Analysis of Selected Fumigants in Water by Microextraction and GC-ECD

Effective Date: 10/25/2010
Revision Date: 10/25/2010

Revision Author: A. Niculescu
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Standard Operation Procedure for:

ANALYSIS OF SELECTED FUMIGANTS IN WATER BY
MICROEXTRACTION AND GAS CHROMATOGRAPHY WITH ELECTRON
CAPTURE DETECTION (GC/ECD)

DEPARTMENT OF ENVIRONMENTAL PROTECTION
CHEMISTRY SECTION
TALLAHASSEE FLORIDA

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CONTENTS

1. SCOPE AND APPLICATION

2. SUMMARY OF THE METHOD

3. INTERFERENCES

4. DEFINITIONS

5. APPARATUS AND EQUIPMENT

5.1. Gas Chromatograph
5.2. Data System
5.3. Gases
5.4 Glassware

6. REAGENTS AND CHEMICALS

6.1. Solvents
6.2. Neat standards
6.3. D.I. water
6.4 Stock and intermediate standards
6.5. Working standard solutions
6.6. Quality Control Check Standards

7. SAMPLE COLLECTION, PRESERVATION, AND HANDLING

8. SAMPLE PREPARATION PROCEDURE

9. GENERAL DESCRIPTION OF GC/ECD ANALYSIS

9.1 Pre-Run GC Maintenance
9.2 Summary of GC/ECD Analysis
9.3 Instrument Initial Calibration
9.5 Continuing calibration
9.4 Analysis Run Sequence
9.5 Data Processing / Reporting
9.6 Reporting results in DEP LIMS

10. QUALITY CONTROL

11. METHOD PERFORMANCE

12. DATA ARCHIVAL

12. SAFETY

13. POLLUTION PREVENTION

14. REFERENCES

14. APPENDIXES

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1. SCOPE AND APPLICATION

1.1. This method is applicable to the determination of 2 organochlorinated fumigants in water
as listed in Table 1. Method Detection Limits and Practical Quantitation Limits yielded
by this method are also provided in Table 1.

1.2. This method is based on EPA method 504. Laboratory Information Management System
(LIMS) test: W-FUM.

1.3. This Standard Operation Procedure is restricted to use by an analyst experienced in the
use of a gas chromatograph, in the interpretation of gas chromatograms, and in the use of
appropriate computer programs. The minimum qualifications required are:
B.S. in Chemistry or Biochemistry with minimum one year of professional chemical
or biochemical experience
Knowledge of principles and practice of gas chromatography
Ability to perform basic laboratory mathematics
Knowledge of EZChrom Chromatography Software, TARGET Chromatography
Software and DEP LIMS.

2. SUMMARY OF THE METHOD

2.1. Thirty five mL of sample are extracted with 2 mL of hexane. Two uL of the extract is
injected and analyzed using a Gas Chromatograph (GC) equipped with two capillary
dissimilar GC columns and two Electron Capture Detectors (ECDs) to provide
confirmatory analyses for all positive hits. Aqueous calibration standards are extracted
and analyzed in an identical manner as the samples in order to compensate for possible
extraction losses. Surrogate is not available.

3. INTERFERENCES

Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample
processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of
these materials must routinely demonstrate to be free from interferences under the conditions of the
analysis by running laboratory reagent blanks as described in Section 10. Glassware must be scrupulously
cleaned. Clean all glassware as soon as possible after use by rinsing with the last solvent used in it. Solvent
rinsing should be followed by detergent washing with hot water, and rinses with tap water and distilled
water. The glassware should then be drained dry, and heated in a muffle furnace at 400 C for 15-30
minutes. Some thermally stable materials may not be eliminated by this treatment. Solvent rinses with
acetone and pesticide quality hexane may be substituted for the muffle furnace heating. Volumetric
glassware should not be heated in a muffle furnace. After drying and cooling, glassware should be sealed
and stored in a clean environment to prevent any accumulation of dust or other contaminants. Store
inverted or capped with aluminum foil. The use of high purity reagents and solvents helps to minimize
interference problems. Purification of solvents by distillation in all-glass systems may be required.
Interferences by phthalate esters can pose a major problem when using the electron capture detector. These
compounds generally appear in the chromatogram as large late eluting peaks. Common flexible plastics
contain varying amounts of phthalates. These phthalates are easily extracted or leached from such materials
during laboratory operations. Cross contamination of clean glassware routinely occurs when plastics are
handled during extraction steps, especially when solvent-wetted surfaces are handled. Interferences from
phthalates can best be minimized by avoiding the use of plastics in the laboratory. Matrix interferences may
be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will
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vary considerably from source to source, depending upon the nature and diversity of the site being sampled.
Impurities in hexane create the greatest analytical problem. Because of the sensitivity of the ECD,
distillation and other cleanup techniques rarely work to remove the interference peaks. Locate a solvent
source that gives few impurities in the elution time range of the analytes. Currently Fisher brand HPLC
grade hexane has been determined to be the best candidate. Use a sealed solvent dispenser to avoid further
contamination. Adjust the GC temperature program accordingly if interferences are detected to attempt to
separate analyte peaks from the impurity peaks. Fumigants can diffuse in and out of Teflon sealed vials.
Therefore do not store samples and sample extracts with fumigant standards or any other samples
containing high concentrations of fumigants. Current column technology suffers from the fact that EDB at
low concentration may be masked by very high levels of dibromochloromethane (DBCM), a common
disinfection by-product of chlorinated drinking water.
In case of observed interferences with the parameters of interest, there are several options the analyst can
use to remove or alleviate the problem:
1. Use another column type, length or diameter (if available)
2. Use another detector type (GC/MS)
3. Dilute
In case the interference cannot be removed increase the MDL to the level of the lowest value obtained
in two channels.

4. DEFINITIONS

4.1. ACCURACY: The closeness of agreement between an observed value and an accepted
reference value. When applied to a set of observed values, accuracy will be a
combination of a random component and of a common systematic error (or bias)
component.

4.2. BATCH: A group of samples which behave similarly with respect to the sampling or the
testing procedures being employed and which are processed as a unit. For QC purposes,
if the number of samples in a group is greater than 20, then each group of 20 samples or
less will all be handled as a separate batch.

4.3. BIAS: The deviation due to matrix effects of the measured value (Xs - Xu) from a known
spiked amount. Bias can be assessedby comparing a measured value to an accepted
reference value in a sample of known concentration or by determining the recovery of a
known amount of contaminant spiked into a sample (matrix spike). Thus, the bias (B) due
to matrix effects based on a matrix spike is calculated as:
B =(Xs - Xu) - K
where:
Xs =measured value for spiked sample,
Xu =measured value for unspiked sample, and
K =known value of the spike in the sample.
Using the following equation yields the percent recovery (%R).
%R =100 (Xs- Xu)/ K

4.4. PRACTICAL QUANTITATION LIMIT (PQL): The lowest concentration that can be
reliably achieved within specified limits of precision and accuracy during routine
laboratory operating conditions. The PQL is generally 5 to 10 times the MDL. However,
it may be nominally chosen within these guidelines to simplify data reporting. For many
analytes the PQL concentration is selected as the lowest non-zero standard in the
calibration curve. Sample PQLs are highly matrix-dependent.

4.5. FIELD DUPLICATES: Independent samples which are collected as close as possible to
the same point in space and time. They are two separate samples taken from the same
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source, stored in separate containers, and analyzed independently. These duplicates are
useful in documenting the precision of the sampling process.

4.6. LABORATORY FORTIFIED BLANK/LABORATORY CONTROