/kg) in low solids was 25 and in high solids
METHOD SUMMARY This method is used to determine
was 87; these were determined in digested sludge (low solids)
176 semivolatile toxic organic pollutants associated with the
and in filter cake or compost (high solids).
CWA (as amended 1987); the RCRA (as amended 1986); the
CERCLA (as amended 1986); and other compounds amenable The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog- deviation (in g/L) was 38.
raphy-mass spectrometry (GC/MS). The labeled and native compound initial accuracy as average
recovery (in g/L) was 59–149.
Stable isotopically-labeled analogs of the compounds of interest
are added to the sample. If the solids content is less than 1%, SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques. flow freely are collected in refrigerated bottles using automatic
sampling equipment. Solid samples are collected as grab sam-
If the solids content is 30% or less, the sample is diluted to 1%
ples using widemouth jars. Maintain samples at 0 to 4C from
solids with reagent water, homogenized ultrasonically, and
the time of collection until extraction. If residual chlorine is
extracted at pH 12–13, then at pH <2 with methylene chloride
present in aqueous samples, add 80 mg sodium thiosulfate/L
using continuous extraction techniques. If the solids content is
of water. Begin sample extraction within 7 days of collection,
greater than 30%, the sample is extracted using ultrasonic
and analyze all extracts within 40 days of extraction.
techniques.
SAMPLE PREPARATION Samples containing 1% solids or
Each extract is dried over sodium sulfate, concentrated to a
less are extracted directly using continuous liquid-liquid
volume of 5 mL, cleaned up using GPC, if necessary, and con-
extraction techniques. Samples containing 1 to 30% solids are
centrated. Extracts are concentrated to 1 mL if GPC is not
diluted to the 1% level with reagent water and extracted using
performed, and to 0.5 mL if GPC is performed.
continuous liquid-liquid extraction techniques. Samples con-
An internal standard is added to the extract, and a 1-mL aliquot taining greater than 30% solids are extracted using ultrasonic
of the extract is injected into the GC. The compounds are techniques.

©1996 CRC Press LLC


Base/neutral extraction — Adjust the pH of the waters in the METHOD SUMMARY This method is used to determine
extractors to 12–13 with 6 N NaOH. Extract with methylene 176 semivolatile toxic organic pollutants associated with the
chloride for 24–48 h. CWA (as amended 1987); the RCRA (as amended 1986); the
Acid extraction — Adjust the pH of the waters in the extractors CERCLA (as amended 1986); and other compounds amenable
to 2 or less using 6 N sulfuric acid. Extract with methylene to extraction and analysis by capillary column gas chromatog-
chloride for 24–48 h. raphy-mass spectrometry (GC/MS).
Ultrasonic extraction of high solids samples — Add anhy-
Stable isotopically-labeled analogs of the compounds of interest
drous sodium sulfate to the sample and QC aliquot(s).
are added to the sample. If the solids content is less than 1%,
Add acetone:methylene chloride (1:1) to the sample and a 1-L sample is extracted at pH 12–13, then at pH <2 with
mix thoroughly methylene chloride using continuous extraction techniques.
Concentrate extracts using a K-D apparatus. If the solids content is 30% or less, the sample is diluted to 1%
QUALITY CONTROL The analyst is permitted to modify solids with reagent water, homogenized ultrasonically, and
this method to improve separations or lower the costs of mea- extracted at pH 12–13, then at pH <2 with methylene chloride
surements, provided all performance specifications are met. using continuous extraction techniques. If the solids content is
Analyses of blanks are required to demonstrate freedom from greater than 30%, the sample is extracted using ultrasonic
contamination. When results of spikes indicate atypical techniques.
method performance for samples, the samples are diluted to Each extract is dried over sodium sulfate, concentrated to a
bring method performance within acceptable limits. volume of 5 mL, cleaned up using GPC, if necessary, and con-
For low solids (aqueous samples), extract, concentrate, and centrated. Extracts are concentrated to 1 mL if GPC is not
analyze two sets of four 1-L aliquots (8 aliquots total) of the performed, and to 0.5 mL if GPC is performed.
precision and recovery standard. For high solids samples, two An internal standard is added to the extract, and a 1-mL aliquot
sets of four 30-g aliquots of the high solids reference matrix of the extract is injected into the GC. The compounds are
are used. separated by GC and detected by a MS. The labeled compounds
Spike all samples with labeled compounds to assess method serve to correct the variability of the analytical technique.
performance. Compute percent recovery of the labeled com- INTERFERENCES Solvents, reagents, glassware, and other
pounds using the internal standard method. Compare the sample processing hardware may yield artifacts and/or elevated
labeled compound recovery for each compound with the cor- baselines causing misinterpretation of chromatograms and
responding labeled compound recovery. spectra. Materials used in the analysis must be demonstrated
to be free from interferences under the conditions of analysis
Reagent water and high solids reference matrix blanks are ana-
by running method blanks initially and with each sample lot
lyzed to demonstrate freedom from contamination. Extract (sample started through the extraction process on a given 8-h
and concentrate a 1-L reagent water blank or a high solids shift, to a maximum of 20). Specific selection of reagents and
reference matrix blank with each sample’s lot (samples started purification of solvents by distillation in all glass systems may
through the extraction process on the same 8-h shift, to a be required. Glassware and, where possible, reagents are
maximum of 20 samples). cleaned by solvent rinse and baking at 450C for 1-h minimum.
Field replicates may be collected to determine the precision of Interferences coextracted from samples will vary considerably
the sampling technique, and spiked samples may be required from source to source, depending on the diversity of the site
to determine the accuracy of the analysis when the internal being sampled.
standard method is used. INSTRUMENTATION Major instrumentation includes a GC
REFERENCE Semivolatile Organic Compounds by Isotope with a splitless or on-column injection port for capillary col-
Dilution GC/MS. Office of Water Regulation and Standards, umn, a MS with 70 eV electron impact ionization, and a data
U.S. EPA Industrial Technology Division, Washington, DC, system to collect and record MS data, and process it. A K-D
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, apparatus is used to concentrate extracts.
U.S. EPA, Office of Water Regulations and Standards, 401 M GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
St., SW, Washington, DC, 20460. Phone: 202-382-7131). vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
2-Picoline EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #109-06-8 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
The minimum level (in g/mL) was 50. This is defined as a
tion GC/MS
minimum level at which the analytical system shall give recog-
MATRIX The compounds may be determined in waters, nizable mass spectra (background corrected) and acceptable
soils, and municipal sludges by this method. calibration points.

©1996 CRC Press LLC


The MDL (in g/kg) in low solids was 25 and in high solids reference matrix blank with each sample’s lot (samples started
was 87; these were determined in digested sludge (low solids) through the extraction process on the same 8-h shift, to a
and in filter cake or compost (high solids). maximum of 20 samples).
The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was 38. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was 59–149. standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from U.S. EPA, Office of Water Regulations and Standards, 401 M
the time of collection until extraction. If residual chlorine is St., SW, Washington, DC, 20460. Phone: 202-382-7131).
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction.
2-Picoline EPA Method 8240
SAMPLE PREPARATION Samples containing 1% solids or CAS #109-06-8
less are extracted directly using continuous liquid-liquid
extraction techniques. Samples containing 1 to 30% solids are TITLE Volatile Organics By GC/MS: Packed Column Technique
diluted to the 1% level with reagent water and extracted using
continuous liquid-liquid extraction techniques. Samples con- MATRIX Nearly all types of sample matarices, regardless of
taining greater than 30% solids are extracted using ultrasonic water content, can be analyzed using this method. This includes
techniques. groundwater, aqueous sludges, caustic liquors, acid liquors,
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
Base/neutral extraction — Adjust the pH of the waters in the metric emulsions, filter cakes, spent carbons, spent catalysts,
extractors to 12–13 with 6 N NaOH. Extract with methylene
soils, and sediments.
chloride for 24–48 h.
Acid extraction — Adjust the pH of the waters in the extractors METHOD SUMMARY Method 8240B covers 80 volatile
to 2 or less using 6 N sulfuric acid. Extract with methylene organic compounds that are introduced into a gas chromato-
chloride for 24–48 h. graph by the purge-and-trap method or by direct injection (in
Ultrasonic extraction of high solids samples — Add anhy- limited applications). For the purge-and-trap method an inert
drous sodium sulfate to the sample and QC aliquot(s). gas (zero grade nitrogen or helium) is bubbled through a 5-mL
Add acetone:methylene chloride (1:1) to the sample and solution at ambient temperature. Purged sample components
mix thoroughly are trapped in a tube of sorbent materials. When purging is
Concentrate extracts using a K-D apparatus. complete, the sorbent tube is heated and backflushed with inert
gas to desorb the trapped components onto a GC column.
QUALITY CONTROL The analyst is permitted to modify
this method to improve separations or lower the costs of mea- INTERFERENCES Impurities in the purge gas and from
surements, provided all performance specifications are met. organic compounds outgassing from the plumbing ahead of
Analyses of blanks are required to demonstrate freedom from the trap account for many contamination problems. Interfer-
contamination. When results of spikes indicate atypical ences purged or coextracted from the samples will vary con-
method performance for samples, the samples are diluted to siderably from source to source. Cross-contamination can
bring method performance within acceptable limits. occur whenever high-level and low-level samples are analyzed
sequentially. Whenever an unusually concentrated sample is
For low solids (aqueous samples), extract, concentrate, and analyzed, it should be followed by the analysis of organic-free
analyze two sets of four 1-L aliquots (8 aliquots total) of the reagent water to check for cross-contamination. Samples also
precision and recovery standard. For high solids samples, two can be contaminated by diffusion of volatile organics (partic-
sets of four 30-g aliquots of the high solids reference matrix ularly methylene chloride and fluorocarbons) through the sep-
are used. tum seal into the sample during shipment and storage. A trip
Spike all samples with labeled compounds to assess method blank can serve as a check on such contamination. The lab
performance. Compute percent recovery of the labeled com- where volatile analysis is performed and also the refrigerated
pounds using the internal standard method. Compare the storage area should be completely free of solvents.
labeled compound recovery for each compound with the cor-
INSTRUMENTATION A gas chromatograph/mass spec-
responding labeled compound recovery.
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
Reagent water and high solids reference matrix blanks are ana- I.D. glass column packed with 1% SP-1000 on Carbopack-B
lyzed to demonstrate freedom from contamination. Extract (60/80 mesh) is required.Also needed is a 5-mL purging device,
and concentrate a 1-L reagent water blank or a high solids a sorbent trap, and a thermal desorption apparatus.

©1996 CRC Press LLC


PRECISION & ACCURACY This method is reported to have SAMPLE PREPARATION
been tested by 15 laboratories using organic-free reagent water, Liquid samples — Remove the plunger from a 5-mL syringe
drinking water, surface water, and industrial wastewaters (not and carefully pour the sample into the syringe barrel to just
specified) fortified at six concentrations over the range 5– short of overflowing. Replace the syringe plunger and compress
600 g/L. the sample. Open the syringe valve and vent any residual air
while adjusting the sample volume to 5.0 mL. If there is only
Sample estimated quantitation limits (EQLs) are highly one volatile organic analysis (VOA) vial, a second syringe
matrix-dependent. The EQLs listed may not always be achiev- should be filled at this time to protect against possible loss of
able. EQLs listed for soils or sediments are based on wet weight. sample integrity. Add 10 L of surrogate spiking solution and
Normally, data is reported on a dry-weight basis; therefore, 10 L of internal standard spiking solution through the valve
EQLs will be higher, based on the percent dry weight of each bore of the 5-mL syringe, then close the valve. The surrogate
sample. Note that EQLs are even more variable than MDLs and and internal standards may be mixed and added as a single
that they are highly variable depending on the matrix being spiking solution.
analyzed.
Sediments, soils, and waste samples — All samples of this type
EQL in groundwater in g/L was not listed. should be screened by GC analysis using a headspace method
EQL in low soil or sediment in g/kg was not listed. (EPA Method 3810) or the hexadecane extraction and screen-
Accuracy (a) in g/L was not listed. ing method (EPA Method 3820). Use the screening data to
Precision (b) in g/L was not listed. determine whether to use the low-concentration method
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
(a) Average recovery found for measurements of samples con-
taining a concentration of C, in g/L. Low-concentration method — The low-concentration method
(b) Overall precision found for measurements of samples with is based on purging a heated sediment or soil sample mixed
average recovery X for samples containing a concentration with organic-free reagent water containing the surrogate and
of C in g/L. internal standards. Analyze all reagent blanks and standards
X = Average recovery found for measurement of samples con- under the same conditions as the samples.
taining a concentration of C in g/L.
Use a 5-g sample if the expected concentration is <0.1 mg/kg
MULTIPLICATION FACTORS FOR OTHER MATRICES or a 1-g sample for expected concentrations between 0.1 and
Other Matrices Factor (a) 1 mg/kg. Mix the contents of the sample container with a nar-
row metal spatula. Weigh the amount of the sample into a tared
Waste miscible liquid waste 50 purge device. Add the spiked water to the purge device, which
High-concentration soil and sludge 125 contains the weighed amount of sample, and connect the
Non-water miscible waste 500 device to the purge-and-trap system.
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous High-concentration method — This method is based on
samples, the factor is on a wet-weight basis. extracting the sediment or soil with methanol. A waste sample
SAMPLING METHOD is either extracted or diluted, depending on its solubility in
Liquid samples — Use a 40-mL glass screw-cap VOA vial with methanol. Wastes that are insoluble in methanol are diluted
a Teflon®-faced silicone septum that has been prewashed, with reagent tetraglyme or possibly polyethylene glycol (PEG).
rinsed with distilled deionized water, and oven dried. However, An aliquot of the extract is added to organic-free reagent water
if residual chlorine is present, collect sample in a 40-oz. soil containing surrogate and internal standards. This is purged at
VOA container which has been pre-preserved with 4 drops of ambient temperature. All samples with an expected concentra-
10% sodium thiosulfate, mix gently, and then transfer the sam- tion of >1.0 mg/kg should be analyzed by this method.
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli- Mix the contents of the sample container with a narrow metal
cate and seal them in separate plastic bags. spatula. For sediments or soils and solid wastes that are insol-
uble in methanol, weigh 4 g (wet weight) of sample into a tared
Soils or sediments, and sludges — Use an 8-oz. widemouth
20-mL vial. For waste that is soluble in methanol, tetraglyme,
glass bottle with a Teflon®-faced silicone septum that has been
or PEG, weigh 1 g (wet weight) into a tared scintillation vial
prewashed with detergent, rinsed with distilled deionized
or culture tube or a 10-mL volumetric flask. Quickly add
water, and oven dried. Tap slightly to eliminate free air space.
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
Collect samples in duplicate and seal them in separate plastic bags. spiking solution to the vial, cap it, and shake it for 2 min.
SAMPLE PRESERVATION METHANOL EXTRACT REQUIRED FOR ANALYSIS
Liquid samples — Add 4 drops of concentrated HCL and
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
immediately cool samples to 4C and store in a solvent-free
refrigerator. Approximate Volume of
Concentration Range Methanol Extract (a)
Soils or sediments, and sludges — Cool samples to 4C and
500–10,000 g/kg 100 L
store in a solvent-free refrigerator.
1,000–20,000 g/kg 50 L
MHT Maximum holding time is 14 days from the date of 5,000–100,000 g/kg 10 L
sample collection. 25,000–500,000 g/kg 100 L of 1/50 dilution (b)

©1996 CRC Press LLC


Calculate appropriate dilution factor for concentrations trated sample is encountered, it should be followed by the
exceeding this table. analysis of blank solvent to check for cross-contamination.
(a) The volume of methanol added to 5 mL of water being purged INSTRUMENTATION A GC/MS and a data system are
should be kept constant. Therefore, add to the 5-mLsyringe whatever required. The GC column used is a 30 m 0.25 mm I.D. (or
volume of methanol is necessary to maintain a volume of 100 L 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
added to the syringe. capillary column. A continuous liquid-liquid extractor
(b) Dilute an aliquot of the methanol extract and then take 100 L equipped with Teflon® or glass connection joints and stopcocks
for analysis. requiring no lubrication, a K-D concentrating apparatus, water
QUALITY CONTROL Demonstrate, through the analysis of bath, and an ultrasonic disrupter with a minimum power of
a reagent water blank, that interferences from the analytical 300 W and with pulsing capability are also required.
system, glassware, and reagents are under control. Blank sam- PRECISION & ACCURACY The estimated quantitation
ples should be carried through all stages of the sample prepa- limit (EQL) of Method 8270B for determining an individual
ration and measurement steps. For each analytical batch (up compound is approximately 1 mg/kg (wet weight) for soil or
to 20 samples), a reagent blank, matrix spike, and matrix spike sediment samples, 1–200 mg/kg for wastes (dependent on
duplicate must be analyzed (the frequency of the spikes may matrix and method of preparation), and 10 g/L for ground-
be different for different monitoring programs). The blank and water samples. EQLs will be proportionately higher for sample
spiked samples must be carried through all stages of the sample extracts that require dilution to avoid saturation of the detector.
preparation and measurement steps. QC samples mentioned
in the section on Interferences will also be needed as appropri- The EQL(b) for groundwater in g/L is not determined.
ate to those situations. The EQL (a, b) for low concentrations in soil and sediment
in g/kg is not determined.
REFERENCE Test Methods for Evaluating Solid Waste (SW- Accuracy as g/L is not listed.
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office Overall precision in g/L is not listed.
of Solid Wastes, Washington, DC.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
2-Picoline EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #109-06-8 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
MATRIX This method is used to determine the concentra- C = True value for concentration, in g/L.
tion of semivolatile organic compounds in extracts prepared X = Average recovery found for measurements of samples con-
from all types of solid waste matrices, soils, and groundwater. taining a concentration of C, in g/L.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers,
lakes, etc. Other Matrices Factor (a)
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile
Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
tion of the sample into the GC/MS system may be appropriate, (a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
but this results in very high detection limits (approximately This estimated EQL is similar to an EPA “Practical Quantitation
10,000 g/L). Typically, a 1-L liquid sample, containing surro- Limit.”
gate, and matrix spiking standards, is extracted in a continuous
SAMPLING METHOD
extractor first under acid conditions and then under basic con-
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate,
and matrix spiking standards, is extracted ultrasonically. After a screw-top Teflon®-lined cover that has been prewashed with
detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an
isopropanol).
internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral Soils, sediments, or sludges — Use an 8-oz. widemouth glass
and 200 ng of acid surrogates (for a 1-L injection). Analysis with a screw-top Teflon®-lined cover that has been prewashed
is performed by GC/MS using a capillary GC column. with detergent and rinsed with distilled water and methanol
(or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam-
ples, and spikes must be evaluated for interferences. Contam- SAMPLE PRESERVATION
ination by carryover can occur whenever high-concentration Liquid samples — If residual chlorine is present, add 3 mL of
and low-concentration samples are sequentially analyzed. To 10% sodium thiosulfate per gallon, cool to 4C and store in a
reduce carryover, the sample syringe must be rinsed out solvent-free refrigerator until analysis; if chlorine is not present,
between samples with solvent. Whenever an unusually concen- then eliminate the sodium thiosulfate addition.

©1996 CRC Press LLC


Soils, sediments, or sludges — Cool samples to 4C and store inspected for malfunctions and corrections must be made, as
in a solvent-free refrigerator. required. If the electron ionization current plot (EICP) area for
any of the internal standards changes by a factor of two from
MHT Liquid samples must be extracted within 7 days and
the last daily calibration standard check, the mass spectrometer
the extracts analyzed within 40 days. Soils, sediments, or slud-
ges may be stored for a maximum of 14 days and the extracts must be inspected for malfunctions and corrections must be
analyzed within 40 days. made, as appropriate.

SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,


Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust
REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for
18–24 h. Dry the extract through a column containing anhy- of Solid Waste, Washington, DC.
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous Piperonyl sulfoxide EPA Method 8270
or wet samples (gummy or clay type) that do not have a free- CAS #120-62-7
flowing sandy texture must be mixed with anhydrous sodium
sulfate until the sample is free flowing. Add 1 mL of surrogate TITLE Semivolatile Organic Compounds by GC/MS
standards to all samples, spikes, standards, and blanks. For the MATRIX This method is used to determine the concentra-
sample in each analytical batch selected for spiking, add 1.0 mL tion of semivolatile organic compounds in extracts prepared
of a matrix spiking standard. For base/neutral acid analysis, the from all types of solid waste matrices, soils, and groundwater.
amount added of the surrogates and matrix spiking com- Although surface waters are not specifically mentioned, this
pounds should result in a final concentration of 100 ng/ L of method should be applicable to water samples from rivers,
each base/neutral analyte and 200 ng/L of each acid analyte lakes, etc.
in the extract to be analyzed (assuming a 1- L injection).
Immediately add a 100-mL mixture of 1:1 methylene chlo- METHOD SUMMARY This method covers 259 semivolatile
ride:acetone and extract the sample ultrasonically for 3 min organic compounds. In very limited applications direct injec-
and then decant or filter the extracts. Repeat the extraction two tion of the sample into the GC/MS system may be appropriate,
or more times. Dry the extract using a column with anhydrous but this results in very high detection limits (approximately
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous
QUALITY CONTROL A methylene chloride solution con-
extractor first under acid conditions and then under basic con-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
ditions. Typically 30 g of a solid sample, containing surrogate,
used for tuning the GC/MS system each 12-h shift. A system
and matrix spiking standards, is extracted ultrasonically. After
performance check also must be made during every 12-h shift.
concentrating the extract to 1 mL it is spiked with 10 L of an
A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
rophenol, and benzidine is required to verify injection port internal standard solution just prior to analysis by GC/MS. The
inertness and GC column performance. A calibration standard volume injected should contain about 100 ng of base/neutral
at mid-concentration, containing each compound of interest, and 200 ng of acid surrogates (for a 1-L injection). Analysis
including all required surrogates, must be performed every 12 h is performed by GC/MS using a capillary GC column.
during analysis. After the system performance check is met, INTERFERENCES Raw GC/MS data from all blanks, sam-
calibration check compounds (CCCs) are used to check the ples, and spikes must be evaluated for interferences. Contam-
validity of the initial calibration. ination by carryover can occur whenever high-concentration
The internal standard responses and retention times in the and low-concentration samples are sequentially analyzed. To
calibration check standard must be evaluated immediately after reduce carryover, the sample syringe must be rinsed out
or during data acquisition. If the retention time for any internal between samples with solvent. Whenever an unusually concen-
standard changes by more than 30 seconds from the last check trated sample is encountered, it should be followed by the
calibration (12 h), the chromatographic system must be analysis of blank solvent to check for cross-contamination.

©1996 CRC Press LLC


INSTRUMENTATION A GC/MS and a data system are MHT Liquid samples must be extracted within 7 days and
required. The GC column used is a 30 m 0.25 mm I.D. (or the extracts analyzed within 40 days. Soils, sediments, or slud-
0.32 mm I.D.) 1um film thickness silicone-coated fused silica ges may be stored for a maximum of 14 days and the extracts
capillary column. A continuous liquid-liquid extractor analyzed within 40 days.
equipped with Teflon® or glass connection joints and stopcocks
SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
PRECISION & ACCURACY The estimated quantitation water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
limit (EQL) of Method 8270B for determining an individual sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
compound is approximately 1 mg/kg (wet weight) for soil or solution into each sample. For the sample in each analytical
sediment samples, 1–200 mg/kg for wastes (dependent on batch selected for spiking, add 1.0 mL of a matrix spiking stan-
matrix and method of preparation), and 10 g/L for ground- dard. For base/neutral acid analysis, the amount of the surro-
water samples. EQLs will be proportionately higher for sample gates and matrix spiking compounds added to the sample
extracts that require dilution to avoid saturation of the detector. should result in a final concentration of 100 ng/L of each
analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is 100. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
Overall precision in g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
(a) EQLs listed for soil/sediment are based on wet weight. Nor- concentrator.
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous
will be higher based on the % dry weight of each sample. or wet samples (gummy or clay type) that do not have a free-
This calculation is based on a 30 g sample and gel perme- flowing sandy texture must be mixed with anhydrous sodium
ation chromatography cleanup. sulfate until the sample is free flowing. Add 1 mL of surrogate
(b) Sample EQLs are highly matrix-dependent. The EQLs are standards to all samples, spikes, standards, and blanks. For the
provided for guidance and may not always be achievable. sample in each analytical batch selected for spiking, add 1.0 mL
C = True value for concentration, in g/L. of a matrix spiking standard. For base/neutral acid analysis, the
X = Average recovery found for measurements of samples con- amount added of the surrogates and matrix spiking com-
taining a concentration of C, in g/L. pounds should result in a final concentration of 100 ng/ L of
each base/neutral analyte and 200 ng/L of each acid analyte
ESTIMATED QUANTITATION LIMIT
in the extract to be analyzed (assuming a 1- L injection).
Other Matrices Factor (a) Immediately add a 100-mL mixture of 1:1 methylene chlo-
High-concentration soil and sludges by sonicator 7.5 ride:acetone and extract the sample ultrasonically for 3 min
Non-water miscible waste 75 and then decant or filter the extracts. Repeat the extraction two
or more times. Dry the extract using a column with anhydrous
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
This estimated EQL is similar to an EPA “Practical Quantitation
Limit.” QUALITY CONTROL A methylene chloride solution con-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD used for tuning the GC/MS system each 12-h shift. A system
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with performance check also must be made during every 12-h shift.
a screw-top Teflon®-lined cover that has been prewashed with A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
detergent and rinsed with distilled water and methanol (or rophenol, and benzidine is required to verify injection port
isopropanol). inertness and GC column performance. A calibration standard
Soils, sediments, or sludges — Use an 8-oz. widemouth glass at mid-concentration, containing each compound of interest,
with a screw-top Teflon®-lined cover that has been prewashed including all required surrogates, must be performed every 12 h
with detergent and rinsed with distilled water and methanol during analysis. After the system performance check is met,
(or isopropanol). calibration check compounds (CCCs) are used to check the
validity of the initial calibration.
SAMPLE PRESERVATION
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
calibration check standard must be evaluated immediately after
10% sodium thiosulfate per gallon, cool to 4C and store in a
or during data acquisition. If the retention time for any internal
solvent-free refrigerator until analysis; if chlorine is not present,
standard changes by more than 30 seconds from the last check
then eliminate the sodium thiosulfate addition.
calibration (12 h), the chromatographic system must be
Soils, sediments, or sludges — Cool samples to 4C and store inspected for malfunctions and corrections must be made, as
in a solvent-free refrigerator. required. If the electron ionization current plot (EICP) area for

©1996 CRC Press LLC


any of the internal standards changes by a factor of two from ACCURACY Mean recovery = 93% 6% of spiked elements
the last daily calibration standard check, the mass spectrometer for all wastes.
must be inspected for malfunctions and corrections must be
SAMPLING METHOD Wash sample container with deter-
made, as appropriate.
gent and tap water, rinse with 1 + 1 nitric acid and tap water,
Demonstrate, through the analysis of a reagent water blank, then rinse with 1 + 1 hydrochloric acid and tap water, then
that interferences from the analytical system, glassware, and rinse with deionized, distilled water in that order. Perform any
reagents are under control. The blank samples should be car- filtration or acid preservation steps when the sample is col-
ried through all stages of the sample preparation and measure- lected or as soon as possible thereafter.
ment steps. For each analytical batch (up to 20 samples), a
reagent blank, matrix spike, and matrix spike duplicate/dupli- STABILITY Cool samples to 4C.
cate must be analyzed (the frequency of the spikes may be MHT 24 h.
different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample QUALITY CONTROL Mixed calibration standards, an
preparation and measurement steps. A QC reference sample instrument check standard, and an interference check solution
concentrate containing each analyte at a concentration of are used in addition to a quality control sample. The quality
100 mg/L in methanol is required. control sample should be prepared in the same acid matrix as
the calibration standards at 10 times the instrumental detection
REFERENCE Test Methods for Evaluating Solid Waste (SW- limits and in accordance with the instructions provided by the
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office supplier. Furthermore, two types of blanks are required: a cal-
of Solid Waste, Washington, DC. ibration blank and a reagent blank.
REFERENCE Method 200.7, U.S. EPA, EMSL-Cincinnati,
OH, Nov. 1980
Potassium EPA Method 200.7
CAS #7440-09-7

TITLE Inductively Coupled Plasma Potassium EPA Method 6010


CAS #7440-09-7
MATRIX Dissolved, suspended or (ICP) total element in
drinking and surface waters and in domestic and industrial TITLE Inductively Coupled Plasma
wastewaters.
MATRIX Applies to all matrices; (ICP) groundwater, EP
APPLICATION The method covers the determination of 25 extracts, soils, sludges, sediments, aqueous samples, solid and
metals. Dissolved elements are determined in filtered and acid- industrial wastes.
ified samples after appropriate digestion (which increases dis-
solved solids). Its primary advantage is that ICP instruments APPLICATION The method covers the determination of 25
allow simultaneous or rapid sequential determination of many metals. Its primary advantage is that ICP instruments allow
elements in a short time. Samples are first nebulized and the simultaneous or rapid sequential determination of many ele-
aerosol is transported to a plasma torch in which element spe- ments in a short time. Samples require digestion prior to anal-
cific atomic line emission spectra are produced by a radio fre- ysis and are first nebulized and the aerosol is transported to a
quency inductively coupled plasma. Background correction is plasma torch in which element specific atomic line emission
required for trace element detection except in the case of line spectra are produced by a radio frequency inductively coupled
broadning. plasma. Background correction is required for trace element
detection except in the case of line broadning.
INTERFERENCES There are spectral, physical, and chemical
interferences. The primary disadvantage of ICP instruments is INTERFERENCES There are spectral, physical, and chemical
background radiation from other elements and the plasma interferences. The primary disadvantage of ICP instruments is
gases (spectral interferences). Changes in sample viscosity and background radiation from other elements and the plasma
surface tension with samples containing high dissolved solids gases (spectral interferences). Changes in sample viscosity and
(especially those exceeding 1500 mg/L) or high acid concentra- surface tension with samples containing high dissolved solids
tions can cause physical interferences. Ionization effects, solute or high acid concentrations can cause physical interferences.
vaporization and molecular compound formation can cause With effects, solute vaporization and molecular compound for-
chemical interferences. mation can cause chemical interferences.
INSTRUMENTATION Inductively coupled argon plasma INSTRUMENTATION Inductively coupled argon plasma
emission spectroscopy. 766.491 nm wavelength emission spectroscopy. 766.491 nm wavelength
RANGE Not listed. RANGE Not listed.
MDL Highly dependent on operating conditions and plasma MDL Highly dependent on operating conditions and plasma
position. position.
PRECISION Not listed. PRECISION Not listed.

©1996 CRC Press LLC


ACCURACY Mean recovery = 93% 6% of spiked elements per day, verify working standard curve. Run an additional stan-
for all wastes. dard at or near mid-range every 10 samples.
SAMPLING METHOD Collect 400 mL of sample in plastic REFERENCE Method 7610, SW-846, 3rd ed., Nov.1986.
or glass containers.
STABILITY Cool samples to 4C.
Prometon EPA Method 507
MHT 6 months
CAS #1610-18-0
QUALITY CONTROL Mixed calibration standards, an
instrument check standard, and an interference check solution TITLE Determination of Nitrogen and Phosphorus-Con-
are used in addition to a quality control sample. The quality taining Pesticides in Water by GC/NPD
control sample should be prepared in the same acid matrix as MATRIX This method is applicable to the determination of
the calibration standards at 10 times the instrumental detection certain nitrogen and phosphorus-containing pesticides in fin-
limits and in accordance with the instructions provided by the ished drinking water and groundwater.
supplier. Furthermore, two types of blanks are required: a cal-
ibration blank and a reagent blank. METHOD SUMMARY Method 507 covers 46 nitrogen- and
phosphorus-containing pesticides. A 1-L sample is fortified
REFERENCE Method 6010, SW-846, 3rd ed., Nov.1986. with a surrogate standard, salted, buffered, extracted with
methylene chloride, and concentrated; then the solvent is
exchanged with methyl tert-butyl ether (MTBE) and concen-
Potassium EPA Method 7610 trated again, and a 2-L aliquot of a sample extract is injected
CAS #7440-09-7 into a GC system equipped with a selective nitrogen-phospho-
rus detector and a capillary column for analysis.
TITLE Atomic Absorption (AA) INTERFERENCES Method interferences may be caused by
MATRIX Drinking, surface, and direct aspiration saline contaminants in solvents, reagents, glassware, and other sample
waters, wastewater. processing apparatus. Interfering contamination may occur
when a sample containing low concentrations of analytes is
APPLICATION Sample is aspirated and atomized in a flame. analyzed immediately following a sample containing relatively
A light beam from a (K) hollow cathode lamp is directed high concentrations. One or more injections of MTBE should
through the flame into monochromator and onto detector. be made following the analysis of a sample with high concen-
Since wavelength of light beam is specific for potassium, light trations of analytes to check for analyte carryover. Matrix inter-
energy absorbed by detector is measure of potassium. ferences may be caused by contaminants that are coextracted
from the sample. The extent of matrix interferences will vary
INTERFERENCES The most troublesomee type is chemical, considerably from source to source, depending upon the water
caused by lack of absorption of atoms bound in molecular sampled.
combination in the flame. High dissolved solids in sample may
result in nonatomic absorbance interference. Other alkali salts INSTRUMENTATION A gas chromatograph system (GC)
in the sample and sodium can interfere. equipped with a nitrogen-phosphorus detector (NPD) is
needed.
INSTRUMENTATION Atomic absorption spectrometer.
Potassium hollow cathode lamp. (766.5 nm wavelength) Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
umn, 0.25 m film thickness, or equivalent.
RANGE 0.1–2 mg/L Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
MDL 0.01 mg/L column, 0.25 m film thickness, or equivalent.

PRECISION Standard deviation = 0.20 and 0.50 at 1.60 and PRECISION & ACCURACY This method has been validated
6.30 mg K/L in a single lab and estimated detection limits (EDLs) have been
determined for each analyte. Observed detection limits may
ACCURACY Recoveries = 103 and 102% at 1.60 and 6.30 mg vary among waters, depending upon the nature of the inter-
K/L ferences in the sample matrix and the specific instrumentation
SAMPLING METHOD Use glass or plastic containers. Col- used. Analytes that are not separated chromatographically can-
lect 200 g of solids and 600 mL of liquid samples. not be individually identified and measured unless an alterna-
tive technique for identification and quantification exist.
STABILITY Cool solid samples to 4C and analyze as soon
as possible. Add nitric acid to liquid samples to pH <2. The estimated detection limit (in g/L) was 0.3. The EDL is
defined as either method detection limit or a level of compound
MHT 6 months. in a sample yielding a peak in the final extract with signal-to-
noise ratio of approximately 5, whichever value is higher.
QUALITY CONTROL At least one duplicate and one spike
sample should be run every 20 samples or with each matrix The concentration used for these measurements (in g/L) was 3.
type to verify precision of the method. For 20 or more samples The accuracy (as % recovery) was 78.

©1996 CRC Press LLC


The precision (% RSD) was 9. 20460. Tel. (202) 260-3040. For further information the EPA
Safe Drinking Water Hotline may be called at: (800) 426-4791.
SAMPLING METHOD Grab samples are collected in 1-L
glass sample bottles (prewashed with detergent and hot tap REFERENCE Methods for the Determination of Organic
water, rinsed with reagent water, and dried in an oven at 400C Compounds in Drinking Water, EPA/600/4-88/039 (revised
for 1 h) with screw caps lined with PTFE-fluorocarbon. July 1991). U.S. EPA Environmental Monitoring Systems Lab-
SAMPLE PRESERVATION Add mercuric chloride to the oratory, Cincinnati, OH, 45268, U.S.A. Available from the
sample bottle in amounts to produce a concentration of National Technical Information Service (NTIS), 5285 Port
10 mg/L. If residual chlorine is present, add 80 mg of sodium Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
thiosulfate/L of sample to the sample bottle prior to collection. Order Number is PB91-231480.
After collection, seal bottle and shake vigorously for 1 min, then
cool the sample to 4C immediately and store it at 4C in the
dark until extraction. Prometryn EPA Method 507
MHT Maximum holding time of the samples, and in some CAS #7287-19-6
cases the extracts, is 14 days.
TITLE Determination of Nitrogen and Phosphorus-Con-
SAMPLE PREPARATION Fortify the sample with 50 L of taining Pesticides in Water by GC/NPD
the surrogate standard solution, adjust to pH 7 with phosphate
buffer, add 100 g NaCl to the sample, and seal and shake to MATRIX This method is applicable to the determination of
dissolve the salt; then extract with methylene chloride in a certain nitrogen and phosphorus-containing pesticides in fin-
separatory funnel or in a mechanical tumbler bottle. Dry the ished drinking water and groundwater.
extract by pouring it through a solvent-rinsed drying column
METHOD SUMMARY Method 507 covers 46 nitrogen- and
containing about 10 cm of anhydrous sodium sulfate. Collect
phosphorus-containing pesticides. A 1-L sample is fortified
the extract in a Kuderna-Danish (K-D) concentrator and rinse
the column with 20–30 mL methylene chloride. Concentrate with a surrogate standard, salted, buffered, extracted with
the extract to about 2 mL and rinse the flask and its lower joint methylene chloride, and concentrated; then the solvent is
into the concentrator tube with 1 to 2 mL of methyl t-butyl exchanged with methyl tert-butyl ether (MTBE) and concen-
ether (MTBE). Add 5–10 mL of MTBE and concentrate the trated again, and a 2-L aliquot of a sample extract is injected
extract twice (adding more MTBE) to a final volume of 5.0 mL into a GC system equipped with a selective nitrogen-phospho-
and store it at 4C until analysis. rus detector and a capillary column for analysis.

Note: If methylene chloride is not completely removed from INTERFERENCES Method interferences may be caused by
the final extract, it may cause detector problems. contaminants in solvents, reagents, glassware, and other sample
processing apparatus. Interfering contamination may occur
QUALITY CONTROL Minimum quality control require- when a sample containing low concentrations of analytes is
ments are initial demonstration of lab capability, determina- analyzed immediately following a sample containing relatively
tion of surrogate compound recoveries in each sample and high concentrations. One or more injections of MTBE should
blank, monitoring internal standard peak area or height in each
be made following the analysis of a sample with high concen-
sample and blank, analysis of lab reagent blanks, lab fortified
trations of analytes to check for analyte carryover. Matrix inter-
samples, lab fortified blanks, and other QC samples. A lab
ferences may be caused by contaminants that are coextracted
reagent blank is analyzed to demonstrate that all glassware and
reagent interferences are under control. from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the water
Initial demonstration of capability is fulfilled by analyzing four sampled.
fortified reagent water samples with the recovery value for each
analyte falling within the acceptable range ( 30% average INSTRUMENTATION A gas chromatograph system (GC)
recovery). Surrogate recoveries from samples or method blanks equipped with a nitrogen-phosphorus detector (NPD) is
must be 70–130%. The internal standard response for any sam- needed.
ple chromatogram should not deviate from the daily calibra- Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
tion check standard’s internal standard response by more than umn, 0.25 m film thickness, or equivalent.
30% or lab fortified blanks and sample matrices are used to Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
assess lab performance and analyte recovery, respectively. column, 0.25 m film thickness, or equivalent.
If the response for the target analyte peak exceeds the working PRECISION & ACCURACY This method has been validated
range of the system, dilute the extract and reanalyze.Alternative in a single lab and estimated detection limits (EDLs) have been
techniques such as an alternate detector or second chromatog-
determined for each analyte. Observed detection limits may
raphy column should be used to confirm peak identification
vary among waters, depending upon the nature of the inter-
when sample components are not resolved adequately.
ferences in the sample matrix and the specific instrumentation
EPA CONTACT & HOTLINE For technical questions contact used. Analytes that are not separated chromatographically can-
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and not be individually identified and measured unless an alterna-
Drinking Water (WH-550D), 401 M St. SW, Washington, DC tive technique for identification and quantification exist.

©1996 CRC Press LLC


The estimated detection limit (in g/L) was 0.19. The EDL is If the response for the target analyte peak exceeds the working
defined as either method detection limit or a level of compound range of the system, dilute the extract and reanalyze.Alternative
in a sample yielding a peak in the final extract with signal-to- techniques such as an alternate detector or second chromatog-
noise ratio of approximately 5, whichever value is higher. raphy column should be used to confirm peak identification
when sample components are not resolved adequately.
The concentration used for these measurements (in g/L) was
1.9. EPA CONTACT & HOTLINE For technical questions contact
The accuracy (as % recovery) was 93. Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and
The precision (% RSD) was 8. Drinking Water (WH-550D), 401 M St. SW, Washington, DC
20460. Tel. (202) 260-3040. For further information the EPA
SAMPLING METHOD Grab samples are collected in 1-L Safe Drinking Water Hotline may be called at: (800) 426-4791.
glass sample bottles (prewashed with detergent and hot tap
water, rinsed with reagent water, and dried in an oven at 400C REFERENCE Methods for the Determination of Organic
for 1 h) with screw caps lined with PTFE-fluorocarbon. Compounds in Drinking Water, EPA/600/4-88/039 (revised
July 1991). U.S. EPA Environmental Monitoring Systems Lab-
SAMPLE PRESERVATION Add mercuric chloride to the oratory, Cincinnati, OH, 45268, U.S.A. Available from the
sample bottle in amounts to produce a concentration of National Technical Information Service (NTIS), 5285 Port
10 mg/L. If residual chlorine is present, add 80 mg of sodium Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
thiosulfate/L of sample to the sample bottle prior to collection. Order Number is PB91-231480.
After collection, seal bottle and shake vigorously for 1 min, then
cool the sample to 4C immediately and store it at 4C in the
dark until extraction.
Pronamide EPA Method 1625
MHT Maximum holding time of the samples, and in some CAS #23950-58-5
cases the extracts, is 14 days.
SAMPLE PREPARATION Fortify the sample with 50 L of TITLE Semivolatile Organic Compounds by Isotope Dilu-
the surrogate standard solution, adjust to pH 7 with phosphate tion GC/MS
buffer, add 100 g NaCl to the sample, and seal and shake to MATRIX The compounds may be determined in waters,
dissolve the salt; then extract with methylene chloride in a soils, and municipal sludges by this method.
separatory funnel or in a mechanical tumbler bottle. Dry the
METHOD SUMMARY This method is used to determine
extract by pouring it through a solvent-rinsed drying column
176 semivolatile toxic organic pollutants associated with the
containing about 10 cm of anhydrous sodium sulfate. Collect
CWA (as amended 1987); the RCRA (as amended 1986); the
the extract in a Kuderna-Danish (K-D) concentrator and rinse
CERCLA (as amended 1986); and other compounds amenable
the column with 20–30 mL methylene chloride. Concentrate
to extraction and analysis by capillary column gas chromatog-
the extract to about 2 mL and rinse the flask and its lower joint
raphy-mass spectrometry (GC/MS).
into the concentrator tube with 1 to 2 mL of methyl t-butyl
ether (MTBE). Add 5–10 mL of MTBE and concentrate the Stable isotopically-labeled analogs of the compounds of interest
extract twice (adding more MTBE) to a final volume of 5.0 mL are added to the sample. If the solids content is less than 1%,
and store it at 4C until analysis. a 1-L sample is extracted at pH 12–13, then at pH <2 with
methylene chloride using continuous extraction techniques.
Note: If methylene chloride is not completely removed from
the final extract, it may cause detector problems. If the solids content is 30% or less, the sample is diluted to 1%
solids with reagent water, homogenized ultrasonically, and
QUALITY CONTROL Minimum quality control require- extracted at pH 12–13, then at pH <2 with methylene chloride
ments are initial demonstration of lab capability, determina- using continuous extraction techniques. If the solids content is
tion of surrogate compound recoveries in each sample and greater than 30%, the sample is extracted using ultrasonic
blank, monitoring internal standard peak area or height in each techniques.
sample and blank, analysis of lab reagent blanks, lab fortified
samples, lab fortified blanks, and other QC samples. A lab Each extract is dried over sodium sulfate, concentrated to a
reagent blank is analyzed to demonstrate that all glassware and volume of 5 mL, cleaned up using GPC, if necessary, and con-
reagent interferences are under control. centrated. Extracts are concentrated to 1 mL if GPC is not
performed, and to 0.5 mL if GPC is performed.
Initial demonstration of capability is fulfilled by analyzing four
fortified reagent water samples with the recovery value for each An internal standard is added to the extract, and a 1-mL aliquot
of the extract is injected into the GC. The compounds are
analyte falling within the acceptable range ( 30% average
separated by GC and detected by a MS. The labeled compounds
recovery). Surrogate recoveries from samples or method blanks
serve to correct the variability of the analytical technique.
must be 70–130%. The internal standard response for any sam-
ple chromatogram should not deviate from the daily calibra- INTERFERENCES Solvents, reagents, glassware, and other
tion check standard’s internal standard response by more than sample processing hardware may yield artifacts and/or elevated
30% or lab fortified blanks and sample matrices are used to baselines causing misinterpretation of chromatograms and
assess lab performance and analyte recovery, respectively. spectra. Materials used in the analysis must be demonstrated

©1996 CRC Press LLC


to be free from interferences under the conditions of analysis Ultrasonic extraction of high solids samples — Add anhy-
by running method blanks initially and with each sample lot drous sodium sulfate to the sample and QC aliquot(s).
(sample started through the extraction process on a given 8-h Add acetone:methylene chloride (1:1) to the sample and
shift, to a maximum of 20). Specific selection of reagents and mix thoroughly
purification of solvents by distillation in all glass systems may
be required. Glassware and, where possible, reagents are Concentrate extracts using a K-D apparatus.
cleaned by solvent rinse and baking at 450C for 1-h minimum. QUALITY CONTROL The analyst is permitted to modify
Interferences coextracted from samples will vary considerably this method to improve separations or lower the costs of mea-
from source to source, depending on the diversity of the site surements, provided all performance specifications are met.
being sampled. Analyses of blanks are required to demonstrate freedom from
INSTRUMENTATION Major instrumentation includes a GC contamination. When results of spikes indicate atypical
with a splitless or on-column injection port for capillary col- method performance for samples, the samples are diluted to
umn, a MS with 70 eV electron impact ionization, and a data bring method performance within acceptable limits.
system to collect and record MS data, and process it. A K-D For low solids (aqueous samples), extract, concentrate, and
apparatus is used to concentrate extracts.
analyze two sets of four 1-L aliquots (8 aliquots total) of the
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% precision and recovery standard. For high solids samples, two
vinyl silicone bonded phased fused silica capillary column. sets of four 30-g aliquots of the high solids reference matrix
are used.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences Spike all samples with labeled compounds to assess method
rather than instrumental limitations. The limits typify the min- performance. Compute percent recovery of the labeled com-
imum quantities that can be detected with no interferences pounds using the internal standard method. Compare the
present. labeled compound recovery for each compound with the cor-
The minimum level (in g/mL) was not listed. This is defined responding labeled compound recovery.
as a minimum level at which the analytical system shall give Reagent water and high solids reference matrix blanks are ana-
recognizable mass spectra (background corrected) and accept- lyzed to demonstrate freedom from contamination. Extract
able calibration points. and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was not listed and in high reference matrix blank with each sample’s lot (samples started
solids was not listed; these were determined in digested sludge through the extraction process on the same 8-h shift, to a
(low solids) and in filter cake or compost (high solids). maximum of 20 samples).
The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was not listed. the sampling technique, and spiked samples may be required
The labeled and native compound initial accuracy as average to determine the accuracy of the analysis when the internal
recovery (in g/L) was not listed. standard method is used.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Semivolatile Organic Compounds by Isotope
Collect samples in glass containers. Aqueous samples which Dilution GC/MS. Office of Water Regulation and Standards,
flow freely are collected in refrigerated bottles using automatic U.S. EPA Industrial Technology Division, Washington, DC,
sampling equipment. Solid samples are collected as grab sam- EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
ples using widemouth jars. Maintain samples at 0 to 4C from U.S. EPA, Office of Water Regulations and Standards, 401 M
the time of collection until extraction. If residual chlorine is St., SW, Washington, DC, 20460. Phone: 202-382-7131).
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction.
Pronamide EPA Method 1625
SAMPLE PREPARATION Samples containing 1% solids or CAS #23950-58-5
less are extracted directly using continuous liquid-liquid
extraction techniques. Samples containing 1 to 30% solids are TITLE Semivolatile Organic Compounds by Isotope Dilu-
diluted to the 1% level with reagent water and extracted using tion GC/MS
continuous liquid-liquid extraction techniques. Samples con-
taining greater than 30% solids are extracted using ultrasonic MATRIX The compounds may be determined in waters,
techniques. soils, and municipal sludges by this method.
Base/neutral extraction — Adjust the pH of the waters in the METHOD SUMMARY This method is used to determine
extractors to 12–13 with 6 N NaOH. Extract with methylene 176 semivolatile toxic organic pollutants associated with the
chloride for 24–48 h. CWA (as amended 1987); the RCRA (as amended 1986); the
Acid extraction — Adjust the pH of the waters in the extractors CERCLA (as amended 1986); and other compounds amenable
to 2 or less using 6 N sulfuric acid. Extract with methylene to extraction and analysis by capillary column gas chromatog-
chloride for 24–48 h. raphy-mass spectrometry (GC/MS).

©1996 CRC Press LLC


Stable isotopically-labeled analogs of the compounds of interest The labeled and native compound initial accuracy as average
are added to the sample. If the solids content is less than 1%, recovery (in g/L) was not listed.
a 1-L sample is extracted at pH 12–13, then at pH <2 with
SAMPLE COLLECTION, PRESERVATION & HANDLING
methylene chloride using continuous extraction techniques.
Collect samples in glass containers. Aqueous samples which
If the solids content is 30% or less, the sample is diluted to 1% flow freely are collected in refrigerated bottles using automatic
solids with reagent water, homogenized ultrasonically, and sampling equipment. Solid samples are collected as grab sam-
extracted at pH 12–13, then at pH <2 with methylene chloride ples using widemouth jars. Maintain samples at 0 to 4C from
using continuous extraction techniques. If the solids content is the time of collection until extraction. If residual chlorine is
greater than 30%, the sample is extracted using ultrasonic present in aqueous samples, add 80 mg sodium thiosulfate/L
techniques. of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a
volume of 5 mL, cleaned up using GPC, if necessary, and con- SAMPLE PREPARATION Samples containing 1% solids or
centrated. Extracts are concentrated to 1 mL if GPC is not less are extracted directly using continuous liquid-liquid
performed, and to 0.5 mL if GPC is performed. extraction techniques. Samples containing 1 to 30% solids are
diluted to the 1% level with reagent water and extracted using
An internal standard is added to the extract, and a 1-mL aliquot continuous liquid-liquid extraction techniques. Samples con-
of the extract is injected into the GC. The compounds are taining greater than 30% solids are extracted using ultrasonic
separated by GC and detected by a MS. The labeled compounds techniques.
serve to correct the variability of the analytical technique.
Base/neutral extraction — Adjust the pH of the waters in the
INTERFERENCES Solvents, reagents, glassware, and other extractors to 12–13 with 6 N NaOH. Extract with methylene
sample processing hardware may yield artifacts and/or elevated chloride for 24–48 h.
baselines causing misinterpretation of chromatograms and Acid extraction — Adjust the pH of the waters in the extractors
spectra. Materials used in the analysis must be demonstrated to 2 or less using 6 N sulfuric acid. Extract with methylene
to be free from interferences under the conditions of analysis chloride for 24–48 h.
by running method blanks initially and with each sample lot Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h drous sodium sulfate to the sample and QC aliquot(s).
shift, to a maximum of 20). Specific selection of reagents and Add acetone:methylene chloride (1:1) to the sample and
purification of solvents by distillation in all glass systems may mix thoroughly
be required. Glassware and, where possible, reagents are
cleaned by solvent rinse and baking at 450C for 1-h minimum. Concentrate extracts using a K-D apparatus.
Interferences coextracted from samples will vary considerably QUALITY CONTROL The analyst is permitted to modify
from source to source, depending on the diversity of the site this method to improve separations or lower the costs of mea-
being sampled. surements, provided all performance specifications are met.
INSTRUMENTATION Major instrumentation includes a GC Analyses of blanks are required to demonstrate freedom from
with a splitless or on-column injection port for capillary col- contamination. When results of spikes indicate atypical
umn, a MS with 70 eV electron impact ionization, and a data method performance for samples, the samples are diluted to
system to collect and record MS data, and process it. A K-D bring method performance within acceptable limits.
apparatus is used to concentrate extracts. For low solids (aqueous samples), extract, concentrate, and
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% analyze two sets of four 1-L aliquots (8 aliquots total) of the
vinyl silicone bonded phased fused silica capillary column. precision and recovery standard. For high solids samples, two
sets of four 30-g aliquots of the high solids reference matrix
PRECISION & ACCURACY The detection limits of the are used.
method are usually dependent on the level of interferences
rather than instrumental limitations. The limits typify the min- Spike all samples with labeled compounds to assess method
imum quantities that can be detected with no interferences performance. Compute percent recovery of the labeled com-
pounds using the internal standard method. Compare the
present.
labeled compound recovery for each compound with the cor-
The minimum level (in g/mL) was not listed. This is defined responding labeled compound recovery.
as a minimum level at which the analytical system shall give
Reagent water and high solids reference matrix blanks are ana-
recognizable mass spectra (background corrected) and accept-
lyzed to demonstrate freedom from contamination. Extract
able calibration points.
and concentrate a 1-L reagent water blank or a high solids
The MDL (in g/kg) in low solids was not listed and in high reference matrix blank with each sample’s lot (samples started
solids was not listed; these were determined in digested sludge through the extraction process on the same 8-h shift, to a
(low solids) and in filter cake or compost (high solids). maximum of 20 samples).
The labeled and native compound initial precision as standard Field replicates may be collected to determine the precision of
deviation (in g/L) was not listed. the sampling technique, and spiked samples may be required

©1996 CRC Press LLC


to determine the accuracy of the analysis when the internal in a sample yielding a peak in the final extract with signal-to-
standard method is used. noise ratio of approximately 5, whichever value is higher.
REFERENCE Semivolatile Organic Compounds by Isotope The concentration used for these measurements (in g/L) was
Dilution GC/MS. Office of Water Regulation and Standards, 7.6.
U.S. EPA Industrial Technology Division, Washington, DC, The accuracy (as % recovery) was 91.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, The precision (% RSD) was 10.
U.S. EPA, Office of Water Regulations and Standards, 401 M
St., SW, Washington, DC, 20460. Phone: 202-382-7131). SAMPLING METHOD Grab samples are collected in 1-L
glass sample bottles (prewashed with detergent and hot tap
water, rinsed with reagent water, and dried in an oven at 400C
for 1 h) with screw caps lined with PTFE-fluorocarbon.
Pronamide EPA Method 507
CAS #23950-58-5 SAMPLE PRESERVATION Add mercuric chloride to the
sample bottle in amounts to produce a concentration of
TITLE Determination of Nitrogen and Phosphorus-Con- 10 mg/L. If residual chlorine is present, add 80 mg of sodium
taining Pesticides in Water by GC/NPD thiosulfate/L of sample to the sample bottle prior to collection.
After collection, seal bottle and shake vigorously for 1 min, then
MATRIX This method is applicable to the determination of cool the sample to 4C immediately and store it at 4C in the
certain nitrogen and phosphorus-containing pesticides in fin- dark until extraction.
ished drinking water and groundwater.
MHT Maximum holding time of the samples, and in some
METHOD SUMMARY Method 507 covers 46 nitrogen- and cases the extracts, is 14 days.
phosphorus-containing pesticides. A 1-L sample is fortified
with a surrogate standard, salted, buffered, extracted with Note: Samples with this compound must be extracted imme-
methylene chloride, and concentrated; then the solvent is diately.
exchanged with methyl tert-butyl ether (MTBE) and concen- SAMPLE PREPARATION Fortify the sample with 50 L of
trated again, and a 2-L aliquot of a sample extract is injected the surrogate standard solution, adjust to pH 7 with phosphate
into a GC system equipped with a selective nitrogen-phospho- buffer, add 100 g NaCl to the sample, and seal and shake to
rus detector and a capillary column for analysis. dissolve the salt; then extract with methylene chloride in a
INTERFERENCES Method interferences may be caused by separatory funnel or in a mechanical tumbler bottle. Dry the
contaminants in solvents, reagents, glassware, and other sample extract by pouring it through a solvent-rinsed drying column
processing apparatus. Interfering contamination may occur containing about 10 cm of anhydrous sodium sulfate. Collect
when a sample containing low concentrations of analytes is the extract in a Kuderna-Danish (K-D) concentrator and rinse
analyzed immediately following a sample containing relatively the column with 20–30 mL methylene chloride. Concentrate
high concentrations. One or more injections of MTBE should the extract to about 2 mL and rinse the flask and its lower joint
be made following the analysis of a sample with high concen- into the concentrator tube with 1 to 2 mL of methyl t-butyl
trations of analytes to check for analyte carryover. Matrix inter- ether (MTBE). Add 5–10 mL of MTBE and concentrate the
ferences may be caused by contaminants that are coextracted extract twice (adding more MTBE) to a final volume of 5.0 mL
from the sample. The extent of matrix interferences will vary and store it at 4C until analysis.
considerably from source to source, depending upon the water
sampled. Note: If methylene chloride is not completely removed from
the final extract, it may cause detector problems.
INSTRUMENTATION A gas chromatograph system (GC)
equipped with a nitrogen-phosphorus detector (NPD) is QUALITY CONTROL Minimum quality control require-
needed. ments are initial demonstration of lab capability, determina-
tion of surrogate compound recoveries in each sample and
Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col- blank, monitoring internal standard peak area or height in each
umn, 0.25 m film thickness, or equivalent. sample and blank, analysis of lab reagent blanks, lab fortified
Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica samples, lab fortified blanks, and other QC samples. A lab
column, 0.25 m film thickness, or equivalent. reagent blank is analyzed to demonstrate that all glassware and
PRECISION & ACCURACY This method has been validated reagent interferences are under control.
in a single lab and estimated detection limits (EDLs) have been Initial demonstration of capability is fulfilled by analyzing four
determined for each analyte. Observed detection limits may fortified reagent water samples with the recovery value for each
vary among waters, depending upon the nature of the inter-
analyte falling within the acceptable range ( 30% average
ferences in the sample matrix and the specific instrumentation
recovery). Surrogate recoveries from samples or method blanks
used. Analytes that are not separated chromatographically can-
must be 70–130%. The internal standard response for any sam-
not be individually identified and measured unless an alterna-
ple chromatogram should not deviate from the daily calibra-
tive technique for identification and quantification exist.
tion check standard’s internal standard response by more than
The estimated detection limit (in g/L) was 0.76. The EDL is 30% or lab fortified blanks and sample matrices are used to
defined as either method detection limit or a level of compound assess lab performance and analyte recovery, respectively.

©1996 CRC Press LLC


If the response for the target analyte peak exceeds the working requiring no lubrication, a K-D concentrating apparatus, water
range of the system, dilute the extract and reanalyze.Alternative bath, and an ultrasonic disrupter with a minimum power of
techniques such as an alternate detector or second chromatog- 300 W and with pulsing capability are also required.
raphy column should be used to confirm peak identification
when sample components are not resolved adequately. PRECISION & ACCURACY The estimated quantitation
limit (EQL) of Method 8270B for determining an individual
EPA CONTACT & HOTLINE For technical questions contact compound is approximately 1 mg/kg (wet weight) for soil or
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and sediment samples, 1–200 mg/kg for wastes (dependent on
Drinking Water (WH-550D), 401 M St. SW, Washington, DC matrix and method of preparation), and 10 g/L for ground-
20460. Tel. (202) 260-3040. For further information the EPA water samples. EQLs will be proportionately higher for sample
Safe Drinking Water Hotline may be called at: (800) 426-4791.
extracts that require dilution to avoid saturation of the detector.
REFERENCE Methods for the Determination of Organic
The EQL(b) for groundwater in g/L is 10.
Compounds in Drinking Water, EPA/600/4-88/039 (revised
The EQL (a, b) for low concentrations in soil and sediment
July 1991). U.S. EPA Environmental Monitoring Systems Lab-
in g/kg is not determined.
oratory, Cincinnati, OH, 45268, U.S.A. Available from the
Accuracy as g/L is not listed.
National Technical Information Service (NTIS), 5285 Port
Overall precision in g/L is not listed.
Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
Order Number is PB91-231480. (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
Pronamide EPA Method 8270 This calculation is based on a 30 g sample and gel perme-
CAS #23950-58-5 ation chromatography cleanup.
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc.
High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec-
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate,
This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately
Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral Soils, sediments, or sludges — Use an 8-oz. widemouth glass
and 200 ng of acid surrogates (for a 1-L injection). Analysis with a screw-top Teflon®-lined cover that has been prewashed
is performed by GC/MS using a capillary GC column. with detergent and rinsed with distilled water and methanol
(or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam-
ples, and spikes must be evaluated for interferences. Contam- SAMPLE PRESERVATION
ination by carryover can occur whenever high-concentration Liquid samples — If residual chlorine is present, add 3 mL of
and low-concentration samples are sequentially analyzed. To 10% sodium thiosulfate per gallon, cool to 4C and store in a
reduce carryover, the sample syringe must be rinsed out solvent-free refrigerator until analysis; if chlorine is not present,
between samples with solvent. Whenever an unusually concen- then eliminate the sodium thiosulfate addition.
trated sample is encountered, it should be followed by the
analysis of blank solvent to check for cross-contamination. Soils, sediments, or sludges — Cool samples to 4C and store
in a solvent-free refrigerator.
INSTRUMENTATION A GC/MS and a data system are
required. The GC column used is a 30 m 0.25 mm I.D. (or MHT Liquid samples must be extracted within 7 days and
0.32 mm I.D.) 1um film thickness silicone-coated fused silica the extracts analyzed within 40 days. Soils, sediments, or slud-
capillary column. A continuous liquid-liquid extractor ges may be stored for a maximum of 14 days and the extracts
equipped with Teflon® or glass connection joints and stopcocks analyzed within 40 days.

©1996 CRC Press LLC


SAMPLE PREPARATION Demonstrate, through the analysis of a reagent water blank,
Liquid samples — Transfer 1 L quantitatively to a continuous that interferences from the analytical system, glassware, and
extractor. If high concentrations are anticipated, a smaller vol- reagents are under control. The blank samples should be car-
ume may be used and then diluted with organic-free reagent ried through all stages of the sample preparation and measure-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ment steps. For each analytical batch (up to 20 samples), a
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking reagent blank, matrix spike, and matrix spike duplicate/dupli-
solution into each sample. For the sample in each analytical cate must be analyzed (the frequency of the spikes may be
batch selected for spiking, add 1.0 mL of a matrix spiking stan- different for different monitoring programs). The blank and
dard. For base/neutral acid analysis, the amount of the surro- spiked samples must be carried through all stages of the sample
gates and matrix spiking compounds added to the sample preparation and measurement steps. A QC reference sample
should result in a final concentration of 100 ng/L of each concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec- 100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust REFERENCE Test Methods for Evaluating Solid Waste (SW-
the pH of the aqueous phase to pH >11 using 10 N sodium 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
hydroxide and extract it with methylene chloride again for of Solid Waste, Washington, DC.
18–24 h. Dry the extract through a column containing anhy-
drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
Propargyl alcohol EPA Method 8240
Soils, sediments, or sludges — Use 30 g of sample. Nonporous CAS #107-19-7
or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium TITLE Volatile Organics By GC/MS: Packed Column Technique
sulfate until the sample is free flowing. Add 1 mL of surrogate
standards to all samples, spikes, standards, and blanks. For the MATRIX Nearly all types of sample matarices, regardless of
sample in each analytical batch selected for spiking, add 1.0 mL water content, can be analyzed using this method. This includes
of a matrix spiking standard. For base/neutral acid analysis, the groundwater, aqueous sludges, caustic liquors, acid liquors,
amount added of the surrogates and matrix spiking com- waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
pounds should result in a final concentration of 100 ng/ L of metric emulsions, filter cakes, spent carbons, spent catalysts,
each base/neutral analyte and 200 ng/L of each acid analyte soils, and sediments.
in the extract to be analyzed (assuming a 1- L injection). METHOD SUMMARY Method 8240B covers 80 volatile
Immediately add a 100-mL mixture of 1:1 methylene chlo- organic compounds that are introduced into a gas chromato-
ride:acetone and extract the sample ultrasonically for 3 min graph by the purge-and-trap method or by direct injection (in
and then decant or filter the extracts. Repeat the extraction two limited applications). For the purge-and-trap method an inert
or more times. Dry the extract using a column with anhydrous gas (zero grade nitrogen or helium) is bubbled through a 5-mL
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. solution at ambient temperature. Purged sample components
QUALITY CONTROL A methylene chloride solution con- are trapped in a tube of sorbent materials. When purging is
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is complete, the sorbent tube is heated and backflushed with inert
used for tuning the GC/MS system each 12-h shift. A system gas to desorb the trapped components onto a GC column.
performance check also must be made during every 12-h shift. INTERFERENCES Impurities in the purge gas and from
A standard containing 50 ng/L each of 4,4-DDT, pentachlo- organic compounds outgassing from the plumbing ahead of
rophenol, and benzidine is required to verify injection port the trap account for many contamination problems. Interfer-
inertness and GC column performance. A calibration standard ences purged or coextracted from the samples will vary con-
at mid-concentration, containing each compound of interest, siderably from source to source. Cross-contamination can
including all required surrogates, must be performed every 12 h occur whenever high-level and low-level samples are analyzed
during analysis. After the system performance check is met, sequentially. Whenever an unusually concentrated sample is
calibration check compounds (CCCs) are used to check the analyzed, it should be followed by the analysis of organic-free
validity of the initial calibration. reagent water to check for cross-contamination. Samples also
can be contaminated by diffusion of volatile organics (partic-
The internal standard responses and retention times in the
ularly methylene chloride and fluorocarbons) through the sep-
calibration check standard must be evaluated immediately after
tum seal into the sample during shipment and storage. A trip
or during data acquisition. If the retention time for any internal
blank can serve as a check on such contamination. The lab
standard changes by more than 30 seconds from the last check
where volatile analysis is performed and also the refrigerated
calibration (12 h), the chromatographic system must be
storage area should be completely free of solvents.
inspected for malfunctions and corrections must be made, as
required. If the electron ionization current plot (EICP) area for INSTRUMENTATION A gas chromatograph/mass spec-
any of the internal standards changes by a factor of two from trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
the last daily calibration standard check, the mass spectrometer I.D. glass column packed with 1% SP-1000 on Carbopack-B
must be inspected for malfunctions and corrections must be (60/80 mesh) is required.Also needed is a 5-mL purging device,
made, as appropriate. a sorbent trap, and a thermal desorption apparatus.

©1996 CRC Press LLC


PRECISION & ACCURACY This method is reported to have SAMPLE PREPARATION
been tested by 15 laboratories using organic-free reagent water, Liquid samples — Remove the plunger from a 5-mL syringe
drinking water, surface water, and industrial wastewaters (not and carefully pour the sample into the syringe barrel to just
specified) fortified at six concentrations over the range 5– short of overflowing. Replace the syringe plunger and compress
600 g/L. the sample. Open the syringe valve and vent any residual air
while adjusting the sample volume to 5.0 mL. If there is only
Sample estimated quantitation limits (EQLs) are highly one volatile organic analysis (VOA) vial, a second syringe
matrix-dependent. The EQLs listed may not always be achiev- should be filled at this time to protect against possible loss of
able. EQLs listed for soils or sediments are based on wet weight. sample integrity. Add 10 L of surrogate spiking solution and
Normally, data is reported on a dry-weight basis; therefore, 10 L of internal standard spiking solution through the valve
EQLs will be higher, based on the percent dry weight of each bore of the 5-mL syringe, then close the valve. The surrogate
sample. Note that EQLs are even more variable than MDLs and and internal standards may be mixed and added as a single
that they are highly variable depending on the matrix being spiking solution.
analyzed.
Sediments, soils, and waste samples — All samples of this type
EQL in groundwater in g/L was not listed. should be screened by GC analysis using a headspace method
EQL in low soil or sediment in g/kg was not listed. (EPA Method 3810) or the hexadecane extraction and screen-
Accuracy (a) in g/L was not listed. ing method (EPA Method 3820). Use the screening data to
Precision (b) in g/L was not listed. determine whether to use the low-concentration method
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
(a) Average recovery found for measurements of samples con-
taining a concentration of C, in g/L. Low-concentration method — The low-concentration method
(b) Overall precision found for measurements of samples with is based on purging a heated sediment or soil sample mixed
average recovery X for samples containing a concentration with organic-free reagent water containing the surrogate and
of C in g/L. internal standards. Analyze all reagent blanks and standards
X = Average recovery found for measurement of samples con- under the same conditions as the samples.
taining a concentration of C in g/L.
Use a 5-g sample if the expected concentration is <0.1 mg/kg
MULTIPLICATION FACTORS FOR OTHER MATRICES or a 1-g sample for expected concentrations between 0.1 and
Other Matrices Factor (a) 1 mg/kg. Mix the contents of the sample container with a nar-
row metal spatula. Weigh the amount of the sample into a tared
Waste miscible liquid waste 50 purge device. Add the spiked water to the purge device, which
High-concentration soil and sludge 125 contains the weighed amount of sample, and connect the
Non-water miscible waste 500 device to the purge-and-trap system.
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous High-concentration method — This method is based on
samples, the factor is on a wet-weight basis. extracting the sediment or soil with methanol. A waste sample
SAMPLING METHOD is either extracted or diluted, depending on its solubility in
Liquid samples — Use a 40-mL glass screw-cap VOA vial with methanol. Wastes that are insoluble in methanol are diluted
a Teflon®-faced silicone septum that has been prewashed, with reagent tetraglyme or possibly polyethylene glycol (PEG).
rinsed with distilled deionized water, and oven dried. However, An aliquot of the extract is added to organic-free reagent water
if residual chlorine is present, collect sample in a 40-oz. soil containing surrogate and internal standards. This is purged at
VOA container which has been pre-preserved with 4 drops of ambient temperature. All samples with an expected concentra-
10% sodium thiosulfate, mix gently, and then transfer the sam- tion of >1.0 mg/kg should be analyzed by this method.
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli- Mix the contents of the sample container with a narrow metal
cate and seal them in separate plastic bags. spatula. For sediments or soils and solid wastes that are insol-
uble in methanol, weigh 4 g (wet weight) of sample into a tared
Soils or sediments, and sludges — Use an 8-oz. widemouth
20-mL vial. For waste that is soluble in methanol, tetraglyme,
glass bottle with a Teflon®-faced silicone septum that has been
or PEG, weigh 1 g (wet weight) into a tared scintillation vial
prewashed with detergent, rinsed with distilled deionized
or culture tube or a 10-mL volumetric flask. Quickly add
water, and oven dried. Tap slightly to eliminate free air space.
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
Collect samples in duplicate and seal them in separate plastic bags. spiking solution to the vial, cap it, and shake it for 2 min.
SAMPLE PRESERVATION METHANOL EXTRACT REQUIRED FOR ANALYSIS
Liquid samples — Add 4 drops of concentrated HCL and
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
immediately cool samples to 4C and store in a solvent-free
refrigerator. Approximate Volume of
Concentration Range Methanol Extract (a)
Soils or sediments, and sludges — Cool samples to 4C and
500–10,000 g/kg 100 L
store in a solvent-free refrigerator.
1,000–20,000 g/kg 50 L
MHT Maximum holding time is 14 days from the date of 5,000–100,000 g/kg 10 L
sample collection. 25,000–500,000 g/kg 100 L of 1/50 dilution (b)

©1996 CRC Press LLC


Calculate appropriate dilution factor for concentrations INSTRUMENTATION A gas chromatograph system (GC)
exceeding this table. equipped with a nitrogen-phosphorus detector (NPD) is
needed.
(a) The volume of methanol added to 5 mL of water being purged
should be kept constant. Therefore, add to the 5-mLsyringe whatever Column 1: 30 m 0.25 mm I.D. DB-5 bonded fused silica col-
volume of methanol is necessary to maintain a volume of 100 L umn, 0.25 m film thickness, or equivalent.
added to the syringe. Column 2: 30 m 0.25 mm I.D. DB-1701 bonded fused silica
(b) Dilute an aliquot of the methanol extract and then take 100 L column, 0.25 m film thickness, or equivalent.
for analysis. PRECISION & ACCURACY This method has been validated
QUALITY CONTROL Demonstrate, through the analysis of in a single lab and estimated detection limits (EDLs) have been
a reagent water blank, that interferences from the analytical determined for each analyte. Observed detection limits may
system, glassware, and reagents are under control. Blank sam- vary among waters, depending upon the nature of the inter-
ferences in the sample matrix and the specific instrumentation
ples should be carried through all stages of the sample prepa-
used. Analytes that are not separated chromatographically can-
ration and measurement steps. For each analytical batch (up
not be individually identified and measured unless an alterna-
to 20 samples), a reagent blank, matrix spike, and matrix spike tive technique for identification and quantification exist.
duplicate must be analyzed (the frequency of the spikes may
be different for different monitoring programs). The blank and The estimated detection limit (in g/L) was 0.13. The EDL is
spiked samples must be carried through all stages of the sample defined as either method detection limit or a level of compound
preparation and measurement steps. QC samples mentioned in a sample yielding a peak in the final extract with signal-to-
in the section on Interferences will also be needed as appropri- noise ratio of approximately 5, whichever value is higher.
ate to those situations. The concentration used for these measurements (in g/L) was
1.3.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
The accuracy (as % recovery) was 92.
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office
The precision (% RSD) was 8.
of Solid Wastes, Washington, DC.
SAMPLING METHOD Grab samples are collected in 1-L
glass sample bottles (prewashed with detergent and hot tap
water, rinsed with reagent water, and dried in an oven at 400C
Propazine EPA Method 507 for 1 h) with screw caps lined with PTFE-fluorocarbon.
CAS #139-40-2
SAMPLE PRESERVATION Add mercuric chloride to the
TITLE Determination of Nitrogen and Phosphorus-Con- sample bottle in amounts to produce a concentration of
taining Pesticides in Water by GC/NPD 10 mg/L. If residual chlorine is present, add 80 mg of sodium
thiosulfate/L of sample to the sample bottle prior to collection.
MATRIX This method is applicable to the determination of After collection, seal bottle and shake vigorously for 1 min, then
certain nitrogen and phosphorus-containing pesticides in fin- cool the sample to 4C immediately and store it at 4C in the
ished drinking water and groundwater. dark until extraction.
METHOD SUMMARY Method 507 covers 46 nitrogen- and MHT Maximum holding time of the samples, and in some
phosphorus-containing pesticides. A 1-L sample is fortified cases the extracts, is 14 days.
with a surrogate standard, salted, buffered, extracted with
SAMPLE PREPARATION Fortify the sample with 50 L of
methylene chloride, and concentrated; then the solvent is
the surrogate standard solution, adjust to pH 7 with phosphate
exchanged with methyl tert-butyl ether (MTBE) and concen-
buffer, add 100 g NaCl to the sample, and seal and shake to
trated again, and a 2-L aliquot of a sample extract is injected dissolve the salt; then extract with methylene chloride in a
into a GC system equipped with a selective nitrogen-phospho- separatory funnel or in a mechanical tumbler bottle. Dry the
rus detector and a capillary column for analysis. extract by pouring it through a solvent-rinsed drying column
INTERFERENCES Method interferences may be caused by containing about 10 cm of anhydrous sodium sulfate. Collect
contaminants in solvents, reagents, glassware, and other sample the extract in a Kuderna-Danish (K-D) concentrator and rinse
the column with 20–30 mL methylene chloride. Concentrate
processing apparatus. Interfering contamination may occur
the extract to about 2 mL and rinse the flask and its lower joint
when a sample containing low concentrations of analytes is
into the concentrator tube with 1 to 2 mL of methyl t-butyl
analyzed immediately following a sample containing relatively ether (MTBE). Add 5–10 mL of MTBE and concentrate the
high concentrations. One or more injections of MTBE should extract twice (adding more MTBE) to a final volume of 5.0 mL
be made following the analysis of a sample with high concen- and store it at 4C until analysis.
trations of analytes to check for analyte carryover. Matrix inter-
ferences may be caused by contaminants that are coextracted Note: If methylene chloride is not completely removed from
from the sample. The extent of matrix interferences will vary the final extract, it may cause detector problems.
considerably from source to source, depending upon the water QUALITY CONTROL Minimum quality control require-
sampled. ments are initial demonstration of lab capability, determination

©1996 CRC Press LLC


of surrogate compound recoveries in each sample and blank, the trap account for many contamination problems. Interfer-
monitoring internal standard peak area or height in each sam- ences purged or coextracted from the samples will vary con-
ple and blank, analysis of lab reagent blanks, lab fortified sam- siderably from source to source. Cross-contamination can
ples, lab fortified blanks, and other QC samples. A lab reagent occur whenever high-level and low-level samples are analyzed
blank is analyzed to demonstrate that all glassware and reagent sequentially. Whenever an unusually concentrated sample is
interferences are under control. analyzed, it should be followed by the analysis of organic-free
reagent water to check for cross-contamination. Samples also
Initial demonstration of capability is fulfilled by analyzing four can be contaminated by diffusion of volatile organics (partic-
fortified reagent water samples with the recovery value for each ularly methylene chloride and fluorocarbons) through the sep-
analyte falling within the acceptable range ( 30% average tum seal into the sample during shipment and storage. A trip
recovery). Surrogate recoveries from samples or method blanks blank can serve as a check on such contamination. The lab
must be 70–130%. The internal standard response for any sam- where volatile analysis is performed and also the refrigerated
ple chromatogram should not deviate from the daily calibra- storage area should be completely free of solvents.
tion check standard’s internal standard response by more than
30% or lab fortified blanks and sample matrices are used to INSTRUMENTATION A gas chromatograph/mass spec-
assess lab performance and analyte recovery, respectively. trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
I.D. glass column packed with 1% SP-1000 on Carbopack-B
If the response for the target analyte peak exceeds the working (60/80 mesh) is required.Also needed is a 5-mL purging device,
range of the system, dilute the extract and reanalyze.Alternative a sorbent trap, and a thermal desorption apparatus.
techniques such as an alternate detector or second chromatog-
raphy column should be used to confirm peak identification PRECISION & ACCURACY This method is reported to have
when sample components are not resolved adequately. been tested by 15 laboratories using organic-free reagent water,
drinking water, surface water, and industrial wastewaters (not
EPA CONTACT & HOTLINE For technical questions contact specified) fortified at six concentrations over the range 5–
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and 600 g/L.
Drinking Water (WH-550D), 401 M St. SW, Washington, DC
20460. Tel. (202) 260-3040. For further information the EPA Sample estimated quantitation limits (EQLs) are highly
Safe Drinking Water Hotline may be called at: (800) 426-4791. matrix-dependent. The EQLs listed may not always be achiev-
able. EQLs listed for soils or sediments are based on wet weight.
REFERENCE Methods for the Determination of Organic Normally, data is reported on a dry-weight basis; therefore,
Compounds in Drinking Water, EPA/600/4-88/039 (revised EQLs will be higher, based on the percent dry weight of each
July 1991). U.S. EPA Environmental Monitoring Systems Lab- sample. Note that EQLs are even more variable than MDLs and
oratory, Cincinnati, OH, 45268, U.S.A. Available from the that they are highly variable depending on the matrix being
National Technical Information Service (NTIS), 5285 Port analyzed.
Royal Road, Springfield, VA 22161; Tel. 800-553-6847. NTIS
EQL in groundwater in g/L was not listed.
Order Number is PB91-231480.
EQL in low soil or sediment in g/kg was not listed.
Accuracy (a) in g/L was not listed.
Precision (b) in g/L was not listed.
-Propiolactone EPA Method 8240
(a) Average recovery found for measurements of samples con-
CAS #57-57-8
taining a concentration of C, in g/L.
(b) Overall precision found for measurements of samples with
TITLE Volatile Organics By GC/MS: Packed Column Technique
average recovery X for samples containing a concentration
MATRIX Nearly all types of sample matarices, regardless of of C in g/L.
water content, can be analyzed using this method. This includes X = Average recovery found for measurement of samples con-
groundwater, aqueous sludges, caustic liquors, acid liquors, taining a concentration of C in g/L.
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
MULTIPLICATION FACTORS FOR OTHER MATRICES
metric emulsions, filter cakes, spent carbons, spent catalysts,
soils, and sediments. Other Matrices Factor (a)

METHOD SUMMARY Method 8240B covers 80 volatile Waste miscible liquid waste 50
organic compounds that are introduced into a gas chromato- High-concentration soil and sludge 125
graph by the purge-and-trap method or by direct injection (in Non-water miscible waste 500
limited applications). For the purge-and-trap method an inert (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
gas (zero grade nitrogen or helium) is bubbled through a 5-mL samples, the factor is on a wet-weight basis.
solution at ambient temperature. Purged sample components
are trapped in a tube of sorbent materials. When purging is SAMPLING METHOD
complete, the sorbent tube is heated and backflushed with inert Liquid samples — Use a 40-mL glass screw-cap VOA vial with
gas to desorb the trapped components onto a GC column. a Teflon®-faced silicone septum that has been prewashed,
rinsed with distilled deionized water, and oven dried. However,
INTERFERENCES Impurities in the purge gas and from if residual chlorine is present, collect sample in a 40-oz. soil
organic compounds outgassing from the plumbing ahead of VOA container which has been pre-preserved with 4 drops of

©1996 CRC Press LLC


10% sodium thiosulfate, mix gently, and then transfer the sam- ambient temperature. All samples with an expected concentra-
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli- tion of >1.0 mg/kg should be analyzed by this method.
cate and seal them in separate plastic bags.
Mix the contents of the sample container with a narrow metal
Soils or sediments, and sludges — Use an 8-oz. widemouth spatula. For sediments or soils and solid wastes that are insol-
glass bottle with a Teflon®-faced silicone septum that has been uble in methanol, weigh 4 g (wet weight) of sample into a tared
prewashed with detergent, rinsed with distilled deionized 20-mL vial. For waste that is soluble in methanol, tetraglyme,
water, and oven dried. Tap slightly to eliminate free air space. or PEG, weigh 1 g (wet weight) into a tared scintillation vial
Collect samples in duplicate and seal them in separate plastic bags. or culture tube or a 10-mL volumetric flask. Quickly add
SAMPLE PRESERVATION 9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
Liquid samples — Add 4 drops of concentrated HCL and spiking solution to the vial, cap it, and shake it for 2 min.
immediately cool samples to 4C and store in a solvent-free METHANOL EXTRACT REQUIRED FOR ANALYSIS
refrigerator. OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
Soils or sediments, and sludges — Cool samples to 4C and Approximate Volume of
store in a solvent-free refrigerator. Concentration Range Methanol Extract (a)
MHT Maximum holding time is 14 days from the date of 500–10,000 g/kg 100 L
sample collection. 1,000–20,000 g/kg 50 L
5,000–100,000 g/kg 10 L
SAMPLE PREPARATION 25,000–500,000 g/kg 100 L of 1/50 dilution (b)
Liquid samples — Remove the plunger from a 5-mL syringe
and carefully pour the sample into the syringe barrel to just Calculate appropriate dilution factor for concentrations
short of overflowing. Replace the syringe plunger and compress exceeding this table.
the sample. Open the syringe valve and vent any residual air
(a) The volume of methanol added to 5 mL of water being purged
while adjusting the sample volume to 5.0 mL. If there is only
should be kept constant. Therefore, add to the 5-mLsyringe whatever
one volatile organic analysis (VOA) vial, a second syringe
should be filled at this time to protect against possible loss of volume of methanol is necessary to maintain a volume of 100 L
added to the syringe.
sample integrity. Add 10 L of surrogate spiking solution and
(b) Dilute an aliquot of the methanol extract and then take 100 L
10 L of internal standard spiking solution through the valve
for analysis.
bore of the 5-mL syringe, then close the valve. The surrogate
and internal standards may be mixed and added as a single QUALITY CONTROL Demonstrate, through the analysis of
spiking solution. a reagent water blank, that interferences from the analytical
Sediments, soils, and waste samples — All samples of this type system, glassware, and reagents are under control. Blank sam-
should be screened by GC analysis using a headspace method ples should be carried through all stages of the sample prepa-
(EPA Method 3810) or the hexadecane extraction and screen- ration and measurement steps. For each analytical batch (up
ing method (EPA Method 3820). Use the screening data to to 20 samples), a reagent blank, matrix spike, and matrix spike
determine whether to use the low-concentration method duplicate must be analyzed (the frequency of the spikes may
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg). be different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample
Low-concentration method — The low-concentration method preparation and measurement steps. QC samples mentioned
is based on purging a heated sediment or soil sample mixed in the section on Interferences will also be needed as appropri-
with organic-free reagent water containing the surrogate and ate to those situations.
internal standards. Analyze all reagent blanks and standards
under the same conditions as the samples. REFERENCE Test Methods for Evaluating Solid Waste (SW-
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office
Use a 5-g sample if the expected concentration is <0.1 mg/kg of Solid Wastes, Washington, DC.
or a 1-g sample for expected concentrations between 0.1 and
1 mg/kg. Mix the contents of the sample container with a nar-
row metal spatula. Weigh the amount of the sample into a tared
purge device. Add the spiked water to the purge device, which Propionitrile EPA Method 8240
contains the weighed amount of sample, and connect the CAS #107-12-0
device to the purge-and-trap system.
TITLE Volatile Organics By GC/MS: Packed Column Technique
High-concentration method — This method is based on
extracting the sediment or soil with methanol. A waste sample MATRIX Nearly all types of sample matarices, regardless of
is either extracted or diluted, depending on its solubility in water content, can be analyzed using this method. This includes
methanol. Wastes that are insoluble in methanol are diluted groundwater, aqueous sludges, caustic liquors, acid liquors,
with reagent tetraglyme or possibly polyethylene glycol (PEG). waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
An aliquot of the extract is added to organic-free reagent water metric emulsions, filter cakes, spent carbons, spent catalysts,
containing surrogate and internal standards. This is purged at soils, and sediments.

©1996 CRC Press LLC


METHOD SUMMARY Method 8240B covers 80 volatile MULTIPLICATION FACTORS FOR OTHER MATRICES
organic compounds that are introduced into a gas chromato- Other Matrices Factor (a)
graph by the purge-and-trap method or by direct injection (in
limited applications). For the purge-and-trap method an inert Waste miscible liquid waste 50
High-concentration soil and sludge 125
gas (zero grade nitrogen or helium) is bubbled through a 5-mL
Non-water miscible waste 500
solution at ambient temperature. Purged sample components
are trapped in a tube of sorbent materials. When purging is (a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous
complete, the sorbent tube is heated and backflushed with inert samples, the factor is on a wet-weight basis.
gas to desorb the trapped components onto a GC column. SAMPLING METHOD
INTERFERENCES Impurities in the purge gas and from Liquid samples — Use a 40-mL glass screw-cap VOA vial with
organic compounds outgassing from the plumbing ahead of a Teflon®-faced silicone septum that has been prewashed,
the trap account for many contamination problems. Interfer- rinsed with distilled deionized water, and oven dried. However,
ences purged or coextracted from the samples will vary con- if residual chlorine is present, collect sample in a 40-oz. soil
VOA container which has been pre-preserved with 4 drops of
siderably from source to source. Cross-contamination can
10% sodium thiosulfate, mix gently, and then transfer the sam-
occur whenever high-level and low-level samples are analyzed
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli-
sequentially. Whenever an unusually concentrated sample is cate and seal them in separate plastic bags.
analyzed, it should be followed by the analysis of organic-free
reagent water to check for cross-contamination. Samples also Soils or sediments, and sludges — Use an 8-oz. widemouth
can be contaminated by diffusion of volatile organics (partic- glass bottle with a Teflon®-faced silicone septum that has been
ularly methylene chloride and fluorocarbons) through the sep- prewashed with detergent, rinsed with distilled deionized
tum seal into the sample during shipment and storage. A trip water, and oven dried. Tap slightly to eliminate free air space.
Collect samples in duplicate and seal them in separate plastic bags.
blank can serve as a check on such contamination. The lab
where volatile analysis is performed and also the refrigerated SAMPLE PRESERVATION
storage area should be completely free of solvents. Liquid samples — Add 4 drops of concentrated HCL and
immediately cool samples to 4C and store in a solvent-free
INSTRUMENTATION A gas chromatograph/mass spec-
refrigerator.
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
I.D. glass column packed with 1% SP-1000 on Carbopack-B Soils or sediments, and sludges — Cool samples to 4C and
(60/80 mesh) is required.Also needed is a 5-mL purging device, store in a solvent-free refrigerator.
a sorbent trap, and a thermal desorption apparatus. MHT Maximum holding time is 14 days from the date of
PRECISION & ACCURACY This method is reported to have sample collection.
been tested by 15 laboratories using organic-free reagent water, SAMPLE PREPARATION
drinking water, surface water, and industrial wastewaters (not Liquid samples — Remove the plunger from a 5-mL syringe
specified) fortified at six concentrations over the range 5– and carefully pour the sample into the syringe barrel to just
600 g/L. short of overflowing. Replace the syringe plunger and compress
the sample. Open the syringe valve and vent any residual air
Sample estimated quantitation limits (EQLs) are highly
while adjusting the sample volume to 5.0 mL. If there is only
matrix-dependent. The EQLs listed may not always be achiev-
one volatile organic analysis (VOA) vial, a second syringe
able. EQLs listed for soils or sediments are based on wet weight. should be filled at this time to protect against possible loss of
Normally, data is reported on a dry-weight basis; therefore, sample integrity. Add 10 L of surrogate spiking solution and
EQLs will be higher, based on the percent dry weight of each 10 L of internal standard spiking solution through the valve
sample. Note that EQLs are even more variable than MDLs and bore of the 5-mL syringe, then close the valve. The surrogate
that they are highly variable depending on the matrix being and internal standards may be mixed and added as a single
analyzed. spiking solution.
EQL in groundwater in g/L was 100. Sediments, soils, and waste samples — All samples of this type
EQL in low soil or sediment in g/kg was 100. should be screened by GC analysis using a headspace method
Accuracy (a) in g/L was not listed. (EPA Method 3810) or the hexadecane extraction and screen-
Precision (b) in g/L was not listed. ing method (EPA Method 3820). Use the screening data to
determine whether to use the low-concentration method
(a) Average recovery found for measurements of samples con-
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
taining a concentration of C, in g/L.
(b) Overall precision found for measurements of samples with Low-concentration method — The low-concentration method
average recovery X for samples containing a concentration is based on purging a heated sediment or soil sample mixed
of C in g/L. with organic-free reagent water containing the surrogate and
X = Average recovery found for measurement of samples con- internal standards. Analyze all reagent blanks and standards
taining a concentration of C in g/L. under the same conditions as the samples.

©1996 CRC Press LLC


Use a 5-g sample if the expected concentration is <0.1 mg/kg
n-Propylamine EPA Method 8240
or a 1-g sample for expected concentrations between 0.1 and
CAS #107-10-8
1 mg/kg. Mix the contents of the sample container with a nar-
row metal spatula. Weigh the amount of the sample into a tared TITLE Volatile Organics By GC/MS: Packed Column Technique
purge device. Add the spiked water to the purge device, which
contains the weighed amount of sample, and connect the MATRIX Nearly all types of sample matarices, regardless of
device to the purge-and-trap system. water content, can be analyzed using this method. This includes
groundwater, aqueous sludges, caustic liquors, acid liquors,
High-concentration method — This method is based on waste solvents, oily wastes, mousses, tars, fibrous wastes, poly-
extracting the sediment or soil with methanol. A waste sample
metric emulsions, filter cakes, spent carbons, spent catalysts,
is either extracted or diluted, depending on its solubility in
soils, and sediments.
methanol. Wastes that are insoluble in methanol are diluted
with reagent tetraglyme or possibly polyethylene glycol (PEG). METHOD SUMMARY Method 8240B covers 80 volatile
An aliquot of the extract is added to organic-free reagent water organic compounds that are introduced into a gas chromato-
containing surrogate and internal standards. This is purged at graph by the purge-and-trap method or by direct injection (in
ambient temperature. All samples with an expected concentra- limited applications). For the purge-and-trap method an inert
tion of >1.0 mg/kg should be analyzed by this method. gas (zero grade nitrogen or helium) is bubbled through a 5-mL
solution at ambient temperature. Purged sample components
Mix the contents of the sample container with a narrow metal
are trapped in a tube of sorbent materials. When purging is
spatula. For sediments or soils and solid wastes that are insol-
complete, the sorbent tube is heated and backflushed with inert
uble in methanol, weigh 4 g (wet weight) of sample into a tared
gas to desorb the trapped components onto a GC column.
20-mL vial. For waste that is soluble in methanol, tetraglyme,
or PEG, weigh 1 g (wet weight) into a tared scintillation vial INTERFERENCES Impurities in the purge gas and from
or culture tube or a 10-mL volumetric flask. Quickly add organic compounds outgassing from the plumbing ahead of
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate the trap account for many contamination problems. Interfer-
spiking solution to the vial, cap it, and shake it for 2 min. ences purged or coextracted from the samples will vary con-
siderably from source to source. Cross-contamination can
METHANOL EXTRACT REQUIRED FOR ANALYSIS
occur whenever high-level and low-level samples are analyzed
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
sequentially. Whenever an unusually concentrated sample is
Approximate Volume of analyzed, it should be followed by the analysis of organic-free
Concentration Range Methanol Extract (a) reagent water to check for cross-contamination. Samples also
500–10,000 g/kg 100 L can be contaminated by diffusion of volatile organics (partic-
1,000–20,000 g/kg 50 L ularly methylene chloride and fluorocarbons) through the sep-
5,000–100,000 g/kg 10 L tum seal into the sample during shipment and storage. A trip
25,000–500,000 g/kg 100 L of 1/50 dilution (b) blank can serve as a check on such contamination. The lab
where volatile analysis is performed and also the refrigerated
Calculate appropriate dilution factor for concentrations storage area should be completely free of solvents.
exceeding this table.
INSTRUMENTATION A gas chromatograph/mass spec-
(a) The volume of methanol added to 5 mL of water being purged trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
should be kept constant. Therefore, add to the 5-mLsyringe whatever I.D. glass column packed with 1% SP-1000 on Carbopack-B
volume of methanol is necessary to maintain a volume of 100 L (60/80 mesh) is required.Also needed is a 5-mL purging device,
added to the syringe. a sorbent trap, and a thermal desorption apparatus.
(b) Dilute an aliquot of the methanol extract and then take 100 L
for analysis. PRECISION & ACCURACY This method is reported to have
been tested by 15 laboratories using organic-free reagent water,
QUALITY CONTROL Demonstrate, through the analysis of drinking water, surface water, and industrial wastewaters (not
a reagent water blank, that interferences from the analytical specified) fortified at six concentrations over the range 5–
system, glassware, and reagents are under control. Blank sam- 600 g/L.
ples should be carried through all stages of the sample prepa-
ration and measurement steps. For each analytical batch (up Sample estimated quantitation limits (EQLs) are highly
to 20 samples), a reagent blank, matrix spike, and matrix spike matrix-dependent. The EQLs listed may not always be achiev-
duplicate must be analyzed (the frequency of the spikes may able. EQLs listed for soils or sediments are based on wet weight.
be different for different monitoring programs). The blank and Normally, data is reported on a dry-weight basis; therefore,
spiked samples must be carried through all stages of the sample EQLs will be higher, based on the percent dry weight of each
preparation and measurement steps. QC samples mentioned sample. Note that EQLs are even more variable than MDLs and
in the section on Interferences will also be needed as appropri- that they are highly variable depending on the matrix being
ate to those situations. analyzed.
REFERENCE Test Methods for Evaluating Solid Waste (SW- EQL in groundwater in g/L was not listed.
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office EQL in low soil or sediment in g/kg was not listed.
of Solid Wastes, Washington, DC. Accuracy (a) in g/L was not listed.

©1996 CRC Press LLC


Precision (b) in g/L was not listed. ing method (EPA Method 3820). Use the screening data to
determine whether to use the low-concentration method
(a) Average recovery found for measurements of samples con- (0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
taining a concentration of C, in g/L.
(b) Overall precision found for measurements of samples with Low-concentration method — The low-concentration method
average recovery X for samples containing a concentration is based on purging a heated sediment or soil sample mixed
of C in g/L. with organic-free reagent water containing the surrogate and
X = Average recovery found for measurement of samples con- internal standards. Analyze all reagent blanks and standards
taining a concentration of C in g/L. under the same conditions as the samples.
MULTIPLICATION FACTORS FOR OTHER MATRICES Use a 5-g sample if the expected concentration is <0.1 mg/kg
Other Matrices Factor (a) or a 1-g sample for expected concentrations between 0.1 and
1 mg/kg. Mix the contents of the sample container with a nar-
Waste miscible liquid waste 50 row metal spatula. Weigh the amount of the sample into a tared
High-concentration soil and sludge 125 purge device. Add the spiked water to the purge device, which
Non-water miscible waste 500 contains the weighed amount of sample, and connect the
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous device to the purge-and-trap system.
samples, the factor is on a wet-weight basis. High-concentration method — This method is based on
extracting the sediment or soil with methanol. A waste sample
SAMPLING METHOD
is either extracted or diluted, depending on its solubility in
Liquid samples — Use a 40-mL glass screw-cap VOA vial with
methanol. Wastes that are insoluble in methanol are diluted
a Teflon®-faced silicone septum that has been prewashed,
with reagent tetraglyme or possibly polyethylene glycol (PEG).
rinsed with distilled deionized water, and oven dried. However,
An aliquot of the extract is added to organic-free reagent water
if residual chlorine is present, collect sample in a 40-oz. soil
containing surrogate and internal standards. This is purged at
VOA container which has been pre-preserved with 4 drops of ambient temperature. All samples with an expected concentra-
10% sodium thiosulfate, mix gently, and then transfer the sam- tion of >1.0 mg/kg should be analyzed by this method.
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli-
cate and seal them in separate plastic bags. Mix the contents of the sample container with a narrow metal
spatula. For sediments or soils and solid wastes that are insol-
Soils or sediments, and sludges — Use an 8-oz. widemouth uble in methanol, weigh 4 g (wet weight) of sample into a tared
glass bottle with a Teflon®-faced silicone septum that has been 20-mL vial. For waste that is soluble in methanol, tetraglyme,
prewashed with detergent, rinsed with distilled deionized or PEG, weigh 1 g (wet weight) into a tared scintillation vial
water, and oven dried. Tap slightly to eliminate free air space. or culture tube or a 10-mL volumetric flask. Quickly add
Collect samples in duplicate and seal them in separate plastic bags. 9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
SAMPLE PRESERVATION spiking solution to the vial, cap it, and shake it for 2 min.
Liquid samples — Add 4 drops of concentrated HCL and METHANOL EXTRACT REQUIRED FOR ANALYSIS
immediately cool samples to 4C and store in a solvent-free OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
refrigerator. Approximate Volume of
Soils or sediments, and sludges — Cool samples to 4C and Concentration Range Methanol Extract (a)
store in a solvent-free refrigerator. 500–10,000 g/kg 100 L
MHT Maximum holding time is 14 days from the date of 1,000–20,000 g/kg 50 L
sample collection. 5,000–100,000 g/kg 10 L
25,000–500,000 g/kg 100 L of 1/50 dilution (b)
SAMPLE PREPARATION
Liquid samples — Remove the plunger from a 5-mL syringe Calculate appropriate dilution factor for concentrations
and carefully pour the sample into the syringe barrel to just exceeding this table.
short of overflowing. Replace the syringe plunger and compress (a) The volume of methanol added to 5 mL of water being purged
the sample. Open the syringe valve and vent any residual air should be kept constant. Therefore, add to the 5-mLsyringe whatever
while adjusting the sample volume to 5.0 mL. If there is only volume of methanol is necessary to maintain a volume of 100 L
one volatile organic analysis (VOA) vial, a second syringe added to the syringe.
should be filled at this time to protect against possible loss of (b) Dilute an aliquot of the methanol extract and then take 100 L
sample integrity. Add 10 L of surrogate spiking solution and for analysis.
10 L of internal standard spiking solution through the valve
QUALITY CONTROL Demonstrate, through the analysis of
bore of the 5-mL syringe, then close the valve. The surrogate
a reagent water blank, that interferences from the analytical
and internal standards may be mixed and added as a single
system, glassware, and reagents are under control. Blank sam-
spiking solution.
ples should be carried through all stages of the sample prepa-
Sediments, soils, and waste samples — All samples of this type ration and measurement steps. For each analytical batch (up
should be screened by GC analysis using a headspace method to 20 samples), a reagent blank, matrix spike, and matrix spike
(EPA Method 3810) or the hexadecane extraction and screen- duplicate must be analyzed (the frequency of the spikes may

©1996 CRC Press LLC


be different for different monitoring programs). The blank and PRECISION & ACCURACY Method detection limits are
spiked samples must be carried through all stages of the sample dependent upon the characteristics of the gas chromatographic
preparation and measurement steps. QC samples mentioned system used. Analytes that are not separated chromatographi-
in the section on Interferences will also be needed as appropri- cally cannot be individually identified and used in the same
ate to those situations. calibration mixture or water samples unless an alternative tech-
nique for identification and quantification, such as mass spec-
REFERENCE Test Methods for Evaluating Solid Waste (SW-
trometry, is used.
846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office
of Solid Wastes, Washington, DC. Electrolytic conductivity detetor (c) range in g/L (a) was
0.02–200.
Electrolytic conductivity detetor (c) MDL in g/L (b) was not
listed.
n-Propylbenzene EPA Method 502 Electrolytic conductivity detetor (c) accuracy as % recoverywas
CAS #103-65-1 not listed.
Electrolytic conductivity detetor (c) precision as % RSD was
TITLE Volatile Organic Compounds in Water By Purge and not listed.
Trap Capillary Column Gas Chromatography with Photoion- Photoionization detector (d) range in g/L (a) was 0.02–200.
ization and Electrolytic Conductivity Detectors in Series. U.S. Photoionization detector (d) MDL in g/L (b) was 0.01.
EPA Method 502.2, Rev. 2.0, 1989. Photoionization detector (d) accuracy as % recovery was 103.
MATRIX Drinking water and raw source water. The latter Photoionization detector (d) precision as % RSD was 2.0.
should include most surface water and groundwater sources. (a) The applicable concentration range of this method is com-
METHOD SUMMARY This method covers 60 volatile pound, instrument, and matrix-dependent. It is listed as
organic compounds that contain halogen atoms and/or that being approximately 0.02 to 200 g/L but no specific infor-
are aromatic. An inert gas (zero grade nitrogen or helium) is mation is provided so caution should be observed.
bubbled through a 25-mL or a 5-mL water sample (depending (b) The method detection limits reports with this method are
on the expected concentration of the analytes). Purged sample compound, instrument, and matrix-dependent. The values
components are trapped in a tube of sorbent materials. When reported were calculated using reagent water fortifi d with
purging is complete, the sorbent tube is heated and backflushed the corresponding compounds at 10 g/L and a
with helium to desorb the trapped sample onto a capillary GC GC-equipped with a 60 m 0.75 mm VOLCOL wide bore
column. The column is temperature programmed to separate capillary column with 1.5 m fi m thickness and using
the method analytes which are then detected with a photoion- helium carrier gas.
ization detector (PID) and a Hall electrolytic conductivity (c) Recoveries and relative standard deviations were deter-
mined from seven samples of reagent water fortifi d with
(HECD) placed in series. The PID is selective for aromatic
compounds and the HECD is selective for halogenated com- 10 g/L of each compound. 2-Bromo-1-chloropropane was
used as the internalstandard forcalculatingaverage recoveries.
pounds.
(d) Recoveries and relative standard deviations were deter-
INTERFERENCES Impurities in the purge gas and from mined from seven samples of reagent water fortifi d with
organic compounds outgassing from the plumbing ahead of 10 g/L of each compound. Fluorobenzene was used as the
the trap account for many contamination problems. Interfer- internal standard for calculating average recoveries.
ences purged or coextracted from the samples will vary con-
SAMPLING METHOD Collect samples using a 40- to
siderably from source to source, depending upon the particular
120-mL screw-cap vial (prewashed with detergent, rinsed with
sample or extract being tested. Cross-contamination can occur
distilled water and oven dried at 105C) with a Teflon®-faced
whenever high-level and low-level samples are analyzed
silicone septum . Collect bubble-free samples and place the sep-
sequentially. Samples also can be contaminated by diffusion of
tum with the Teflon® side down on the water.
volatile organics (particularly methylene chloride and fluoro-
carbons) through the septum seal into the sample during ship- SAMPLE PRESERVATION If residual chlorine is present in
ment and storage. The lab where volatile analysis is performed the water add about 25 mg of ascorbic acid to each vial before
and also the refrigerated storage area should be completely free samples are collected to remove the chlorine. Add hydrochloric
of solvents. acid to reduce pH to <2, immediately cool samples to 4 C, and
store them in a solvent-free refrigerator at 4C until analysis.
INSTRUMENTATION A GC containing a series configura-
tion of a high temperature photoionization detector (PID) MHT The maximum holding time for samples is 14 days
equipped with 10.0 eV (nominal) lamp and Hall electrolytic from the time they were collected.
conductivity detector (HECD) is required. Also required is an SAMPLE PREPARATION Remove the plungers from two
all-glass 5-mL purging device, a sorbent trap, and a thermal 5-mL syringes and attach a closed syringe valve to each. Warm
desorption apparatus which is connected to the GC system. the sample to room temperature, open the sample bottle, and
Column 1: VOCOL glass wide-bore capillary column. carefully pour the sample into one of the syringe barrels to just
Column 2: RTX–502.2 mega-bore capillary column. short of overflowing. Replace the syringe plunger, invert the
Column 3: DB-62 mega-bore capillary column. syringe, and compress the sample. Open the syringe valve and

©1996 CRC Press LLC


vent any residual air while adjusting the sample volume to sample or extract being tested. Cross-contamination can occur
5.0 mL. Add 10 L of the internal calibration standard to the whenever high-level and low-level samples are analyzed
sample through the syringe valve. Close the valve. Fill the sec- sequentially. Samples also can be contaminated by diffusion of
ond syringe in an identical manner from the same sample volatile organics (particularly methylene chloride and fluoro-
bottle. Reserve this second syringe for a reanalysis if necessary. carbons) through the septum seal into the sample during ship-
QUALITY CONTROL As an initial demonstration of lab ment and storage.
accuracy and precision, analyze 4 to 7 replicates of a lab fortified INSTRUMENTATION A GC/MS with a data system
blank containing analyte at 0.1–5 g/L. Collect all samples in equipped with one of the following capillary GC columns:
duplicate. Surrogate analytes (similar to those of the analytes
of interest), whose concentration is known in every sample, are Column 1: VOCOL glass wide bore capillary column.
measured using the same internal standard calibration proce- Column 2: DB-624 fused silica capillary column.
dure. Duplicate field reagent water blanks (trip blanks) must Column 3: DB-5 fused silica capillary column.
be analyzed with each set of samples, lab reagent blanks Also required is an all-glass 25 mL or 5-mL purging device, a
(method blanks) must be analyzed with each batch of samples sorbent trap, and a thermal desorption apparatus which is
processed as a group within a work shift. Also, a single lab- connected to the GC/MS system.
fortified blank that contains each of the analytes of interest
should be analyzed with each batch of samples processed as a PRECISION & ACCURACY Method detection limits are
group within a work shift. A 3- to 5-point calibration curve is compound- and instrument-dependent, and may vary from
needed depending on the calibration range factor required. approximately 0.02–0.35 g/L. Note in the table below that the
“true” concentration range used for accuracy and precision
EPA CONTACT & HOTLINE For technical questions contact measurements was quite narrow. However, the applicable con-
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and centration range of this method is primarily column dependent
Drinking Water (WH-550D), 401 M St. SW, Washington, DC
and is approximately 0.02 to 200 g/L for the wide-bore thick-
20460. Tel. (202) 260-3040. For further information the EPA
film columns. Narrow-bore thin-film columns may have a
Safe Drinking Water Hotline may be called at: (800) 426-4791.
capacity which limits the range to about 0.02 to 20 g/L. Ana-
REFERENCE Methods for the Determination of Organic lytes that are inefficiently purged from water will not be
Compounds in Drinking Water, EPA/600/4-88/039 (revised detected when present at low concentrations, but they can be
July 1991; Final Rule for determination of compliance with the measured with acceptable accuracy and precision when present
MCL for Total Trihalomethanes under 141.30, in 40 CFR Part in sufficient amounts.
141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S.
EPA Environmental Monitoring Systems Laboratory, Cincin- Analytes that are not separated chromatographically, but which
nati, OH, 45268, U.S.A. Available from the National Technical have different mass spectra and non-interfering quantification
Information Service (NTIS), 5285 Port Royal Road, Spring- ions, can be identified and measured in the same calibration
field, VA 22161; Tel. 800-553-6847. NTIS Order Number is mixture or water sample.Analytes which have very similar mass
PB91-231480. spectra cannot be individually identified and measured in the
same calibration mixture or water samples unless they have
different retention times. Co-eluting compounds with very
similar mass spectra, typically many structural isomers, must
n-Propylbenzene EPA Method 524 be reported as an isomeric group or pair.
CAS #103-65-1
The range (in g/L) was 0.1–10.
TITLE Measurement of Purgeable Organic Compounds in The Method Detection Limig (in g/L) was 0.04.
Water by Capillary Column GC/MS. The accuracy (as % recovery) was 100.
The precision (in %) was 5.8.
MATRIX Drinking water and raw source water; the latter
should include most surface water and groundwater sources. Note: Data were obtained from 16–31 determinations using a
wide-bore capillary column and a jet separator interfaced to a
METHOD SUMMARY Method 524.2 covers 60 volatile quadrupole mass spectrometer. All analytes were in a reagent
organic compounds. An inert gas (zero grade nitrogen or water matrix.
helium) is bubbled through a 25-mL or a 5-mL water sample
(depending on the expected concentration of the analytes). SAMPLING METHOD Collect samples using a 40- to
Purged sample components are trapped in a tube of sorbent 120-mL screw-cap vial (prewashed with detergent, rinsed with
materials. When purging is complete, the sorbent tube is heated distilled water and oven dried at 105C) with a Teflon®-faced
and backflushed with helium to desorb the trapped sample silicone septum . Collect bubble-free samples and place the sep-
onto a capillary GC column. tum with the Teflon® side down on the water.
INTERFERENCES Impurities in the purge gas and from SAMPLE PRESERVATION If residual chlorine is present in
organic compounds outgassing from the plumbing ahead of the water add about 25 mg of ascorbic acid to each vial before
the trap account for many contamination problems. Interfer- samples are collected to remove the chlorine. Add hydrochloric
ences purged or coextracted from the samples will vary con- acid to reduce pH to <2, and immediately cool samples to 4 C,
siderably from source to source, depending upon the particular and store them in a solvent-free refrigerator at 4C until analysis.

©1996 CRC Press LLC


MHT The maximum holding time for samples is 14 days aqueous sludges, caustic liquors, acid liquors, waste solvents,
from the time they were collected. oily wastes, mousses, tars, fibrous wastes, polymeric emulsions,
filter cakes, spent carbons, spent catalysts, soils, and sediments.
SAMPLE PREPARATION Remove the plungers from two
25-mL (or 5-mL depending on sample size) syringes and attach METHOD SUMMARY This method is used to determine 60
a closed syringe valve to each. Warm the sample to room tem- volatile organic compounds in a variety of solid waste matrices.
perature, open the sample bottle, and carefully pour the sample It provides GC conditions for the detection of halogenated and
into one of the syringe barrels to just short of overflowing. aromatic volatile organic compounds. Samples can be analyzed
Replace the syringe plunger, invert the syringe, and compress using direct injection or purge-and-trap (EPA Method 5030).
the sample. Open the syringe valve and vent any residual air Groundwater samples must be analyzed using EPA Method
while adjusting the sample volume to 25.0 mL (or 5 mL). For 5030 (where applicable). A temperature program is used with
samples and blanks, add 5 L of the fortification solution con- the GC. Detection is achieved by a photoionization detector
taining the internal standard and the surrogates to the sample (PID) and a Hall electrolytic conductivity detector (HECD) in
through the syringe valve. For calibration standards and lab series.
fortified blanks, add 5 L of the fortification solution contain-
INTERFERENCES Samples can be contaminated by diffu-
ing the internal standard only. Close the valve. Fill the second
sion of volatile organics (particularly chlorofluorocarbons and
syringe in an identical manner from the same sample bottle.
methylene chloride) through the sample container septum dur-
Reserve this second syringe for a reanalysis if necessary.
ing shipment and storage.
QUALITY CONTROL As an initial demonstration of lab
INSTRUMENTATION A GC-equipped with variable-con-
accuracy and precision, analyze 4 to 7 replicates of a lab fortified
stant differential flow controllers, subambient oven controller,
blank containing analyte at 0.2–5 g/L. Collect all samples in
PID and HECD detectors connected with a short piece of
duplicate. Surrogate analytes (similar to those of the analytes
uncoated capillary tubing and a data system.
of interest), whose concentration is known in every sample, are
measured using the same internal standard calibration proce- Column: 60 m 0.75 mm I.D.VOCOLwide-bore capillary col-
dure. Duplicate field reagent water blanks (trip blanks) must umn with 1.5 m film thickness.
be analyzed with each set of samples, lab reagent blanks
PRECISION & ACCURACY MDLs are compound-depen-
(method blanks) must be analyzed with each batch of samples
processed as a group within a work shift. Also, a single lab- dent and vary with purging efficiency and concentration. The
fortified blank that contains each of the analytes of interest applicable concentration range of this method is compound-
should be analyzed with each batch of samples processed as a and instrument-dependent but is approximately 0.1 to
group within a work shift. A 3- to 5-point calibration curve is 200 g/L. Analytes that are inefficiently purged from water will
needed depending on the calibration range factor required. not be detected when present at low concentrations, but they
can be measured with acceptable accuracy and precision when
EPA CONTACT & HOTLINE For technical questions contact present in sufficient amounts. The estimated quantitation limit
Dr. Baldev Bathija, U.S. EPA, Office of Ground Water and (EQL) for an individual compound is approximately 1 g/kg
Drinking Water (WH-550D), 401 M St. SW, Washington, DC (wet weight) for soil/sediment samples, 100 g/kg (wet weight)
20460. Tel. (202) 260-3040. For further information the EPA for wastes, and 1 g/L for groundwater. EQLs will be propor-
Safe Drinking Water Hotline may be called at: (800) 426-4791. tionately higher for sample extracts and samples that require
REFERENCE Methods for the Determination of Organic dilution or reduced sample size to avoid saturation of the detector.
Compounds in Drinking Water, EPA/600/4-88/039 (revised MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
July 1991; Final Rule for determination of compliance with the Matrix Factor (b)
MCL for Total Trihalomethanes under 141.30, in 40 CFR Part
141, Vol. 58, No. 147, Fed. Reg., Tuesday Aug. 3, 1993). U.S. Groundwater 10
EPA Environmental Monitoring Systems Laboratory, Cincin- Low-concentration soil 10
nati, OH, 45268, U.S.A. Available from the National Technical Water miscible liquid waste 500
Information Service (NTIS), 5285 Port Royal Road, Spring- High-concentration soil and sludge 1250
field, VA 22161; Tel. 800-553-6847. NTIS Order Number is Non-water miscible waste 1250
PB91-231480. (a) Sample EQLs are highly matrix-dependent. The EQLs listed
herein are provided for guidance and may not always be achievable.
(b) EQL = [Method detection limit] [Factor]. For non-aqueous
n-Propylbenzene EPA Method 8021 samples, the factor is on a wet-weight basis.
CAS #103-65-1 SINGLE LABORATORY ACCURACY & PRECISION DATA
FOR VOCs IN WATER
TITLE Halogenated Volatile by Gas Chromatography Using This method was tested in a single lab using water spiked at
Photoionization and Electrolytic Conductivity Detectors in 10 g/L and the following data was reported:
Series: Capillary Column Technique
Recoveries and standard deviations were determined from
MATRIX This method is applicable to nearly all types of seven samples and spiked at 10 g/L of each analyte. Recoveries
samples, regardless of water content, including groundwater, were determined by the internal standard method. Internal

©1996 CRC Press LLC


standards were: Fluorobenzene for PID and 2-Bromo-1-chlo- QUALITY CONTROL Calculate surrogate standard recovery
ropropane for HECD. on all samples, blanks, and spikes.A trip blank is recommended
to check on sampling, storage, and handling contamination.
The average recovery (in percent) for the PID was 103.
Calibration standards, at a minimum of five concentration lev-
The standard deviation of the recovery for the PID was 2.0.
els, are prepared in organic-free reagent water. One of the con-
The MDL (in g/mL) for the PID was 0.004.
centration levels should be at a concentration near, but above,
The average recovery (in percent) for the HECD was none (no
the method detection limit.
response for this detector).
The standard deviation of the recovery for the HECD was none A combination of bromochloromethane, 2-bromo-1-chloro-
(no response for this detector). propane, 1,4-dichlorobutane, and bromochlorobenzene are
The MDL (in g/mL) for the HECD was none (no response recommended as surrogate standards to encompass the range
for this detector). of the temperature program used in this method.
SAMPLE COLLECTION, PRESERVATION & HANDLING REFERENCE Test Methods for Evaluating Solid Waste, Phys-
Volatile Organics — Standard 40-mL glass screw-cap VOA vials ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
with Teflon®-faced silicone septum may be used for both liquid of Solid Waste, Washington, DC, EPA Method 8021A, Rev. 1,
and solid matrices. When collecting samples, liquids and solids Nov. 1992.
should be introduced into the vials gently to reduce agitation
which might drive off volatile compounds. If there are any air
bubbles present the sample must be retaken. Tap slightly as n-Propylbenzene EPA Method 8260
they are filled to try and eliminate as much free air space as CAS #103-65-1
possible. The two vials from each sampling locations should
be sealed in separate plastic bags to prevent cross-contamina- TITLE Volatile Organic Compounds by GC/MS: Capillary
tion between samples particularly if the sampled waste is sus- Column Technique
pected of containing high levels of volatile organics.
MATRIX This method is applicable to nearly all types of
Semivolatile organics — Containers used to collect samples for samples, regardless of water content, including groundwater,
the determination of semivolatile organic compounds should soils, and sediments.
be soap and water washed followed by methanol (or isopro-
panol) rinsing. The sample containers should be of glass or METHOD SUMMARY Method 8260A covers 58 volatile
Teflon® and have screw-top covers with Teflon® liners. organic compounds that are introduced into a gas chromato-
graph by the purge-and-trap method or by direct injection (in
Preservation for volatile organics — No preservation is used limited applications). Zero-grade helium is bubbled through a
with concentrated waste samples. With liquid samples contain- 5-mL solution at ambient temperature. Purged sample com-
ing no residual chlorine, 4 drops of concentrated hydrochloric ponents are trapped in a tube containing suitable sorbent mate-
acid are added and the samples are immediately cooled to 4 C. rials. When purging is complete, the sorbent tube is heated and
When liquid samples contain residual chlorine, they are treated backflushed with helium to desorb trapped sample compo-
as above and, in addition, 4 drops of 4% aqueous sodium nents. The analytes are desorbed directly to a large bore capil-
thiosulfate are added. Soil, sediment, and sludge samples are lary or cryofocussed on a capillary precolumn before being
only cooled to 4C. flash evaporated to a narrow bore capillary for analysis.
Preservation for semivolatile organics — No preservation is INTERFERENCES Major contaminant sources are volatile
used with concentrated waste samples. With liquid samples materials in the lab and impurities in the inert purging gas and
containing no residual chlorine and with soil, sediment, and in the sorbent trap. Interfering contamination may occur when
sludge samples, immediately cooling to 4C is the only preser- a sample containing low concentrations of volatile organic
vation used. When residual chlorine is present then 3 mL of compounds is analyzed immediately after a sample containing
10% aqueous sodium sulfate is added for each gallon of sample high concentrations of volatile organic compounds. After anal-
collected, followed by cooling to 4C. ysis of a sample containing high concentrations of volatile
organic compounds, one or more calibration blanks should be
MHT The holding time for all volatile organics samples is analyzed to check for cross-contamination. Screening of the
14 days. Liquid samples must be extracted within 7 days and samples prior to purge-and-trap GC/MS analysis is highly rec-
their extracts analyzed within 40 days. Concentrated waste, soil, ommended to prevent contamination of the system. This is
sediment, and sludge samples must be extracted within 14 days especially true for soil and waste samples.
and their extracts analyzed within 40 days.
Special precautions must be taken to analyze for methylene
SAMPLE PREPARATION Volatile compounds are intro- chloride. The analytical and sample storage area should be
duced into the gas chromatograph either by direct injector or isolated from all atmospheric sources of methylene chloride.
purge-and-trap (EPA Method 5030). EPA Method 5030 may All gas chromatography carrier gas lines and purge gas plumb-
be used directly on groundwater samples or low-concentration ing should be constructed from stainless steel or copper tubing.
contaminated soils and sediments. For medium-concentration Laboratory clothing previously exposed to methylene chloride
soils or sediments, methanolic extraction, as described in EPA fumes during liquid-liquid extraction procedures can contrib-
Method 5030, may be necessary prior to purge-and-trap analysis. ute to sample contamination.

©1996 CRC Press LLC


Samples can also be contaminated by diffusion of volatile short of overflowing. Replace the syringe plunger and compress
organics (particularly methylene chloride and fluorocarbons) the sample. Open the syringe valve and vent any residual air
through the septum seal during shipment and storage. A trip while adjusting the sample volume to 5.0 mL. If there is only
blank can serve as a check on such contamination. one volatile organic analysis (VOA) vial, a second syringe
INSTRUMENTATION GC/MS with a temperature-pro- should be filled at this time to protect against possible loss of
grammable chromatograph suitable for splitless injection sample integrity. Add 10 L of surrogate spiking solution and
equipped with variable constant differential flow controllers, a 10 L of internal standard spiking solution through the valve
subambient oven controller, a purging device, sorbent trap, a bore of the 5-mL syringe, then close the valve. The surrogate
thermal desorption apparatus and a capillary precolumn inter- and internal standards may be mixed and added as a single
face when using cryogenic cooling will be needed. The follow- spiking solution.
ing GC columns may be used:
Sediments, soils, and waste samples — All samples of this type
Column 1: 60 m 0.75mm I.D. capillary column coated with should be screened by GC analysis using a headspace method
VOCOL, 1.5 m film thickness. (EPA Method 3810) or the hexadecane extraction and screen-
Column 2: 30 m 0.53mm capillary column coated with DB- ing method (EPA Method 3820). Use the screening data to
624 or VOCOL, 3 m film thickness. determine whether to use the low-concentration method
Column 3: 30 m 0.32mm I.D. capillary column coated with
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg).
DB-5 or SE-54, 1-m film thickness.
Low-concentration method — The low-concentration method
PRECISION & ACCURACY This method has been tested in
is based on purging a heated sediment or soil sample mixed
a single lab using spiked water. Using a wide-bore capillary
column, water was spiked at concentrations between 0.5 and with organic-free reagent water containing the surrogate and
10 g/L. Single lab accuracy and precision data are presented. internal standards. Analyze all reagent blanks and standards
The MDL actually achieved in a given analysis will vary under the same conditions as the samples.
depending on instrument sensitivity and matrix effects. Use a 5-g sample if the expected concentration is <0.1 mg/kg
The MDL (a) in g/L was 0.04. or a 1-g sample for expected concentrations between 0.1 and
The concentration range in g/L was 0.1–10. 1 mg/kg. Mix the contents of the sample container with a nar-
The mean accuracy (% of true value) was 100. row metal spatula. Weigh the amount of the sample into a tared
The precision as relative standard deviation was 5.8. purge device. Add the spiked water to the purge device, which
Note: The MDL is based on a 25-mL sample volume instead contains the weighed amount of sample, and connect the
of a 5-mL sample volume. device to the purge-and-trap system.

SAMPLING METHOD High-concentration method — This method is based on


Liquid samples — Use a 40-mL glass screw-cap VOA vial with extracting the sediment or soil with methanol. A waste sample
a Teflon®-faced silicone septum that has been prewashed, is either extracted or diluted, depending on its solubility in
rinsed with distilled deionized water, and oven dried. If residual methanol. Wastes that are insoluble in methanol are diluted
chlorine is present, collect the sample in a 4-oz soil VOA con- with reagent tetraglyme or possibly polyethylene glycol (PEG).
tainer which has been pre-preserved with 4 drops of 10% An aliquot of the extract is added to organic-free reagent water
sodium thiosulfate. Mix gently and transfer the sample to a containing surrogate and internal standards. This is purged at
40-mL VOA vial. Collect bubble-free samples in duplicate and ambient temperature. All samples with an expected concentra-
seal each sample in a separate plastic bag. tion of >1.0 mg/kg should be analyzed by this method.
Soils, sediments and sludges — Use an 8-oz widemouth glass Mix the contents of the sample container with a narrow metal
bottle with Teflon®-faced silicone septum that has been pre- spatula. For sediments or soils and solid wastes that are insol-
washed, rinsed with distilled deionized water, and oven dried.
uble in methanol, weigh 4 g (wet weight) of sample into a tared
Do not heat the septum for more than 1 h. Tap slightly to
20-mL vial. For waste that is soluble in methanol, tetraglyme,
eliminate any free air space. Collect samples in duplicate and
seal each one in a separate plastic bag. or PEG, weigh 1 g (wet weight) into a tared scintillation vial
or culture tube or a 10-mL volumetric flask. Quickly add
SAMPLE PRESERVATION 9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
Liquid samples — Add 4 drops of concentrated HCL, cool to spiking solution to the vial, cap it, and shake it for 2 min.
4C and store in a solvent-free refrigerator.
METHANOL EXTRACT REQUIRED FOR ANALYSIS
Soils, sediments and sludges — Cool samples to 4C and store OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
in a solvent-free refrigerator.
Approximate Volume of
MHT The maximum holding time of any sample (liquids, Concentration Range Methanol Extract (a)
soils, sediments, and sludges) is 14 days.
500–10,000 g/kg 100 L
SAMPLE PREPARATION 1,000–20,000 g/kg 50 L
Liquid samples — Remove the plunger from a 5-mL syringe 5,000–100,000 g/kg 10 L
and carefully pour the sample into the syringe barrel to just 25,000–500,000 g/kg 100 L of 1/50 dilution (b)

©1996 CRC Press LLC


Calculate appropriate dilution factor for concentrations INSTRUMENTATION Purge and Trap GC w/photoioniza-
exceeding this table. tion detector. ( Two GC columns are recommended);
Column 1: 5% SP-1200 and 1.75% Bentone 34 on Supelcoport;
(a) The volume of methanol added to 5 mL of water being purged
Column 2: 1,2,3-tris(2-cyanoethoxy)propane on Chromosorb W.
should be kept constant. Therefore, add to the 5-mLsyringe whatever
volume of methanol is necessary to maintain a volume of 100 L RANGE 2.2–600 g/L. (Drinking water)
added to the syringe.
MDL 0.009 g/L in water
(b) Dilute an aliquot of the methanol extract and then take 100 L
for analysis. PRECISION RSD = 9.3% at 0.40 g/L conc.; 7 samples
QUALITY CONTROL Demonstrate, through the analysis of ACCURACY Average recovery = 83% at 0.40 g/L conc.;
a reagent water blank, that interferences from the analytical 7 samples
system, glassware, and reagents are under control. Blank sam-
SAMPLING METHOD Use a 40–120-mL screw-cap vial
ples should be carried through all stages of the sample prepa- (prewashed with detergent, rinsed with distilled water and oven
ration and measurement steps. For each analytical batch (up
dried at 105C) with a PTFE-faced silicone septum . If residual
to 20 samples), a reagent blank, matrix spike, and matrix spike chlorine is in the water add about 25 mg of ascorbic acid to
duplicate must be analyzed (the frequency of the spikes may each vial before sample collection. Collect bubble-free samples.
be different for different monitoring programs). The blank and
spiked samples must be carried through all stages of the sample STABILITY Cool to 4C; HCl to pH <2.
preparation and measurement steps. QC samples mentioned MHT 14 days.
in the section on Interferences will also be needed as appropri-
ate to those situations. QUALITY CONTROL As initial demonstration of lab accu-
racy and precision, analyze 4 to 7 replicates of a lab fortified
Matrix spiking standards should be prepared from volatile blank containing the analyte at 0.1–5 g/L. Collect all samples
organic compounds which will be representative of the com- in duplicate.
pounds being investigated. The recommended internal stan-
dards are chlorobenzene-d 5, 1,4 -difluorobenzene, REFERENCE Method 503.1, Volatile Aromatic & Unsatur-
1,4-dichlorobenzene-d4, and pentafluorobenzene. Using stock ated Organic Compounds in H2O by Purge and Trap GC, EPA
standard solutions, prepare secondary dilution standards con- 600/4-88/039.
taining the compounds of interest, either singly or mixed
together in methanol. Store them in a vial with no headspace
for no more than one week. Surrogates recommended are tol- Propylthiouracil EPA Method 8270
uene-d8, 4-bromofluorobenzene, and dibromofluoromethane. CAS #51-52-5
Each sample undergoing GC/MS analysis must be spiked with
10 L of the surrogate spiking solution prior to analysis. TITLE Semivolatile Organic Compounds by GC/MS
REFERENCE Test Methods for Evaluating Solid Waste (SW- MATRIX This method is used to determine the concentra-
846). U.S. EPA 1983, Method 8260A, Rev. 1, Nov. 1990. Office tion of semivolatile organic compounds in extracts prepared
of Solid Waste, Washington, DC. from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this
method should be applicable to water samples from rivers,
lakes, etc.
n-Propylbenzene EPA Method 503.1
CAS #103-65-1 METHOD SUMMARY This method covers 259 semivolatile
organic compounds. In very limited applications direct injec-
TITLE Aromatic & Unsaturated VOCs Water tion of the sample into the GC/MS system may be appropriate,
but this results in very high detection limits (approximately
MATRIX Drinking water (finished or in any treatment stage)
and raw source water. 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous
APPLICATION Method covers 28 aromatic and unsaturated extractor first under acid conditions and then under basic con-
VOCs. An inert gas is bubbled through a 5-mL water sample. ditions. Typically 30 g of a solid sample, containing surrogate,
Purged sample components are trapped in tube of sorbent and matrix spiking standards, is extracted ultrasonically. After
materials. When purging is complete, sorbent tube is heated concentrating the extract to 1 mL it is spiked with 10 L of an
and backflushed with inert gas to desorb trapped sample onto internal standard solution just prior to analysis by GC/MS. The
a packed GC column. volume injected should contain about 100 ng of base/neutral
and 200 ng of acid surrogates (for a 1-L injection). Analysis
INTERFERENCES During analysis, major contaminant
is performed by GC/MS using a capillary GC column.
sources are volatile materials in the lab and impurities in purg-
ing gas and sorbent trap. With high and low level samples, there INTERFERENCES Raw GC/MS data from all blanks, sam-
can be carryover contamination. Excess water causes a negative ples, and spikes must be evaluated for interferences. Contam-
baseline deflection. ination by carryover can occur whenever high-concentration

©1996 CRC Press LLC


and low-concentration samples are sequentially analyzed. To solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out then eliminate the sodium thiosulfate addition.
between samples with solvent. Whenever an unusually concen-
Soils, sediments, or sludges — Cool samples to 4C and store
trated sample is encountered, it should be followed by the
in a solvent-free refrigerator.
analysis of blank solvent to check for cross-contamination.
MHT Liquid samples must be extracted within 7 days and
INSTRUMENTATION A GC/MS and a data system are
the extracts analyzed within 40 days. Soils, sediments, or slud-
required. The GC column used is a 30 m 0.25 mm I.D. (or
ges may be stored for a maximum of 14 days and the extracts
0.32 mm I.D.) 1um film thickness silicone-coated fused silica
analyzed within 40 days.
capillary column. A continuous liquid-liquid extractor
equipped with Teflon® or glass connection joints and stopcocks SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
PRECISION & ACCURACY The estimated quantitation
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
limit (EQL) of Method 8270B for determining an individual
solution into each sample. For the sample in each analytical
compound is approximately 1 mg/kg (wet weight) for soil or
batch selected for spiking, add 1.0 mL of a matrix spiking stan-
sediment samples, 1–200 mg/kg for wastes (dependent on
dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground-
gates and matrix spiking compounds added to the sample
water samples. EQLs will be proportionately higher for sample
should result in a final concentration of 100 ng/L of each
extracts that require dilution to avoid saturation of the detector.
analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is 100. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
Overall precision in g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
concentrator.
(a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous
will be higher based on the % dry weight of each sample. or wet samples (gummy or clay type) that do not have a free-
This calculation is based on a 30 g sample and gel perme- flowing sandy texture must be mixed with anhydrous sodium
ation chromatography cleanup. sulfate until the sample is free flowing. Add 1 mL of surrogate
(b) Sample EQLs are highly matrix-dependent. The EQLs are standards to all samples, spikes, standards, and blanks. For the
provided for guidance and may not always be achievable. sample in each analytical batch selected for spiking, add 1.0 mL
C = True value for concentration, in g/L. of a matrix spiking standard. For base/neutral acid analysis, the
X = Average recovery found for measurements of samples con- amount added of the surrogates and matrix spiking com-
taining a concentration of C, in g/L. pounds should result in a final concentration of 100 ng/ L of
ESTIMATED QUANTITATION LIMIT each base/neutral analyte and 200 ng/L of each acid analyte
in the extract to be analyzed (assuming a 1- L injection).
Other Matrices Factor (a) Immediately add a 100-mL mixture of 1:1 methylene chlo-
High-concentration soil and sludges by sonicator 7.5 ride:acetone and extract the sample ultrasonically for 3 min
Non-water miscible waste 75 and then decant or filter the extracts. Repeat the extraction two
or more times. Dry the extract using a column with anhydrous
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
This estimated EQL is similar to an EPA “Practical Quantitation
Limit.” QUALITY CONTROL A methylene chloride solution con-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
SAMPLING METHOD
used for tuning the GC/MS system each 12-h shift. A system
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
performance check also must be made during every 12-h shift.
a screw-top Teflon®-lined cover that has been prewashed with
A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
detergent and rinsed with distilled water and methanol (or
rophenol, and benzidine is required to verify injection port
isopropanol).
inertness and GC column performance. A calibration standard
Soils, sediments, or sludges — Use an 8-oz. widemouth glass at mid-concentration, containing each compound of interest,
with a screw-top Teflon®-lined cover that has been prewashed including all required surrogates, must be performed every 12 h
with detergent and rinsed with distilled water and methanol during analysis. After the system performance check is met,
(or isopropanol). calibration check compounds (CCCs) are used to check the
validity of the initial calibration.
SAMPLE PRESERVATION
Liquid samples — If residual chlorine is present, add 3 mL of The internal standard responses and retention times in the
10% sodium thiosulfate per gallon, cool to 4C and store in a calibration check standard must be evaluated immediately after

©1996 CRC Press LLC


or during data acquisition. If the retention time for any internal separated by GC and detected by a MS. The labeled compounds
standard changes by more than 30 seconds from the last check serve to correct the variability of the analytical technique.
calibration (12 h), the chromatographic system must be
INTERFERENCES Solvents, reagents, glassware, and other
inspected for malfunctions and corrections must be made, as
sample processing hardware may yield artifacts and/or elevated
required. If the electron ionization current plot (EICP) area for
baselines causing misinterpretation of chromatograms and
any of the internal standards changes by a factor of two from
spectra. Materials used in the analysis must be demonstrated
the last daily calibration standard check, the mass spectrometer
to be free from interferences under the conditions of analysis
must be inspected for malfunctions and corrections must be
by running method blanks initially and with each sample lot
made, as appropriate.
(sample started through the extraction process on a given 8-h
Demonstrate, through the analysis of a reagent water blank, shift, to a maximum of 20). Specific selection of reagents and
that interferences from the analytical system, glassware, and purification of solvents by distillation in all glass systems may
reagents are under control. The blank samples should be car- be required. Glassware and, where possible, reagents are
ried through all stages of the sample preparation and measure- cleaned by solvent rinse and baking at 450C for 1-h minimum.
ment steps. For each analytical batch (up to 20 samples), a Interferences coextracted from samples will vary considerably
reagent blank, matrix spike, and matrix spike duplicate/dupli- from source to source, depending on the diversity of the site
cate must be analyzed (the frequency of the spikes may be being sampled.
different for different monitoring programs). The blank and
INSTRUMENTATION Major instrumentation includes a GC
spiked samples must be carried through all stages of the sample
with a splitless or on-column injection port for capillary col-
preparation and measurement steps. A QC reference sample
umn, a MS with 70 eV electron impact ionization, and a data
concentrate containing each analyte at a concentration of
system to collect and record MS data, and process it. A K-D
100 mg/L in methanol is required.
apparatus is used to concentrate extracts.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
vinyl silicone bonded phased fused silica capillary column.
of Solid Waste, Washington, DC.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
rather than instrumental limitations. The limits typify the min-
Pyrene EPA Method 1625
imum quantities that can be detected with no interferences
CAS #129-00-0
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was 10. This is defined as a
tion GC/MS minimum level at which the analytical system shall give recog-
nizable mass spectra (background corrected) and acceptable
MATRIX The compounds may be determined in waters,
calibration points.
soils, and municipal sludges by this method.
The MDL (in g/kg) in low solids was 40 and in high solids
METHOD SUMMARY This method is used to determine
was 48; these were determined in digested sludge (low solids)
176 semivolatile toxic organic pollutants associated with the
and in filter cake or compost (high solids).
CWA (as amended 1987); the RCRA (as amended 1986); the
CERCLA (as amended 1986); and other compounds amenable The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog- deviation (in g/L) was 19.
raphy-mass spectrometry (GC/MS). The labeled and native compound initial accuracy as average
recovery (in g/L) was 76–152.
Stable isotopically-labeled analogs of the compounds of interest
are added to the sample. If the solids content is less than 1%, SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques. flow freely are collected in refrigerated bottles using automatic
sampling equipment. Solid samples are collected as grab sam-
If the solids content is 30% or less, the sample is diluted to 1%
ples using widemouth jars. Maintain samples at 0 to 4C from
solids with reagent water, homogenized ultrasonically, and
the time of collection until extraction. If residual chlorine is
extracted at pH 12–13, then at pH <2 with methylene chloride
present in aqueous samples, add 80 mg sodium thiosulfate/L
using continuous extraction techniques. If the solids content is
of water. Begin sample extraction within 7 days of collection,
greater than 30%, the sample is extracted using ultrasonic
and analyze all extracts within 40 days of extraction.
techniques.
SAMPLE PREPARATION Samples containing 1% solids or
Each extract is dried over sodium sulfate, concentrated to a
less are extracted directly using continuous liquid-liquid
volume of 5 mL, cleaned up using GPC, if necessary, and con-
extraction techniques. Samples containing 1 to 30% solids are
centrated. Extracts are concentrated to 1 mL if GPC is not
diluted to the 1% level with reagent water and extracted using
performed, and to 0.5 mL if GPC is performed.
continuous liquid-liquid extraction techniques. Samples con-
An internal standard is added to the extract, and a 1-mL aliquot taining greater than 30% solids are extracted using ultrasonic
of the extract is injected into the GC. The compounds are techniques.

©1996 CRC Press LLC


Base/neutral extraction — Adjust the pH of the waters in the METHOD SUMMARY This method is used to determine
extractors to 12–13 with 6 N NaOH. Extract with methylene 176 semivolatile toxic organic pollutants associated with the
chloride for 24–48 h. CWA (as amended 1987); the RCRA (as amended 1986); the
Acid extraction — Adjust the pH of the waters in the extractors CERCLA (as amended 1986); and other compounds amenable
to 2 or less using 6 N sulfuric acid. Extract with methylene to extraction and analysis by capillary column gas chromatog-
chloride for 24–48 h. raphy-mass spectrometry (GC/MS).
Ultrasonic extraction of high solids samples — Add anhy-
Stable isotopically-labeled analogs of the compounds of interest
drous sodium sulfate to the sample and QC aliquot(s).
are added to the sample. If the solids content is less than 1%,
Add acetone:methylene chloride (1:1) to the sample and a 1-L sample is extracted at pH 12–13, then at pH <2 with
mix thoroughly methylene chloride using continuous extraction techniques.
Concentrate extracts using a K-D apparatus. If the solids content is 30% or less, the sample is diluted to 1%
QUALITY CONTROL The analyst is permitted to modify solids with reagent water, homogenized ultrasonically, and
this method to improve separations or lower the costs of mea- extracted at pH 12–13, then at pH <2 with methylene chloride
surements, provided all performance specifications are met. using continuous extraction techniques. If the solids content is
Analyses of blanks are required to demonstrate freedom from greater than 30%, the sample is extracted using ultrasonic
contamination. When results of spikes indicate atypical techniques.
method performance for samples, the samples are diluted to Each extract is dried over sodium sulfate, concentrated to a
bring method performance within acceptable limits. volume of 5 mL, cleaned up using GPC, if necessary, and con-
For low solids (aqueous samples), extract, concentrate, and centrated. Extracts are concentrated to 1 mL if GPC is not
analyze two sets of four 1-L aliquots (8 aliquots total) of the performed, and to 0.5 mL if GPC is performed.
precision and recovery standard. For high solids samples, two An internal standard is added to the extract, and a 1-mL aliquot
sets of four 30-g aliquots of the high solids reference matrix of the extract is injected into the GC. The compounds are
are used. separated by GC and detected by a MS. The labeled compounds
Spike all samples with labeled compounds to assess method serve to correct the variability of the analytical technique.
performance. Compute percent recovery of the labeled com- INTERFERENCES Solvents, reagents, glassware, and other
pounds using the internal standard method. Compare the sample processing hardware may yield artifacts and/or elevated
labeled compound recovery for each compound with the cor- baselines causing misinterpretation of chromatograms and
responding labeled compound recovery. spectra. Materials used in the analysis must be demonstrated
to be free from interferences under the conditions of analysis
Reagent water and high solids reference matrix blanks are ana-
by running method blanks initially and with each sample lot
lyzed to demonstrate freedom from contamination. Extract (sample started through the extraction process on a given 8-h
and concentrate a 1-L reagent water blank or a high solids shift, to a maximum of 20). Specific selection of reagents and
reference matrix blank with each sample’s lot (samples started purification of solvents by distillation in all glass systems may
through the extraction process on the same 8-h shift, to a be required. Glassware and, where possible, reagents are
maximum of 20 samples). cleaned by solvent rinse and baking at 450C for 1-h minimum.
Field replicates may be collected to determine the precision of Interferences coextracted from samples will vary considerably
the sampling technique, and spiked samples may be required from source to source, depending on the diversity of the site
to determine the accuracy of the analysis when the internal being sampled.
standard method is used. INSTRUMENTATION Major instrumentation includes a GC
REFERENCE Semivolatile Organic Compounds by Isotope with a splitless or on-column injection port for capillary col-
Dilution GC/MS. Office of Water Regulation and Standards, umn, a MS with 70 eV electron impact ionization, and a data
U.S. EPA Industrial Technology Division, Washington, DC, system to collect and record MS data, and process it. A K-D
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, apparatus is used to concentrate extracts.
U.S. EPA, Office of Water Regulations and Standards, 401 M GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
St., SW, Washington, DC, 20460. Phone: 202-382-7131). vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
Pyrene EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #129-00-0 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
The minimum level (in g/mL) was 10. This is defined as a
tion GC/MS
minimum level at which the analytical system shall give recog-
MATRIX The compounds may be determined in waters, nizable mass spectra (background corrected) and acceptable
soils, and municipal sludges by this method. calibration points.

©1996 CRC Press LLC


The MDL (in g/kg) in low solids was 40 and in high solids through the extraction process on the same 8-h shift, to a
was 48; these were determined in digested sludge (low solids) maximum of 20 samples).
and in filter cake or compost (high solids).
Field replicates may be collected to determine the precision of
The labeled and native compound initial precision as standard the sampling technique, and spiked samples may be required
deviation (in g/L) was 19. to determine the accuracy of the analysis when the internal
The labeled and native compound initial accuracy as average standard method is used.
recovery (in g/L) was 76–152.
REFERENCE Semivolatile Organic Compounds by Isotope
SAMPLE COLLECTION, PRESERVATION & HANDLING Dilution GC/MS. Office of Water Regulation and Standards,
Collect samples in glass containers. Aqueous samples which U.S. EPA Industrial Technology Division, Washington, DC,
flow freely are collected in refrigerated bottles using automatic EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
sampling equipment. Solid samples are collected as grab sam- U.S. EPA, Office of Water Regulations and Standards, 401 M
ples using widemouth jars. Maintain samples at 0 to 4C from St., SW, Washington, DC, 20460. Phone: 202-382-7131).
the time of collection until extraction. If residual chlorine is
present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
and analyze all extracts within 40 days of extraction. Pyrene EPA Method 625
CAS #129-00-0
SAMPLE PREPARATION Samples containing 1% solids or
less are extracted directly using continuous liquid-liquid TITLE Base/Neutrals and Acids, U.S. EPA Method 625
extraction techniques. Samples containing 1 to 30% solids are
diluted to the 1% level with reagent water and extracted using MATRIX This methods covers municipal and industrial
continuous liquid-liquid extraction techniques. Samples con- wastewaters.
taining greater than 30% solids are extracted using ultrasonic METHOD SUMMARY Approximately 1 L of sample is seri-
techniques. ally extracted with methylene chloride at a pH greater than 11
and again at a pH less than 2 using a separatory funnel or a
Base/neutral extraction — Adjust the pH of the waters in the
extractors to 12–13 with 6 N NaOH. Extract with methylene continuous extractor. The methylene chloride extract is dried,
concentrated to a volume of 1 mL, and analyzed by GC/MS.
chloride for 24–48 h.
Acid extraction — Adjust the pH of the waters in the extractors Qualitative identification of the parameters in the extract is
to 2 or less using 6 N sulfuric acid. Extract with methylene performed using the retention time and the relative abundance
chloride for 24–48 h. of three characteristic masses (m/z). Qualitative analysis is per-
Ultrasonic extraction of high solids samples — Add anhy- formed using either external or internal standard techniques
with a single characteristic m/z.
drous sodium sulfate to the sample and QC aliquot(s).
Add acetone:methylene chloride (1:1) to the sample and INTERFERENCES Method interferences may be caused by
mix thoroughly contaminants in solvents, reagents, glassware, and other sample
Concentrate extracts using a K-D apparatus. processing hardware. Glassware must be scrupulously cleaned.
Glassware should be heated in a muffle furnace at 400C for 5
QUALITY CONTROL The analyst is permitted to modify to 30 min. Some thermally stable materials, such as PCBs, may
this method to improve separations or lower the costs of mea- not be eliminated by this treatment. Solvent rinses with acetone
surements, provided all performance specifications are met. and pesticide quality hexane may be substituted for the muffle
Analyses of blanks are required to demonstrate freedom from furnace heating. Matrix interferences may be caused by con-
contamination. When results of spikes indicate atypical taminants that are coextracted from the sample. The base-
method performance for samples, the samples are diluted to neutral extraction may cause significantly reduced recovery of
bring method performance within acceptable limits. phenols. The packed gas chromatographic columns recom-
mended for the basic fraction may not exhibit sufficient reso-
For low solids (aqueous samples), extract, concentrate, and
lution for some analytes.
analyze two sets of four 1-L aliquots (8 aliquots total) of the
precision and recovery standard. For high solids samples, two INSTRUMENTATION A GC/MS system with an injection
sets of four 30-g aliquots of the high solids reference matrix port designed for on-column injection when using packed col-
are used. umns and for splitless injection when using capillary columns.
Spike all samples with labeled compounds to assess method Column for base/neutrals: 1.8 m long  2 mm I.D. glass,
performance. Compute percent recovery of the labeled com- packed with 3% SP-2550 on Supelcoport (100/120 mesh)
pounds using the internal standard method. Compare the or equivalent.
labeled compound recovery for each compound with the cor- Column for acids: 1.8 m long 2 mm I.D. glass, packed with 1%
responding labeled compound recovery. SP-1240DA on Supelcoport (100/120 mesh) or equivalent.
Reagent water and high solids reference matrix blanks are ana- PRECISION & ACCURACY The MDL concentrations were
lyzed to demonstrate freedom from contamination. Extract obtained using reagent water. The MDL actually achieved in a
and concentrate a 1-L reagent water blank or a high solids given analysis will vary depending on instrument sensitivity
reference matrix blank with each sample’s lot (samples started and matrix effects. This method was tested by 15 laboratories

©1996 CRC Press LLC


using reagent water, drinking water, surface water, and indus- REFERENCE Federal Register, Vol. 49, No. 209. Friday, Oct.
trial wastewaters spiked at six concentrations over the range 5 26, 1984.
to 100 g/L. Single operator precision, overall precision, and
method accuracy were found to be directly related to the con-
centration of the parameter matrix.
Pyrene EPA Method 8270
The MDL (in g/L) in reagent water was 1.9. CAS #129-00-0
The standard deviation (in g/L based on 4 recovery measure-
ments) was 25.2. TITLE Semivolatile Organic Compounds by GC/MS
The range (in g/L) for average recovery for 4 measurements MATRIX This method is used to determine the concentra-
was 69.6–100.0. tion of semivolatile organic compounds in extracts prepared
The range (in %) for percent recovery was 52–115. from all types of solid waste matrices, soils, and groundwater.
Accuracy (in g/L) as expected recovery for one or more mea- Although surface waters are not specifically mentioned, this
surements of a sample containing a true concentration of method should be applicable to water samples from rivers,
C was 0.84C-0.16. lakes, etc.
Precision (in g/L) as expected single analyst standard devia-
tion of measurements at an average concentration found at METHOD SUMMARY This method covers 259 semivolatile
X was 0.16X + 0.06. organic compounds. In very limited applications direct injec-
Overall precision (in g/L) as expected interlaboratory stan- tion of the sample into the GC/MS system may be appropriate,
dard deviation of measurements in an average concentra- but this results in very high detection limits (approximately
tion found at X was 0.15X + 0.31. 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous
C = True value of the concentration in g/L. extractor first under acid conditions and then under basic con-
X = Average recovery found for measurements of samples con- ditions. Typically 30 g of a solid sample, containing surrogate,
taining a concentration at C in g/L. and matrix spiking standards, is extracted ultrasonically. After
SAMPLE PREPARATION Adjust the pH to >11 with sodium concentrating the extract to 1 mL it is spiked with 10 L of an
internal standard solution just prior to analysis by GC/MS. The
hydroxide and serially extract in a separatory funnel with meth-
volume injected should contain about 100 ng of base/neutral
ylene chloride or else in a continuous extractor. Next, adjust
and 200 ng of acid surrogates (for a 1-L injection). Analysis
the pH to <2 with sulfuric acid and serially extract in a sepa-
is performed by GC/MS using a capillary GC column.
ratory funnel with methylene chloride or else in a continuous
extractor. Dry the extracts separately through a column of INTERFERENCES Raw GC/MS data from all blanks, sam-
anhydrous sodium sulfate and then concentrate each of the ples, and spikes must be evaluated for interferences. Contam-
extracts to 1.0 mL using a K-D apparatus. ination by carryover can occur whenever high-concentration
and low-concentration samples are sequentially analyzed. To
SAMPLE COLLECTION, PRESERVATION & HANDLING reduce carryover, the sample syringe must be rinsed out
Grab samples must be collected in glass containers. All samples between samples with solvent. Whenever an unusually concen-
must be refrigerated at 4C from the time of collection until trated sample is encountered, it should be followed by the
extraction. If residual chlorine is present, add 80 mg of sodium analysis of blank solvent to check for cross-contamination.
thiosulfate/L of sample and mix well. All samples must be
extracted within 7 days of collection and completely analyzed INSTRUMENTATION A GC/MS and a data system are
within 40 days of extraction. required. The GC column used is a 30 m 0.25 mm I.D. (or
0.32 mm I.D.) 1um film thickness silicone-coated fused silica
QUALITY CONTROL Make an initial, one-time, demonstra- capillary column. A continuous liquid-liquid extractor
tion of the ability to generate acceptable accuracy and precision equipped with Teflon® or glass connection joints and stopcocks
with this method. Before processing any samples, the analyst requiring no lubrication, a K-D concentrating apparatus, water
must analyze a reagent water blank to demonstrate that inter- bath, and an ultrasonic disrupter with a minimum power of
ferences from the analytical system and glassware are under 300 W and with pulsing capability are also required.
control. Each time a set of samples is extracted or reagents are
PRECISION & ACCURACY The estimated quantitation
changed, a reagent water blank must be processed. Spike and limit (EQL) of Method 8270B for determining an individual
analyze a minimum of 5% of all samples to monitor and eval- compound is approximately 1 mg/kg (wet weight) for soil or
uate lab data quality. A QC check sample concentrate that sediment samples, 1–200 mg/kg for wastes (dependent on
contains each parameter of interest at a concentration of matrix and method of preparation), and 10 g/L for ground-
100 g/mL in acetone is required. PCBs and multicomponent water samples. EQLs will be proportionately higher for sample
pesticides may be omitted from this test. extracts that require dilution to avoid saturation of the detector.
After analysis of five spiked wastewater samples, calculate the The EQL(b) for groundwater in g/L is 10.
average percent recovery and the standard deviation of the The EQL (a, b) for low concentrations in soil and sediment
percent recovery. Spike all samples with the surrogate standard in g/kg is 660.
spiking solution and calculate the percent recovery of each Accuracy as g/L is 0.84C–0.16.
surrogate compound. Overall precision in g/L is 0.15X + 0.31.

©1996 CRC Press LLC


(a) EQLs listed for soil/sediment are based on wet weight. Nor- drous sodium sulfate and concentrate it to 1 mL using a K-D
mally data is reported in a dry-weight basis; therefore, EQLs concentrator.
will be higher based on the % dry weight of each sample.
Soils, sediments, or sludges — Use 30 g of sample. Nonporous
This calculation is based on a 30 g sample and gel perme- or wet samples (gummy or clay type) that do not have a free-
ation chromatography cleanup. flowing sandy texture must be mixed with anhydrous sodium
(b) Sample EQLs are highly matrix-dependent. The EQLs are sulfate until the sample is free flowing. Add 1 mL of surrogate
provided for guidance and may not always be achievable. standards to all samples, spikes, standards, and blanks. For the
C = True value for concentration, in g/L. sample in each analytical batch selected for spiking, add 1.0 mL
X = Average recovery found for measurements of samples con- of a matrix spiking standard. For base/neutral acid analysis, the
taining a concentration of C, in g/L. amount added of the surrogates and matrix spiking com-
ESTIMATED QUANTITATION LIMIT pounds should result in a final concentration of 100 ng/ L of
Other Matrices Factor (a) each base/neutral analyte and 200 ng/L of each acid analyte
in the extract to be analyzed (assuming a 1- L injection).
High-concentration soil and sludges by sonicator 7.5 Immediately add a 100-mL mixture of 1:1 methylene chlo-
Non-water miscible waste 75 ride:acetone and extract the sample ultrasonically for 3 min
(a) EQL forother matrices =[EQL forlow soil/sediment] [Factor]. and then decant or filter the extracts. Repeat the extraction two
This estimated EQL is similar to an EPA “Practical Quantitation or more times. Dry the extract using a column with anhydrous
Limit.” sodium sulfate and concentrate it to 1 mL in a K-D concentrator.

SAMPLING METHOD QUALITY CONTROL A methylene chloride solution con-


Liquid samples — Use a 1 or 2½ gallon amber glass bottle with taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
a screw-top Teflon®-lined cover that has been prewashed with used for tuning the GC/MS system each 12-h shift. A system
detergent and rinsed with distilled water and methanol (or performance check also must be made during every 12-h shift.
isopropanol). A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
rophenol, and benzidine is required to verify injection port
Soils, sediments, or sludges — Use an 8-oz. widemouth glass inertness and GC column performance. A calibration standard
with a screw-top Teflon®-lined cover that has been prewashed at mid-concentration, containing each compound of interest,
with detergent and rinsed with distilled water and methanol including all required surrogates, must be performed every 12 h
(or isopropanol). during analysis. After the system performance check is met,
calibration check compounds (CCCs) are used to check the
SAMPLE PRESERVATION
Liquid samples — If residual chlorine is present, add 3 mL of validity of the initial calibration.
10% sodium thiosulfate per gallon, cool to 4C and store in a The internal standard responses and retention times in the
solvent-free refrigerator until analysis; if chlorine is not present, calibration check standard must be evaluated immediately after
then eliminate the sodium thiosulfate addition. or during data acquisition. If the retention time for any internal
standard changes by more than 30 seconds from the last check
Soils, sediments, or sludges — Cool samples to 4C and store
calibration (12 h), the chromatographic system must be
in a solvent-free refrigerator.
inspected for malfunctions and corrections must be made, as
MHT Liquid samples must be extracted within 7 days and required. If the electron ionization current plot (EICP) area for
the extracts analyzed within 40 days. Soils, sediments, or slud- any of the internal standards changes by a factor of two from
ges may be stored for a maximum of 14 days and the extracts the last daily calibration standard check, the mass spectrometer
analyzed within 40 days. must be inspected for malfunctions and corrections must be
made, as appropriate.
SAMPLE PREPARATION
Liquid samples — Transfer 1 L quantitatively to a continuous Demonstrate, through the analysis of a reagent water blank,
extractor. If high concentrations are anticipated, a smaller vol- that interferences from the analytical system, glassware, and
ume may be used and then diluted with organic-free reagent reagents are under control. The blank samples should be car-
water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V) ried through all stages of the sample preparation and measure-
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking ment steps. For each analytical batch (up to 20 samples), a
solution into each sample. For the sample in each analytical reagent blank, matrix spike, and matrix spike duplicate/dupli-
batch selected for spiking, add 1.0 mL of a matrix spiking stan- cate must be analyzed (the frequency of the spikes may be
dard. For base/neutral acid analysis, the amount of the surro- different for different monitoring programs). The blank and
gates and matrix spiking compounds added to the sample spiked samples must be carried through all stages of the sample
should result in a final concentration of 100 ng/L of each preparation and measurement steps. A QC reference sample
concentrate containing each analyte at a concentration of
analyte in the extract to be analyzed (assuming a 1- L injec-
100 mg/L in methanol is required.
tion). Extract with methylene chloride for 18–24 h. Next, adjust
the pH of the aqueous phase to pH >11 using 10 N sodium REFERENCE Test Methods for Evaluating Solid Waste (SW-
hydroxide and extract it with methylene chloride again for 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
18–24 h. Dry the extract through a column containing anhy- of Solid Waste, Washington, DC.

©1996 CRC Press LLC


Pyrene EPA Method 8100 Pyrene EPA Method 8310
CAS #129-00-0 CAS #129-00-0

TITLE Polynuclear Aromatic Hydrocarbons TITLE Polynuclear Aromatic Hydrocarbons


MATRIX Groundwater, soils, sludges, water miscible liquid MATRIX Groundwater, soils, sludges, water miscible liquid
wastes, and non-water miscible wastes. wastes, and non-water miscible wastes.
APPLICATION This method is used for the analysis of var- APPLICATION This method is used for the analysis of 16
ious PAHs. Samples are extracted, concentrated, and analyzed polynuclear aromatic hydrocarbons (PAHs). Samples are
using direct injection of both neat and diluted organic liquids. extracted, concentrated, and analyzed using HPLC with detec-
The method provides two optional GC columns that are better tion by UV and fluorescence detectors.
than Column 1 and that may help resolve analytes from inter-
ferences. INTERFERENCES Solvents, reagents, and glassware may
introduce artifacts. Other interferences may come from coex-
INTERFERENCES Solvents, reagents, and glassware may tracted compounds from samples.
introduce artifacts. Other interferences may come from coex-
tracted compounds from samples. INSTRUMENTATION HPLC with a gradient pumping sys-
tem and a 250 mm by 2.6 mm reverse phase HC-ODS Sil-X
INSTRUMENTATION GC capable of on-column injections
5-micron particle-size column. The fluorescence detector uses
and a flame with detector (FID). Column 1: a 1.8 m by 2 mm
an excitation wavelength of 280 nm and emission greater than
3% OV-17 on Chromosorb W-AW-DCMS column. Column 2:
a 30 m by 0.25 mm SE-54 fused silica capillary colunm. Col- 389 nm cutoff with dispersive optics.
umn 3: a 30 m by 0.32 mm SE-54 fused silica capillary column. RANGE 0.1–425 g/L
RANGE 0.1–425 g/L MDL 0.27 g/L (fluorescence; reagent water).
MDL Not reported. PQL FACTORS FOR MULTIPLYING  FID MDL VALUE
PQL FACTORS FOR MULTIPLYING FID MDL Matrix Multiplication Factor
VALUE Not available. Groundwater 10
PRECISION 0.42X–0.00 g/L (overall precision). Low-level soil by sonication with GPC cleanup 670
High-level soil and sludge by sonication 10,000
ACCURACY 0.69C–0.12 g/L (as recovery). Non-water miscible waste 100,000
SAMPLING METHOD Use 8-oz. widemouth glass bottles PRECISION 0.42X–0.00 g/L (overall precision).
with Teflon®-lined caps for concentrated waste samples, soils,
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles ACCURACY 0.69C–0.12 g/L (as recovery).
with Teflon®-lined caps for liquid (water) samples. SAMPLING METHOD Use 8-oz. widemouth glass bottles
STABILITY Cool soil, sediment, sludge, and liquid samples with Teflon®-lined caps for concentrated waste samples, soils,
to 4C. If residual chlorine is present in liquid samples add sediments, and sludges. Use 1 or 2½ gallon amber glass bottles
3 mL of 10% sodium thiosulfate per gallon of sample and cool with Teflon®-lined caps for liquid (water) samples.
to 4C.
STABILITY Cool soil, sediment, sludge, and liquid samples
MHT 14 days for concentrated waste, soil, sediment, or to 4C. If residual chlorine is present in liquid samples add
sludge; 7 days for liquid samples; all extracts must be analyzed 3 mL of 10% sodium thiosulfate per gallon of sample and cool
within 40 days. to 4C.
QUALITY CONTROL A quality control check sample con- MHT 14 days for concentrated waste, soil, sediment, or
centrate containing each analyte of interest is required. The QC sludge; 7 days for liquid samples; all extracts must be analyzed
check sample concentrate may be prepared from pure standard within 40 days.
materials or purchased as certified solutions Use appropriate
trip, matrix, control site, method, reagent, and solvent blanks. QUALITY CONTROL Internal, surrogate, and five concen-
Internal, surrogate, and five concentration level calibration tration level calibration standards are used. The calibration
standards are used. The quality control check sample concen- standards must be used with the analytical method blank. A
trate should contain pyrene at 10 g/mL in acetonitrile. quality control check sample concentrate containing pyrene at
10 g/mL is required. The QC check sample concentrate may
REFERENCE Test Methods for Evaluating Solid Waste be prepared from pure standard materials or purchased as cer-
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
tified solutions. Use appropriate trip, matrix, control site,
Method 8100, Nov. 1986.
method, reagent, and solvent blanks.
REFERENCE Test Methods for Evaluating Solid Waste
(SW-846), U.S. EPA Office of Solid Waste, Washington, DC,
Method 8310, Rev. 0, Nov. 1986.

©1996 CRC Press LLC


rather than instrumental limitations. The limits typify the min-
Pyridine EPA Method 1625
CAS #110-86-1 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu- The minimum level (in g/mL) was not listed. This is defined
tion GC/MS as a minimum level at which the analytical system shall give
MATRIX The compounds may be determined in waters, recognizable mass spectra (background corrected) and accept-
soils, and municipal sludges by this method. able calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was not listed and in high
176 semivolatile toxic organic pollutants associated with the solids was not listed; these were determined in digested sludge
CWA (as amended 1987); the RCRA (as amended 1986); the (low solids) and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
The labeled and native compound initial precision as standard
to extraction and analysis by capillary column gas chromatog-
deviation (in g/L) was not listed.
raphy-mass spectrometry (GC/MS).
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%,
a 1-L sample is extracted at pH 12–13, then at pH <2 with SAMPLE COLLECTION, PRESERVATION & HANDLING
methylene chloride using continuous extraction techniques. Collect samples in glass containers. Aqueous samples which
flow freely are collected in refrigerated bottles using automatic
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from
extracted at pH 12–13, then at pH <2 with methylene chloride the time of collection until extraction. If residual chlorine is
using continuous extraction techniques. If the solids content is present in aqueous samples, add 80 mg sodium thiosulfate/L
greater than 30%, the sample is extracted using ultrasonic of water. Begin sample extraction within 7 days of collection,
techniques. and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a SAMPLE PREPARATION Samples containing 1% solids or
volume of 5 mL, cleaned up using GPC, if necessary, and con-
less are extracted directly using continuous liquid-liquid
centrated. Extracts are concentrated to 1 mL if GPC is not
extraction techniques. Samples containing 1 to 30% solids are
performed, and to 0.5 mL if GPC is performed.
diluted to the 1% level with reagent water and extracted using
An internal standard is added to the extract, and a 1-mL aliquot continuous liquid-liquid extraction techniques. Samples con-
of the extract is injected into the GC. The compounds are taining greater than 30% solids are extracted using ultrasonic
separated by GC and detected by a MS. The labeled compounds techniques.
serve to correct the variability of the analytical technique.
Base/neutral extraction — Adjust the pH of the waters in the
INTERFERENCES Solvents, reagents, glassware, and other extractors to 12–13 with 6 N NaOH. Extract with methylene
sample processing hardware may yield artifacts and/or elevated chloride for 24–48 h.
baselines causing misinterpretation of chromatograms and Acid extraction — Adjust the pH of the waters in the extractors
spectra. Materials used in the analysis must be demonstrated to 2 or less using 6 N sulfuric acid. Extract with methylene
to be free from interferences under the conditions of analysis
chloride for 24–48 h.
by running method blanks initially and with each sample lot
Ultrasonic extraction of high solids samples — Add anhy-
(sample started through the extraction process on a given 8-h
drous sodium sulfate to the sample and QC aliquot(s).
shift, to a maximum of 20). Specific selection of reagents and
purification of solvents by distillation in all glass systems may Add acetone:methylene chloride (1:1) to the sample and
be required. Glassware and, where possible, reagents are mix thoroughly
cleaned by solvent rinse and baking at 450C for 1-h minimum. Concentrate extracts using a K-D apparatus.
Interferences coextracted from samples will vary considerably
from source to source, depending on the diversity of the site QUALITY CONTROL The analyst is permitted to modify
being sampled. this method to improve separations or lower the costs of mea-
surements, provided all performance specifications are met.
INSTRUMENTATION Major instrumentation includes a GC Analyses of blanks are required to demonstrate freedom from
with a splitless or on-column injection port for capillary col- contamination. When results of spikes indicate atypical
umn, a MS with 70 eV electron impact ionization, and a data
method performance for samples, the samples are diluted to
system to collect and record MS data, and process it. A K-D
bring method performance within acceptable limits.
apparatus is used to concentrate extracts.
For low solids (aqueous samples), extract, concentrate, and
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
analyze two sets of four 1-L aliquots (8 aliquots total) of the
vinyl silicone bonded phased fused silica capillary column.
precision and recovery standard. For high solids samples, two
PRECISION & ACCURACY The detection limits of the sets of four 30-g aliquots of the high solids reference matrix
method are usually dependent on the level of interferences are used.

©1996 CRC Press LLC


Spike all samples with labeled compounds to assess method INTERFERENCES Solvents, reagents, glassware, and other
performance. Compute percent recovery of the labeled com- sample processing hardware may yield artifacts and/or elevated
pounds using the internal standard method. Compare the baselines causing misinterpretation of chromatograms and
labeled compound recovery for each compound with the cor- spectra. Materials used in the analysis must be demonstrated
responding labeled compound recovery. to be free from interferences under the conditions of analysis
Reagent water and high solids reference matrix blanks are ana- by running method blanks initially and with each sample lot
lyzed to demonstrate freedom from contamination. Extract (sample started through the extraction process on a given 8-h
and concentrate a 1-L reagent water blank or a high solids shift, to a maximum of 20). Specific selection of reagents and
reference matrix blank with each sample’s lot (samples started purification of solvents by distillation in all glass systems may
through the extraction process on the same 8-h shift, to a be required. Glassware and, where possible, reagents are
maximum of 20 samples). cleaned by solvent rinse and baking at 450C for 1-h minimum.
Interferences coextracted from samples will vary considerably
Field replicates may be collected to determine the precision of
the sampling technique, and spiked samples may be required from source to source, depending on the diversity of the site
to determine the accuracy of the analysis when the internal being sampled.
standard method is used. INSTRUMENTATION Major instrumentation includes a GC
REFERENCE Semivolatile Organic Compounds by Isotope with a splitless or on-column injection port for capillary col-
Dilution GC/MS. Office of Water Regulation and Standards, umn, a MS with 70 eV electron impact ionization, and a data
U.S. EPA Industrial Technology Division, Washington, DC, system to collect and record MS data, and process it. A K-D
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, apparatus is used to concentrate extracts.
U.S. EPA, Office of Water Regulations and Standards, 401 M GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
St., SW, Washington, DC, 20460. Phone: 202-382-7131). vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
Pyridine EPA Method 1625
rather than instrumental limitations. The limits typify the min-
CAS #110-86-1
imum quantities that can be detected with no interferences
TITLE Semivolatile Organic Compounds by Isotope Dilu- present.
tion GC/MS The minimum level (in g/mL) was not listed. This is defined
MATRIX The compounds may be determined in waters, as a minimum level at which the analytical system shall give
soils, and municipal sludges by this method. recognizable mass spectra (background corrected) and accept-
able calibration points.
METHOD SUMMARY This method is used to determine
176 semivolatile toxic organic pollutants associated with the The MDL (in g/kg) in low solids was not listed and in high
CWA (as amended 1987); the RCRA (as amended 1986); the solids was not listed; these were determined in digested sludge
CERCLA (as amended 1986); and other compounds amenable (low solids) and in filter cake or compost (high solids).
to extraction and analysis by capillary column gas chromatog- The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS). deviation (in g/L) was not listed.
Stable isotopically-labeled analogs of the compounds of interest The labeled and native compound initial accuracy as average
are added to the sample. If the solids content is less than 1%, recovery (in g/L) was not listed.
a 1-L sample is extracted at pH 12–13, then at pH <2 with
SAMPLE COLLECTION, PRESERVATION & HANDLING
methylene chloride using continuous extraction techniques.
Collect samples in glass containers. Aqueous samples which
If the solids content is 30% or less, the sample is diluted to 1% flow freely are collected in refrigerated bottles using automatic
solids with reagent water, homogenized ultrasonically, and sampling equipment. Solid samples are collected as grab sam-
extracted at pH 12–13, then at pH <2 with methylene chloride ples using widemouth jars. Maintain samples at 0 to 4C from
using continuous extraction techniques. If the solids content is the time of collection until extraction. If residual chlorine is
greater than 30%, the sample is extracted using ultrasonic present in aqueous samples, add 80 mg sodium thiosulfate/L
techniques. of water. Begin sample extraction within 7 days of collection,
Each extract is dried over sodium sulfate, concentrated to a and analyze all extracts within 40 days of extraction.
volume of 5 mL, cleaned up using GPC, if necessary, and con- SAMPLE PREPARATION Samples containing 1% solids or
centrated. Extracts are concentrated to 1 mL if GPC is not less are extracted directly using continuous liquid-liquid
performed, and to 0.5 mL if GPC is performed. extraction techniques. Samples containing 1 to 30% solids are
An internal standard is added to the extract, and a 1-mL aliquot diluted to the 1% level with reagent water and extracted using
of the extract is injected into the GC. The compounds are continuous liquid-liquid extraction techniques. Samples con-
separated by GC and detected by a MS. The labeled compounds taining greater than 30% solids are extracted using ultrasonic
serve to correct the variability of the analytical technique. techniques.

©1996 CRC Press LLC


Base/neutral extraction — Adjust the pH of the waters in the metric emulsions, filter cakes, spent carbons, spent catalysts,
extractors to 12–13 with 6 N NaOH. Extract with methylene soils, and sediments.
chloride for 24–48 h.
METHOD SUMMARY Method 8240B covers 80 volatile
Acid extraction — Adjust the pH of the waters in the extractors
organic compounds that are introduced into a gas chromato-
to 2 or less using 6 N sulfuric acid. Extract with methylene
graph by the purge-and-trap method or by direct injection (in
chloride for 24–48 h.
limited applications). For the purge-and-trap method an inert
Ultrasonic extraction of high solids samples — Add anhy-
gas (zero grade nitrogen or helium) is bubbled through a 5-mL
drous sodium sulfate to the sample and QC aliquot(s).
solution at ambient temperature. Purged sample components
Add acetone:methylene chloride (1:1) to the sample and
are trapped in a tube of sorbent materials. When purging is
mix thoroughly
complete, the sorbent tube is heated and backflushed with inert
Concentrate extracts using a K-D apparatus. gas to desorb the trapped components onto a GC column.
QUALITY CONTROL The analyst is permitted to modify INTERFERENCES Impurities in the purge gas and from
this method to improve separations or lower the costs of mea- organic compounds outgassing from the plumbing ahead of
surements, provided all performance specifications are met. the trap account for many contamination problems. Interfer-
Analyses of blanks are required to demonstrate freedom from ences purged or coextracted from the samples will vary con-
contamination. When results of spikes indicate atypical siderably from source to source. Cross-contamination can
method performance for samples, the samples are diluted to occur whenever high-level and low-level samples are analyzed
bring method performance within acceptable limits. sequentially. Whenever an unusually concentrated sample is
analyzed, it should be followed by the analysis of organic-free
For low solids (aqueous samples), extract, concentrate, and
reagent water to check for cross-contamination. Samples also
analyze two sets of four 1-L aliquots (8 aliquots total) of the
can be contaminated by diffusion of volatile organics (partic-
precision and recovery standard. For high solids samples, two
ularly methylene chloride and fluorocarbons) through the sep-
sets of four 30-g aliquots of the high solids reference matrix
tum seal into the sample during shipment and storage. A trip
are used.
blank can serve as a check on such contamination. The lab
Spike all samples with labeled compounds to assess method where volatile analysis is performed and also the refrigerated
performance. Compute percent recovery of the labeled com- storage area should be completely free of solvents.
pounds using the internal standard method. Compare the
INSTRUMENTATION A gas chromatograph/mass spec-
labeled compound recovery for each compound with the cor-
trometry/data system (GC/MS) equipped with a 6 ft 0.1 in
responding labeled compound recovery.
I.D. glass column packed with 1% SP-1000 on Carbopack-B
Reagent water and high solids reference matrix blanks are ana- (60/80 mesh) is required.Also needed is a 5-mL purging device,
lyzed to demonstrate freedom from contamination. Extract a sorbent trap, and a thermal desorption apparatus.
and concentrate a 1-L reagent water blank or a high solids
PRECISION & ACCURACY This method is reported to have
reference matrix blank with each sample’s lot (samples started
been tested by 15 laboratories using organic-free reagent water,
through the extraction process on the same 8-h shift, to a
drinking water, surface water, and industrial wastewaters (not
maximum of 20 samples).
specified) fortified at six concentrations over the range 5–
Field replicates may be collected to determine the precision of 600 g/L.
the sampling technique, and spiked samples may be required
Sample estimated quantitation limits (EQLs) are highly
to determine the accuracy of the analysis when the internal
matrix-dependent. The EQLs listed may not always be achiev-
standard method is used.
able. EQLs listed for soils or sediments are based on wet weight.
REFERENCE Semivolatile Organic Compounds by Isotope Normally, data is reported on a dry-weight basis; therefore,
Dilution GC/MS. Office of Water Regulation and Standards, EQLs will be higher, based on the percent dry weight of each
U.S. EPA Industrial Technology Division, Washington, DC, sample. Note that EQLs are even more variable than MDLs and
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, that they are highly variable depending on the matrix being
U.S. EPA, Office of Water Regulations and Standards, 401 M analyzed.
St., SW, Washington, DC, 20460. Phone: 202-382-7131).
EQL in groundwater in g/L was not listed.
EQL in low soil or sediment in g/kg was not listed.
Accuracy (a) in g/L was not listed.
Pyridine EPA Method 8240 Precision (b) in g/L was not listed.
CAS #110-86-1
(a) Average recovery found for measurements of samples con-
taining a concentration of C, in g/L.
TITLE Volatile Organics By GC/MS: Packed Column Technique
(b) Overall precision found for measurements of samples with
MATRIX Nearly all types of sample matarices, regardless of average recovery X for samples containing a concentration
water content, can be analyzed using this method. This includes of C in g/L.
groundwater, aqueous sludges, caustic liquors, acid liquors, X = Average recovery found for measurement of samples con-
waste solvents, oily wastes, mousses, tars, fibrous wastes, poly- taining a concentration of C in g/L.

©1996 CRC Press LLC


MULTIPLICATION FACTORS FOR OTHER MATRICES Use a 5-g sample if the expected concentration is <0.1 mg/kg
Other Matrices Factor (a) or a 1-g sample for expected concentrations between 0.1 and
1 mg/kg. Mix the contents of the sample container with a nar-
Waste miscible liquid waste 50 row metal spatula. Weigh the amount of the sample into a tared
High-concentration soil and sludge 125 purge device. Add the spiked water to the purge device, which
Non-water miscible waste 500 contains the weighed amount of sample, and connect the
(a) EQL = [EQL for low soil/sediment] [Factor].For non-aqueous device to the purge-and-trap system.
samples, the factor is on a wet-weight basis. High-concentration method — This method is based on
SAMPLING METHOD extracting the sediment or soil with methanol. A waste sample
Liquid samples — Use a 40-mL glass screw-cap VOA vial with is either extracted or diluted, depending on its solubility in
a Teflon®-faced silicone septum that has been prewashed, methanol. Wastes that are insoluble in methanol are diluted
rinsed with distilled deionized water, and oven dried. However, with reagent tetraglyme or possibly polyethylene glycol (PEG).
if residual chlorine is present, collect sample in a 40-oz. soil An aliquot of the extract is added to organic-free reagent water
VOA container which has been pre-preserved with 4 drops of containing surrogate and internal standards. This is purged at
10% sodium thiosulfate, mix gently, and then transfer the sam- ambient temperature. All samples with an expected concentra-
ple to a 40-mL VOA vial. Collect bubble-free samples in dupli- tion of >1.0 mg/kg should be analyzed by this method.
cate and seal them in separate plastic bags. Mix the contents of the sample container with a narrow metal
Soils or sediments, and sludges — Use an 8-oz. widemouth spatula. For sediments or soils and solid wastes that are insol-
glass bottle with a Teflon®-faced silicone septum that has been uble in methanol, weigh 4 g (wet weight) of sample into a tared
20-mL vial. For waste that is soluble in methanol, tetraglyme,
prewashed with detergent, rinsed with distilled deionized
or PEG, weigh 1 g (wet weight) into a tared scintillation vial
water, and oven dried. Tap slightly to eliminate free air space.
or culture tube or a 10-mL volumetric flask. Quickly add
Collect samples in duplicate and seal them in separate plastic bags.
9.0 mL of appropriate solvent then add 1.0 mL of a surrogate
SAMPLE PRESERVATION spiking solution to the vial, cap it, and shake it for 2 min.
Liquid samples — Add 4 drops of concentrated HCL and
METHANOL EXTRACT REQUIRED FOR ANALYSIS
immediately cool samples to 4C and store in a solvent-free
OF HIGH-CONCENTRATION SOILS OR SEDIMENTS
refrigerator.
Approximate Volume of
Soils or sediments, and sludges — Cool samples to 4C and Concentration Range Methanol Extract (a)
store in a solvent-free refrigerator.
500–10,000 g/kg 100 L
MHT Maximum holding time is 14 days from the date of 1,000–20,000 g/kg 50 L
sample collection. 5,000–100,000 g/kg 10 L
25,000–500,000 g/kg 100 L of 1/50 dilution (b)
SAMPLE PREPARATION
Liquid samples — Remove the plunger from a 5-mL syringe Calculate appropriate dilution factor for concentrations
and carefully pour the sample into the syringe barrel to just exceeding this table.
short of overflowing. Replace the syringe plunger and compress
the sample. Open the syringe valve and vent any residual air (a) The volume of methanol added to 5 mL of water being purged
while adjusting the sample volume to 5.0 mL. If there is only should be kept constant. Therefore, add to the 5-mLsyringe whatever
one volatile organic analysis (VOA) vial, a second syringe volume of methanol is necessary to maintain a volume of 100 L
added to the syringe.
should be filled at this time to protect against possible loss of
(b) Dilute an aliquot of the methanol extract and then take 100 L
sample integrity. Add 10 L of surrogate spiking solution and
for analysis.
10 L of internal standard spiking solution through the valve
bore of the 5-mL syringe, then close the valve. The surrogate QUALITY CONTROL Demonstrate, through the analysis of
and internal standards may be mixed and added as a single a reagent water blank, that interferences from the analytical
spiking solution. system, glassware, and reagents are under control. Blank sam-
ples should be carried through all stages of the sample prepa-
Sediments, soils, and waste samples — All samples of this type ration and measurement steps. For each analytical batch (up
should be screened by GC analysis using a headspace method to 20 samples), a reagent blank, matrix spike, and matrix spike
(EPA Method 3810) or the hexadecane extraction and screen- duplicate must be analyzed (the frequency of the spikes may
ing method (EPA Method 3820). Use the screening data to be different for different monitoring programs). The blank and
determine whether to use the low-concentration method spiked samples must be carried through all stages of the sample
(0.005–1 mg/kg) or the high-concentration method (>1 mg/kg). preparation and measurement steps. QC samples mentioned
Low-concentration method — The low-concentration method in the section on Interferences will also be needed as appropri-
is based on purging a heated sediment or soil sample mixed ate to those situations.
with organic-free reagent water containing the surrogate and REFERENCE Test Methods for Evaluating Solid Waste (SW-
internal standards. Analyze all reagent blanks and standards 846). U.S. EPA. 1983. Method 8240B, Rev. 2, Nov. 1990. Office
under the same conditions as the samples. of Solid Wastes, Washington, DC.

©1996 CRC Press LLC


This calculation is based on a 30 g sample and gel perme-
Pyridine EPA Method 8270
ation chromatography cleanup.
CAS #110-86-1
(b) Sample EQLs are highly matrix-dependent. The EQLs are
TITLE Semivolatile Organic Compounds by GC/MS provided for guidance and may not always be achievable.
C = True value for concentration, in g/L.
MATRIX This method is used to determine the concentra- X = Average recovery found for measurements of samples con-
tion of semivolatile organic compounds in extracts prepared taining a concentration of C, in g/L.
from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this ESTIMATED QUANTITATION LIMIT
method should be applicable to water samples from rivers, Other Matrices Factor (a)
lakes, etc. High-concentration soil and sludges by sonicator 7.5
METHOD SUMMARY This method covers 259 semivolatile Non-water miscible waste 75
organic compounds. In very limited applications direct injec- (a) EQL forother matrices =[EQL forlow soil/sediment] [Factor].
tion of the sample into the GC/MS system may be appropriate, This estimated EQL is similar to an EPA “Practical Quantitation
but this results in very high detection limits (approximately Limit.”
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous SAMPLING METHOD
extractor first under acid conditions and then under basic con- Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
ditions. Typically 30 g of a solid sample, containing surrogate, a screw-top Teflon®-lined cover that has been prewashed with
and matrix spiking standards, is extracted ultrasonically. After detergent and rinsed with distilled water and methanol (or
concentrating the extract to 1 mL it is spiked with 10 L of an isopropanol).
internal standard solution just prior to analysis by GC/MS. The Soils, sediments, or sludges — Use an 8-oz. widemouth glass
volume injected should contain about 100 ng of base/neutral with a screw-top Teflon®-lined cover that has been prewashed
and 200 ng of acid surrogates (for a 1-L injection). Analysis with detergent and rinsed with distilled water and methanol
is performed by GC/MS using a capillary GC column. (or isopropanol).
INTERFERENCES Raw GC/MS data from all blanks, sam- SAMPLE PRESERVATION
ples, and spikes must be evaluated for interferences. Contam- Liquid samples — If residual chlorine is present, add 3 mL of
ination by carryover can occur whenever high-concentration 10% sodium thiosulfate per gallon, cool to 4C and store in a
and low-concentration samples are sequentially analyzed. To solvent-free refrigerator until analysis; if chlorine is not present,
reduce carryover, the sample syringe must be rinsed out then eliminate the sodium thiosulfate addition.
between samples with solvent. Whenever an unusually concen-
trated sample is encountered, it should be followed by the Soils, sediments, or sludges — Cool samples to 4C and store
analysis of blank solvent to check for cross-contamination. in a solvent-free refrigerator.

INSTRUMENTATION A GC/MS and a data system are MHT Liquid samples must be extracted within 7 days and
required. The GC column used is a 30 m 0.25 mm I.D. (or the extracts analyzed within 40 days. Soils, sediments, or slud-
0.32 mm I.D.) 1um film thickness silicone-coated fused silica ges may be stored for a maximum of 14 days and the extracts
capillary column. A continuous liquid-liquid extractor analyzed within 40 days.
equipped with Teflon® or glass connection joints and stopcocks SAMPLE PREPARATION
requiring no lubrication, a K-D concentrating apparatus, water Liquid samples — Transfer 1 L quantitatively to a continuous
bath, and an ultrasonic disrupter with a minimum power of extractor. If high concentrations are anticipated, a smaller vol-
300 W and with pulsing capability are also required. ume may be used and then diluted with organic-free reagent
PRECISION & ACCURACY The estimated quantitation water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
limit (EQL) of Method 8270B for determining an individual sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
compound is approximately 1 mg/kg (wet weight) for soil or solution into each sample. For the sample in each analytical
sediment samples, 1–200 mg/kg for wastes (dependent on batch selected for spiking, add 1.0 mL of a matrix spiking stan-
dard. For base/neutral acid analysis, the amount of the surro-
matrix and method of preparation), and 10 g/L for ground-
gates and matrix spiking compounds added to the sample
water samples. EQLs will be proportionately higher for sample
extracts that require dilution to avoid saturation of the detector. should result in a final concentration of 100 ng/L of each
analyte in the extract to be analyzed (assuming a 1- L injec-
The EQL(b) for groundwater in g/L is not determined. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL (a, b) for low concentrations in soil and sediment the pH of the aqueous phase to pH >11 using 10 N sodium
in g/kg is not determined. hydroxide and extract it with methylene chloride again for
Accuracy as g/L is not listed. 18–24 h. Dry the extract through a column containing anhy-
Overall precision in g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
(a) EQLs listed for soil/sediment are based on wet weight. Nor- concentrator.
mally data is reported in a dry-weight basis; therefore, EQLs Soils, sediments, or sludges — Use 30 g of sample. Nonporous or
will be higher based on the % dry weight of each sample. wet samples (gummy or clay type) that do not have a free-flowing

©1996 CRC Press LLC


sandy texture must be mixed with anhydrous sodium sulfate The internal standard responses and retention times in the
until the sample is free flowing. Add 1 mL of surrogate stan- calibration check standard must be evaluated immediately after
dards to all samples, spikes, standards, and blanks. For the or during data acquisition. If the retention time for any internal
sample in each analytical batch selected for spiking, add 1.0 mL standard changes by more than 30 seconds from the last check
of a matrix spiking standard. For base/neutral acid analysis, the calibration (12 h), the chromatographic system must be
amount added of the surrogates and matrix spiking com- inspected for malfunctions and corrections must be made, as
pounds should result in a final concentration of 100 ng/ L of required. If the electron ionization current plot (EICP) area for
each base/neutral analyte and 200 ng/L of each acid analyte any of the internal standards changes by a factor of two from
in the extract to be analyzed (assuming a 1- L injection). the last daily calibration standard check, the mass spectrometer
Immediately add a 100-mL mixture of 1:1 methylene chlo- must be inspected for malfunctions and corrections must be
ride:acetone and extract the sample ultrasonically for 3 min made, as appropriate.
and then decant or filter the extracts. Repeat the extraction two Demonstrate, through the analysis of a reagent water blank,
or more times. Dry the extract using a column with anhydrous that interferences from the analytical system, glassware, and
sodium sulfate and concentrate it to 1 mL in a K-D concentrator. reagents are under control. The blank samples should be car-
QUALITY CONTROL A methylene chloride solution con- ried through all stages of the sample preparation and measure-
taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is ment steps. For each analytical batch (up to 20 samples), a
used for tuning the GC/MS system each 12-h shift. A system reagent blank, matrix spike, and matrix spike duplicate/dupli-
performance check also must be made during every 12-h shift. cate must be analyzed (the frequency of the spikes may be
different for different monitoring programs). The blank and
A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
spiked samples must be carried through all stages of the sample
rophenol, and benzidine is required to verify injection port
preparation and measurement steps. A QC reference sample
inertness and GC column performance. A calibration standard
concentrate containing each analyte at a concentration of
at mid-concentration, containing each compound of interest,
100 mg/L in methanol is required.
including all required surrogates, must be performed every 12 h
during analysis. After the system performance check is met, REFERENCE Test Methods for Evaluating Solid Waste (SW-
calibration check compounds (CCCs) are used to check the 846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
validity of the initial calibration. of Solid Waste, Washington, DC.

©1996 CRC Press LLC


R
Residue, Filterable (TDS) EPA Method 160.1 MDL Not listed.
PRECISION SD = 11 mg/L at 170 mg/L volatile residue
TITLE Physical Properties
concentration.
MATRIX Drinking, surface, and saline waters. Wastewater.
ACCURACY Not listed.
APPLICATION Date issued 1971. Also referred to as total
SAMPLING METHOD Plastic or glass. (100 mL).
dissolved solids. A well mixed sample is filtered through a stan-
dard glass fiber filter. The filtrate is evaporated and dried to STABILITY Cool, 4C.
constant weight at 180C. The increase in dish weight repre-
sents the total dissolved solids. (The filtrate from residue, non- MHT 7 days.
filterable may be used). QUALITY CONTROL Ignite residue from (a), (b), or (c) (see
INTERFERENCES Highly mineralized waters with consider- applicability) to constant weight in a muffle furnace at 550 c.
able calcium, magnesium, chloride, and/or sulfate content may Usually 15 to 20 min ignition is required. Cool and weigh.
be hygroscopic and will require prolonged drying, desiccation Repeat cycle of igniting, cooling, desiccating and weighing to
and rapid weighing. Samples with high concentrations of bicar- constant weight.
bonates require prolonged drying. REFERENCE Methods for the Chemical Analysis of Water
INSTRUMENTATION Glass fiber filter discs (Reeves Angel and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979.
934-AH, or equiv). Drying oven @180c.
RANGE 10–20,000 mg/L.
Resorcinol EPA Method 8270
MDL Not listed. CAS #108-46-3
PRECISION Not listed.
TITLE Semivolatile Organic Compounds by GC/MS
ACCURACY Not listed.
MATRIX This method is used to determine the concentra-
SAMPLING METHOD Plastic or glass. (100 mL). tion of semivolatile organic compounds in extracts prepared
STABILITY Cool, 4C. from all types of solid waste matrices, soils, and groundwater.
Although surface waters are not specifically mentioned, this
MHT 48 h. method should be applicable to water samples from rivers,
QUALITY CONTROL Too much residue in evaporating dish lakes, etc.
will crust over and entrap water that will not be driven off METHOD SUMMARY This method covers 259 semivolatile
during drying. Limit total residue to 200 mg. organic compounds. In very limited applications direct injec-
REFERENCE EPA Methods for the Chemical Analysis of tion of the sample into the GC/MS system may be appropriate,
Water and Wastes, EPA-600/4-79-020, U.S. EPA, EMSL, 1979. but this results in very high detection limits (approximately
10,000 g/L). Typically, a 1-L liquid sample, containing surro-
gate, and matrix spiking standards, is extracted in a continuous
extractor first under acid conditions and then under basic con-
Residue, Volatile (VSS) and (VS) EPA Method 160.4 ditions. Typically 30 g of a solid sample, containing surrogate,
and matrix spiking standards, is extracted ultrasonically. After
TITLE Physical Properties concentrating the extract to 1 mL it is spiked with 10 L of an
MATRIX Sewage, sludge, waste, and sediments. internal standard solution just prior to analysis by GC/MS. The
volume injected should contain about 100 ng of base/neutral
APPLICATION Date issued 1971. Also referred to as volatile and 200 ng of acid surrogates (for a 1-L injection). Analysis
suspended solids and soluble solids. Residue from determina- is performed by GC/MS using a capillary GC column.
tion of total (a), filterable (b), or non-filterable (c) residue is
ignited in a muffle furnace. (The loss of wt on ignition is INTERFERENCES Raw GC/MS data from all blanks, sam-
reported as volatile solids). VSS = ignited solids from (c). VS = ples, and spikes must be evaluated for interferences. Contam-
ignited solids from (a). ination by carryover can occur whenever high-concentration
and low-concentration samples are sequentially analyzed. To
INTERFERENCES Big source of error is failure to obtain reduce carryover, the sample syringe must be rinsed out
representative sample. The test is subject to errors due to loss between samples with solvent. Whenever an unusually concen-
of water of crystall, loss of volatile organic matter prior to
trated sample is encountered, it should be followed by the
combustion, incomplete oxidation of certain complex organics
analysis of blank solvent to check for cross-contamination.
and decomposition of mineral salts.
INSTRUMENTATION A GC/MS and a data system are
INSTRUMENTATION Muffle furnace at 550C
required. The GC column used is a 30 m 0.25 mm I.D. (or
RANGE Not listed. 0.32 mm I.D.) 1um film thickness silicone-coated fused silica

©1996 CRC Press LLC


capillary column. A continuous liquid-liquid extractor SAMPLE PREPARATION
equipped with Teflon® or glass connection joints and stopcocks Liquid samples — Transfer 1 L quantitatively to a continuous
requiring no lubrication, a K-D concentrating apparatus, water extractor. If high concentrations are anticipated, a smaller vol-
bath, and an ultrasonic disrupter with a minimum power of ume may be used and then diluted with organic-free reagent
300 W and with pulsing capability are also required. water to 1 L. Adjust pH, if necessary, to pH <2 using 1:1 (V/V)
sulfuric acid. Pipette 1.0 mL of a surrogate standard spiking
PRECISION & ACCURACY The estimated quantitation solution into each sample. For the sample in each analytical
limit (EQL) of Method 8270B for determining an individual batch selected for spiking, add 1.0 mL of a matrix spiking stan-
compound is approximately 1 mg/kg (wet weight) for soil or dard. For base/neutral acid analysis, the amount of the surro-
sediment samples, 1–200 mg/kg for wastes (dependent on gates and matrix spiking compounds added to the sample
matrix and method of preparation), and 10 g/L for ground- should result in a final concentration of 100 ng/L of each
water samples. EQLs will be proportionately higher for sample analyte in the extract to be analyzed (assuming a 1- L injec-
extracts that require dilution to avoid saturation of the detector. tion). Extract with methylene chloride for 18–24 h. Next, adjust
The EQL(b) for groundwater in g/L is 100. the pH of the aqueous phase to pH >11 using 10 N sodium
The EQL (a, b) for low concentrations in soil and sediment hydroxide and extract it with methylene chloride again for
in g/kg is not determined. 18–24 h. Dry the extract through a column containing anhy-
Accuracy as g/L is not listed. drous sodium sulfate and concentrate it to 1 mL using a K-D
Overall precision in g/L is not listed. concentrator.

(a) EQLs listed for soil/sediment are based on wet weight. Nor- Soils, sediments, or sludges — Use 30 g of sample. Nonporous
mally data is reported in a dry-weight basis; therefore, EQLs or wet samples (gummy or clay type) that do not have a free-
flowing sandy texture must be mixed with anhydrous sodium
will be higher based on the % dry weight of each sample.
sulfate until the sample is free flowing. Add 1 mL of surrogate
This calculation is based on a 30 g sample and gel perme-
standards to all samples, spikes, standards, and blanks. For the
ation chromatography cleanup.
sample in each analytical batch selected for spiking, add 1.0 mL
(b) Sample EQLs are highly matrix-dependent. The EQLs are
of a matrix spiking standard. For base/neutral acid analysis, the
provided for guidance and may not always be achievable. amount added of the surrogates and matrix spiking com-
C = True value for concentration, in g/L. pounds should result in a final concentration of 100 ng/ L of
X = Average recovery found for measurements of samples con-
each base/neutral analyte and 200 ng/L of each acid analyte
taining a concentration of C, in g/L. in the extract to be analyzed (assuming a 1- L injection).
ESTIMATED QUANTITATION LIMIT Immediately add a 100-mL mixture of 1:1 methylene chlo-
Other Matrices Factor (a) ride:acetone and extract the sample ultrasonically for 3 min
and then decant or filter the extracts. Repeat the extraction two
High-concentration soil and sludges by sonicator 7.5 or more times. Dry the extract using a column with anhydrous
Non-water miscible waste 75 sodium sulfate and concentrate it to 1 mL in a K-D concentrator.
(a) EQL forother matrices =[EQLforlow soil/sediment] [Factor]. QUALITY CONTROL A methylene chloride solution con-
This estimated EQL is similar to an EPA “Practical Quantitation taining 50 ng/L of decafluorotriphenylphosphine (DFTPP) is
Limit.” used for tuning the GC/MS system each 12-h shift. A system
performance check also must be made during every 12-h shift.
SAMPLING METHOD
A standard containing 50 ng/L each of 4,4-DDT, pentachlo-
Liquid samples — Use a 1 or 2½ gallon amber glass bottle with
rophenol, and benzidine is required to verify injection port
a screw-top Teflon®-lined cover that has been prewashed with
inertness and GC column performance. A calibration standard
detergent and rinsed with distilled water and methanol (or
at mid-concentration, containing each compound of interest,
isopropanol). including all required surrogates, must be performed every 12 h
Soils, sediments, or sludges — Use an 8-oz. widemouth glass during analysis. After the system performance check is met,
with a screw-top Teflon®-lined cover that has been prewashed calibration check compounds (CCCs) are used to check the
with detergent and rinsed with distilled water and methanol validity of the initial calibration.
(or isopropanol). The internal standard responses and retention times in the
SAMPLE PRESERVATION calibration check standard must be evaluated immediately after
Liquid samples — If residual chlorine is present, add 3 mL of or during data acquisition. If the retention time for any internal
10% sodium thiosulfate per gallon, cool to 4C and store in a standard changes by more than 30 seconds from the last check
solvent-free refrigerator until analysis; if chlorine is not present, calibration (12 h), the chromatographic system must be
then eliminate the sodium thiosulfate addition. inspected for malfunctions and corrections must be made, as
required. If the electron ionization current plot (EICP) area for
Soils, sediments, or sludges — Cool samples to 4C and store any of the internal standards changes by a factor of two from
in a solvent-free refrigerator. the last daily calibration standard check, the mass spectrometer
must be inspected for malfunctions and corrections must be
MHT Liquid samples must be extracted within 7 days and
made, as appropriate.
the extracts analyzed within 40 days. Soils, sediments, or slud-
ges may be stored for a maximum of 14 days and the extracts Demonstrate, through the analysis of a reagent water blank,
analyzed within 40 days. that interferences from the analytical system, glassware, and
©1996 CRC Press LLC
reagents are under control. The blank samples should be car- Use of a flame photometric detector (FPD) in the phosphorus
ried through all stages of the sample preparation and measure- mode will minimize interferences from materials that do not
ment steps. For each analytical batch (up to 20 samples), a contain phosphorus. Elemental sulfur, however, may interfere
reagent blank, matrix spike, and matrix spike duplicate/dupli- with the determination of certain organophosphorus com-
cate must be analyzed (the frequency of the spikes may be pounds by flame photometric gas chromatography. Sulfur
different for different monitoring programs). The blank and cleanup using EPA Method 3660 may alleviate this interference.
spiked samples must be carried through all stages of the sample A nitrogen phosphorus detector (NPD) is also recommended.
preparation and measurement steps. A QC reference sample
A few analytes coelute on certain columns. Therefore, select a
concentrate containing each analyte at a concentration of
second column for confirmation where coelution of the ana-
100 mg/L in methanol is required.
lytes of interest does not occur.
REFERENCE Test Methods for Evaluating Solid Waste (SW-
Method interferences may be caused by contaminants in sol-
846). U.S. EPA 1983, Method 8270B, Rev. 2, Nov. 1990. Office
vents, reagents, glassware, and other sample processing hard-
of Solid Waste, Washington, DC.
ware that lead to discrete artifacts or elevated baselines in gas
chromatograms. All these materials must be routinely demon-
strated to be free from interferences under the conditions of
Ronnel EPA Method 8141 the analysis by analyzing reagent blanks.
CAS #299-84-3
INSTRUMENTATION A GC with a NPD or a FPD will be
TITLE Organophosphorus Compounds by Gas Chromatog- needed. A data system or integrator is recommended for mea-
raphy: Capillary Column Technique suring peak areas and/or peak heights. A Kuderna-Danish
(K-D) apparatus will be needed for extract concentration.
MATRIX This method covers aqueous and solid matrices.
This includes a wide variety such as drinking water, ground- Column 1: 15 m  0.53 mm megabore capillary column,
water, industrial wastewaters, surface waters, soils, solids, and 1.0 m film thickness, DB-210.
sediments. Column 2: 15 m  0.53 mm megabore capillary column,
1.5 m film thickness, SPB-608.
METHOD SUMMARY This is a GC method used to deter- Column 3: 15 m  0.53 mm megabore capillary column,
mine the concentration of 28 organophosphorus pesticides. 1.0 m film thickness, DB-5.
The use of Gel Permeation Cleanup (EPA Method 3640) for Three megabore capillary columns are included for analysis of
sample cleanup has been demonstrated to yield recoveries of organophosphates by this method. Column 1 (DB-210 or
less than 85% for many method analytes and is therefore not equivalent) and Column 2 (SPB-608 or equivalent) are recom-
recommended for use with this method. mended if a large number of organophosphorus analytes are
This method provides GC conditions for the detection of ppb to be determined. If the superior resolution offered by Column
concentrations of organophosphorus compounds. Prior to the 1 and Column 2 is not required, Column 3 (DB-5 or equiva-
use of this method, appropriate sample preparation techniques lent) may be used. For megabore capillary columns, automatic
must be used. Water samples are extracted at a neutral pH with injections of 1 L are recommended.
methylene chloride as a solvent by using a separatory funnel PRECISION & ACCURACY The MDL actually achieved in
(EPA Method 3510) or a continuous liquid-liquid extractor a given analysis will vary, as it is dependent on instrument
(EPA Method 3520). Soxhlet extraction (EPA Method 3540) or sensitivity and matrix effects. Single operator accuracy and
ultrasonic extraction (EPA Method 3550) using methylene precision studies have been conducted with spiked water and
chloride/acetone (1:1) are used for solid samples. Both neat soil samples.
and diluted organic liquids (EPA Method 3580) may be ana-
lyzed by direct injection. Spiked samples are used to verify the MULTIPLICATION FACTORS FOR OTHER MATRICES (a)
applicability of the chosen extraction technique to each new Matrix Factor (b)
sample type. A GC with a flame photometric (FPD) or nitro- Groundwater 10
gen-phosphorus detector (NPD) is used for this multiresidue (EPA Method 3510 or EPA Method 3520)
procedure. Low-concentration soil by Soxhlet and no cleanup 10 (c)
INTERFERENCES The use of Florisil cleanup materials (EPA Low-concentration soil by ultrasonic extraction 6.7 (c)
Method 3620) for some of the compounds in this method has with GPC cleanup
been demonstrated to yield recoveries less than 85% and is High-concentration soil and sludges 500 (c)
therefore not recommended for all compounds. Use of phos- by ultrasonic extraction
phorus or halogen specific detectors, however, often obviates Non-water miscible waste (EPA Method 3580) 1000 (c)
the necessity for cleanup for relatively clean sample matrices. (a) SampleEQLs are highly matrix-dependent. TheEQLslisted here
If particular circumstances demand the use of an alternative are provided for guidance and may not always be achievable.
cleanup procedure, the analyst must determine the elution pro- (b) EQL = [Method detection limit] [Factor]. For non-aqueous
file and demonstrate that the recovery of each analyte is no less samples the factor is on a wet-weight basis.
than 85%. (c) Multiply this factory times the soil MDL.
©1996 CRC Press LLC
The MDL (in g/L) when reagent water was extracted using a with isooctane. One of the concentrations should be at a con-
separatory funnel was 0.07. centration near, but above, the MDL.
The MDL (in g/kg) when soil was extracted using Soxhlet
Include a mid-level check standard after each group of 10 sam-
extraction (EPA Method 3540) was 3.5.
ples in the analysis sequence. GC/MS techniques should be
Accuracy (as % recovery) with separatory funnel extraction
judiciously employed to support qualitative identifications
ranged from 67 (with low spikes) to 87 (with high spikes).
made with this method. Follow the GC/MS operating require-
Accuracy (as % recovery) with continuous liquid-liquid extrac-
ments specified in EPA Method 8270.
tion ranged from 82 (with low spikes) to 89 (with high
spikes). When available, chemical ionization mass spectra may be
Accuracy (as % recovery) with Soxhlet extraction of soils employed to aid in the qualitative identification process. To
ranged from not recovered (with low spikes to 79 (with high confirm an identification of a compound, the background-
spikes). corrected mass spectrum of the compound must be obtained
Accuracy (as % recovery) with ultrasonic extraction of soils from the sample extract and must be compared with a mass
ranged from 70 (with low spikes) to 81 (with high spikes). spectrum from a stock or calibration standard analyzed under
the same chromatographic conditions. The molecular ion and
SAMPLE COLLECTION, PRESERVATION & HANDLING all other ions present above 20% relative abundance in the mass
Containers used to collect samples for the determination of spectrum of the standard must be present in the mass spectrum
semivolatile organic compounds should be soap and water
of the sample with agreement to 20%. The retention time of
washed followed by methanol (or isopropanol) rinsing. The
the compound in the sample must be within six seconds of the
sample containers should be of glass or Teflon® and have screw-
retention time for the same compound in the standard solution.
top covers with Teflon® liners.
Should the MS procedure fail to provide satisfactory results,
No preservation is used with concentrated waste samples. With
additional steps may be taken before reanalysis. These steps
liquid samples containing no residual chlorine and with soil,
may include the use of alternate packed or capillary GC col-
sediment, and sludge samples, immediately cooling to 4C is umns or additional sample cleanup.
the only preservation used. When residual chlorine is present
then 3 mL of 10% aqueous sodium sulfate is added for each REFERENCE Test Methods for Evaluating Solid Waste, Phys-
gallon of sample collected, followed by cooling to 4C. ical/Chemical Methods, SW-846, 3rd Edition, U.S. EPA, Office
of Solid Waste, Washington, DC, EPA Method 8141 July 1992.
Liquid samples must be extracted within 7 days and their
extracts analyzed within 40 days. Concentrated waste, soil, sed-
iment, and sludge samples must be extracted within 14 days
and their extracts analyzed within 40 days. Ronnel EPA Method 8140
CAS #299-84-3
SAMPLE PREPARATION In general, water samples are
extracted at a neutral pH with methylene chloride, using either TITLE Organophosphorus Pesticides
EPA Method 3510 or EPA Method 3520. Solid samples are
extracted using either EPA Method 3540 or EPA Method 3550 MATRIX Groundwater, soils, sludges, water miscible liquid
with methylene chloride/acetone (1:1) as the extraction solvent. wastes, and non-water miscible wastes.

Prior to GC analysis, the extraction solvent may be exchanged APPLICATION This method is used for the analysis of 21
to hexane. Single lab data indicates that samples should not be organophosphorus pesticides. Samples are extracted, concen-
transferred with 100% hexane during sample workup as the trated, and analyzed using direct injection of both neat and
more water soluble organophosphorus compounds may be lost. diluted organic liquid into a gas chromatograph (GC).

If cleanup is performed on the samples, the analyst should INTERFERENCES Solvents, reagents, and glassware may
analyze the samples by GC. This will confirm elution patterns introduce artifacts. Other interferences may come from coex-
and the absence of interferences from the reagents. If peak tracted compounds from samples. The use of Florisil cleanup
detection and identification is prevented by the presence of materials may produce low recoveries. Elemental sulfur may
interferences, further cleanup is required. interfere with some compounds when using a flame photomet-
ric detector. Sulfur cleanup (Method 3660) may alleviate sulfur
QUALITY CONTROL The analyst should monitor the per- interference.
formance of the extraction, cleanup (when used), and analyt-
ical system and the effectiveness of the method in dealing with INSTRUMENTATION GC capable of on-column injections
and a flame photometric detector (FPD) or a thermionic detec-
each sample matrix by spiking each sample, standard, and
tor. Column 1: 1.8 m by 2 mm with 5% SP-2401 on Supelco-
blank with one or two surrogates (e.g., organophosphorus
port. Column 2: 1.8 m by 2 mm with 3% SP-2401 on
compounds not expected to be present in the sample). Deu-
Supelcoport. Column 3: 50 cm by in Teflon® with 15% SE-
terated analogs of analytes should not be used as surrogates for
54 on Gas Chrom Q. The preferred column is Column Number 2.
gas chromatographic analysis due to coelution problems.
RANGE 1.0–50 g/L
A minimum of five concentrations for each analyte of interest
should be prepared through dilution of the stock standards MDL 0.3 g/L (in reagent water).

©1996 CRC Press LLC


PQL FACTORS FOR MULTIPLYING  FID MDL VALUE 3 mL of 10% sodium thiosulfate per gallon of sample and cool
Matrix Multiplication Factor to 4C.
Groundwater 10 MHT 14 days for concentrated waste, soil, sediment, or
Low-level soil by sonication with GPC cleanup 670 sludge; 7 days for liquid samples; all extracts must be analyzed
High-level soil and sludge by sonication 10,000 within 40 days.
Non-water miscible waste 100,000
QUALITY CONTROL A quality control check sample con-
PRECISION 5.6% (single operator standard deviation)
centrate containing this compound in acetone at a concentra-
ACCURACY 99.2% (single operator average recovery) tion 1,000 times more concentrated than the selected spike
concentration is required. The QC check sample concentrate
SAMPLING METHOD Use 8-oz. widemouth glass bottles
with Teflon®-lined caps for concentrated waste samples, soils, may be prepared from pure standard materials or purchased
sediments, and sludges. Use 1 or 2½ gallon amber glass bottles as certified solutions. Use appropriate trip, matrix, control site,
with Teflon®-lined caps for liquid (water) samples. method, reagent, and solvent blanks. Internal, surrogate, and
five concentration level calibration standards are used.
STABILITY Cool soil, sediment, sludge, and liquid samples
to 4C. If residual chlorine is present in liquid samples add REFERENCE Method 8140, SW-846, 3rd ed., Sept. 1986.

©1996 CRC Press LLC


S
Safrole EPA Method 1625 PRECISION & ACCURACY The detection limits of the
CAS #94-59-7 method are usually dependent on the level of interferences
rather than instrumental limitations. The limits typify the min-
TITLE Semivolatile Organic Compounds by Isotope Dilu- imum quantities that can be detected with no interferences
tion GC/MS present.
MATRIX The compounds may be determined in waters, The minimum level (in g/mL) was not listed. This is defined
soils, and municipal sludges by this method. as a minimum level at which the analytical system shall give
recognizable mass spectra (background corrected) and accept-
METHOD SUMMARY This method is used to determine
able calibration points.
176 semivolatile toxic organic pollutants associated with the
CWA (as amended 1987); the RCRA (as amended 1986); the The MDL (in g/kg) in low solids was not listed and in high
CERCLA (as amended 1986); and other compounds amenable solids was not listed; these were determined in digested sludge
to extraction and analysis by capillary column gas chromatog- (low solids) and in filter cake or compost (high solids).
raphy-mass spectrometry (GC/MS).
The labeled and native compound initial precision as standard
Stable isotopically-labeled analogs of the compounds of interest deviation (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%, The labeled and native compound initial accuracy as average
a 1-L sample is extracted at pH 12–13, then at pH <2 with recovery (in g/L) was not listed.
methylene chloride using continuous extraction techniques.
SAMPLE COLLECTION, PRESERVATION & HANDLING
If the solids content is 30% or less, the sample is diluted to 1% Collect samples in glass containers. Aqueous samples which
solids with reagent water, homogenized ultrasonically, and flow freely are collected in refrigerated bottles using automatic
extracted at pH 12–13, then at pH <2 with methylene chloride sampling equipment. Solid samples are collected as grab sam-
using continuous extraction techniques. If the solids content is ples using widemouth jars. Maintain samples at 0 to 4C from
greater than 30%, the sample is extracted using ultrasonic the time of collection until extraction. If residual chlorine is
techniques. present in aqueous samples, add 80 mg sodium thiosulfate/L
of water. Begin sample extraction within 7 days of collection,
Each extract is dried over sodium sulfate, concentrated to a
and analyze all extracts within 40 days of extraction.
volume of 5 mL, cleaned up using GPC, if necessary, and con-
centrated. Extracts are concentrated to 1 mL if GPC is not SAMPLE PREPARATION Samples containing 1% solids or
performed, and to 0.5 mL if GPC is performed. less are extracted directly using continuous liquid-liquid
extraction techniques. Samples containing 1 to 30% solids are
An internal standard is added to the extract, and a 1-mL aliquot
diluted to the 1% level with reagent water and extracted using
of the extract is injected into the GC. The compounds are
continuous liquid-liquid extraction techniques. Samples con-
separated by GC and detected by a MS. The labeled compounds
taining greater than 30% solids are extracted using ultrasonic
serve to correct the variability of the analytical technique.
techniques.
INTERFERENCES Solvents, reagents, glassware, and other
Base/neutral extraction — Adjust the pH of the waters in the
sample processing hardware may yield artifacts and/or elevated
extractors to 12–13 with 6 N NaOH. Extract with methylene
baselines causing misinterpretation of chromatograms and
chloride for 24–48 h.
spectra. Materials used in the analysis must be demonstrated
Acid extraction — Adjust the pH of the waters in the extractors
to be free from interferences under the conditions of analysis
to 2 or less using 6 N sulfuric acid. Extract with methylene
by running method blanks initially and with each sample lot
chloride for 24–48 h.
(sample started through the extraction process on a given 8-h
Ultrasonic extraction of high solids samples — Add anhy-
shift, to a maximum of 20). Specific selection of reagents and
drous sodium sulfate to the sample and QC aliquot(s).
purification of solvents by distillation in all glass systems may
Add acetone:methylene chloride (1:1) to the sample and
be required. Glassware and, where possible, reagents are
mix thoroughly
cleaned by solvent rinse and baking at 450C for 1-h minimum.
Interferences coextracted from samples will vary considerably Concentrate extracts using a K-D apparatus.
from source to source, depending on the diversity of the site
QUALITY CONTROL The analyst is permitted to modify
being sampled.
this method to improve separations or lower the costs of mea-
INSTRUMENTATION Major instrumentation includes a GC surements, provided all performance specifications are met.
with a splitless or on-column injection port for capillary col- Analyses of blanks are required to demonstrate freedom from
umn, a MS with 70 eV electron impact ionization, and a data contamination. When results of spikes indicate atypical
system to collect and record MS data, and process it. A K-D method performance for samples, the samples are diluted to
apparatus is used to concentrate extracts. bring method performance within acceptable limits.
GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1% For low solids (aqueous samples), extract, concentrate, and
vinyl silicone bonded phased fused silica capillary column. analyze two sets of four 1-L aliquots (8 aliquots total) of the

©1996 CRC Press LLC


precision and recovery standard. For high solids samples, two An internal standard is added to the extract, and a 1-mL aliquot
sets of four 30-g aliquots of the high solids reference matrix of the extract is injected into the GC. The compounds are
are used. separated by GC and detected by a MS. The labeled compounds
serve to correct the variability of the analytical technique.
Spike all samples with labeled compounds to assess method
performance. Compute percent recovery of the labeled com- INTERFERENCES Solvents, reagents, glassware, and other
pounds using the internal standard method. Compare the sample processing hardware may yield artifacts and/or elevated
labeled compound recovery for each compound with the cor- baselines causing misinterpretation of chromatograms and
responding labeled compound recovery. spectra. Materials used in the analysis must be demonstrated
to be free from interferences under the conditions of analysis
Reagent water and high solids reference matrix blanks are ana- by running method blanks initially and with each sample lot
lyzed to demonstrate freedom from contamination. Extract (sample started through the extraction process on a given 8-h
and concentrate a 1-L reagent water blank or a high solids shift, to a maximum of 20). Specific selection of reagents and
reference matrix blank with each sample’s lot (samples started purification of solvents by distillation in all glass systems may
through the extraction process on the same 8-h shift, to a be required. Glassware and, where possible, reagents are
maximum of 20 samples). cleaned by solvent rinse and baking at 450C for 1-h minimum.
Field replicates may be collected to determine the precision of Interferences coextracted from samples will vary considerably
the sampling technique, and spiked samples may be required from source to source, depending on the diversity of the site
to determine the accuracy of the analysis when the internal being sampled.
standard method is used. INSTRUMENTATION Major instrumentation includes a GC
REFERENCE Semivolatile Organic Compounds by Isotope with a splitless or on-column injection port for capillary col-
Dilution GC/MS. Office of Water Regulation and Standards, umn, a MS with 70 eV electron impact ionization, and a data
U.S. EPA Industrial Technology Division, Washington, DC, system to collect and record MS data, and process it. A K-D
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard, apparatus is used to concentrate extracts.
U.S. EPA, Office of Water Regulations and Standards, 401 M GC Column: 30 m 0.25 mm I.D. 5% phenyl, 94% methyl, 1%
St., SW, Washington, DC, 20460. Phone: 202-382-7131). vinyl silicone bonded phased fused silica capillary column.
PRECISION & ACCURACY The detection limits of the
method are usually dependent on the level of interferences
Safrole EPA Method 1625 rather than instrumental limitations. The limits typify the min-
CAS #94-59-7 imum quantities that can be detected with no interferences
present.
TITLE Semivolatile Organic Compounds by Isotope Dilu-
tion GC/MS The minimum level (in g/mL) was not listed. This is defined
as a minimum level at which the analytical system shall give
MATRIX The compounds may be determined in waters, recognizable mass spectra (background corrected) and accept-
soils, and municipal sludges by this method. able calibration points.
METHOD SUMMARY This method is used to determine The MDL (in g/kg) in low solids was not listed and in high
176 semivolatile toxic organic pollutants associated with the solids was not listed; these were determined in digested sludge
CWA (as amended 1987); the RCRA (as amended 1986); the (low solids) and in filter cake or compost (high solids).
CERCLA (as amended 1986); and other compounds amenable
to extraction and analysis by capillary column gas chromatog- The labeled and native compound initial precision as standard
raphy-mass spectrometry (GC/MS). deviation (in g/L) was not listed.
The labeled and native compound initial accuracy as average
Stable isotopically-labeled analogs of the compounds of interest recovery (in g/L) was not listed.
are added to the sample. If the solids content is less than 1%,
SAMPLE COLLECTION, PRESERVATION & HANDLING
a 1-L sample is extracted at pH 12–13, then at pH <2 with
Collect samples in glass containers. Aqueous samples which
methylene chloride using continuous extraction techniques.
flow freely are collected in refrigerated bottles using automatic
If the solids content is 30% or less, the sample is diluted to 1% sampling equipment. Solid samples are collected as grab sam-
solids with reagent water, homogenized ultrasonically, and ples using widemouth jars. Maintain samples at 0 to 4C from
extracted at pH 12–13, then at pH <2 with methylene chloride the time of collection until extraction. If residual chlorine is
using continuous extraction techniques. If the solids content is present in aqueous samples, add 80 mg sodium thiosulfate/L
greater than 30%, the sample is extracted using ultrasonic of water. Begin sample extraction within 7 days of collection,
techniques. and analyze all extracts within 40 days of extraction.
Each extract is dried over sodium sulfate, concentrated to a SAMPLE PREPARATION Samples containing 1% solids or
volume of 5 mL, cleaned up using GPC, if necessary, and con- less are extracted directly using continuous liquid-liquid extrac-
centrated. Extracts are concentrated to 1 mL if GPC is not tion techniques. Samples containing 1 to 30% solids are diluted
performed, and to 0.5 mL if GPC is performed. to the 1% level with reagent water and extracted using continuous

©1996 CRC Press LLC


liquid-liquid extraction techniques. Samples containing greater from all types of solid waste matrices, soils, and groundwater.
than 30% solids are extracted using ultrasonic techniques. Although surface waters are not specifically mentioned, this
method should be applicable to water samples from rivers,
Base/neutral extraction — Adjust the pH of the waters in the
lakes, etc.
extractors to 12–13 with 6 N NaOH. Extract with methylene
chloride for 24–48 h. METHOD SUMMARY This method covers 259 semivolatile
Acid extraction — Adjust the pH of the waters in the extractors organic compounds. In very limited applications direct injec-
to 2 or less using 6 N sulfuric acid. Extract with methylene tion of the sample into the GC/MS system may be appropriate,
chloride for 24–48 h. but this results in very high detection limits (approximately
Ultrasonic extraction of high solids samples — Add anhy- 10,000 g/L). Typically, a 1-L liquid sample, containing surro-
drous sodium sulfate to the sample and QC aliquot(s). gate, and matrix spiking standards, is extracted in a continuous
Add acetone:methylene chloride (1:1) to the sample and extractor first under acid conditions and then under basic con-
mix thoroughly ditions. Typically 30 g of a solid sample, containing surrogate,
and matrix spiking standards, is extracted ultrasonically. After
Concentrate extracts using a K-D apparatus.
concentrating the extract to 1 mL it is spiked with 10 L of an
QUALITY CONTROL The analyst is permitted to modify internal standard solution just prior to analysis by GC/MS. The
this method to improve separations or lower the costs of mea- volume injected should contain about 100 ng of base/neutral
surements, provided all performance specifications are met. and 200 ng of acid surrogates (for a 1-L injection). Analysis
Analyses of blanks are required to demonstrate freedom from is performed by GC/MS using a capillary GC column.
contamination. When results of spikes indicate atypical
INTERFERENCES Raw GC/MS data from all blanks, sam-
method performance for samples, the samples are diluted to
ples, and spikes must be evaluated for interferences. Contam-
bring method performance within acceptable limits.
ination by carryover can occur whenever high-concentration
For low solids (aqueous samples), extract, concentrate, and and low-concentration samples are sequentially analyzed. To
analyze two sets of four 1-L aliquots (8 aliquots total) of the reduce carryover, the sample syringe must be rinsed out
precision and recovery standard. For high solids samples, two between samples with solvent. Whenever an unusually concen-
sets of four 30-g aliquots of the high solids reference matrix trated sample is encountered, it should be followed by the
are used. analysis of blank solvent to check for cross-contamination.
Spike all samples with labeled compounds to assess method INSTRUMENTATION A GC/MS and a data system are
performance. Compute percent recovery of the labeled com- required. The GC column used is a 30 m 0.25 mm I.D. (or
pounds using the internal standard method. Compare the 0.32 mm I.D.) 1um film thickness silicone-coated fused silica
labeled compound recovery for each compound with the cor- capillary column. A continuous liquid-liquid extractor
responding labeled compound recovery. equipped with Teflon® or glass connection joints and stopcocks
requiring no lubrication, a K-D concentrating apparatus, water
Reagent water and high solids reference matrix blanks are ana-
bath, and an ultrasonic disrupter with a minimum power of
lyzed to demonstrate freedom from contamination. Extract
300 W and with pulsing capability are also required.
and concentrate a 1-L reagent water blank or a high solids
reference matrix blank with each sample’s lot (samples started PRECISION & ACCURACY The estimated quantitation
through the extraction process on the same 8-h shift, to a limit (EQL) of Method 8270B for determining an individual
maximum of 20 samples). compound is approximately 1 mg/kg (wet weight) for soil or
sediment samples, 1–200 mg/kg for wastes (dependent on
Field replicates may be collected to determine the precision of
the sampling technique, and spiked samples may be required matrix and method of preparation), and 10 g/L for ground-
to determine the accuracy of the analysis when the internal water samples. EQLs will be proportionately higher for sample
standard method is used. extracts that require dilution to avoid saturation of the detector.
The EQL(b) for groundwater in g/L is 10.
REFERENCE Semivolatile Organic Compounds by Isotope
The EQL (a, b) for low concentrations in soil and sediment
Dilution GC/MS. Office of Water Regulation and Standards,
in g/kg is not determined.
U.S. EPA Industrial Technology Division, Washington, DC,
Accuracy as g/L is not listed.
EPA Method 1625, Rev. C, June 1989 (contact W.A. Telliard,
Overall precision in g/L is not listed.
U.S. EPA, Office of Water Regulations and Standards, 401 M
St., SW, Washington, DC, 20460. Phone: 202-382-7131). (a) EQLs listed for soil/sediment are based on wet weight. Nor-
mally data is reported in a dry-weight basis; therefore, EQLs
will be higher based on the % dry weight of each sample.
This calculation is based on a 30 g sample and gel perme-
Safrole EPA Method 8270
ation chromatography cleanup.
CAS #94-59-7
(b) Sample EQLs are highly matrix-dependent. The EQLs are
provided for guidance and may not always be achievable.
TITLE Semivolatile Organic Compounds by GC/MS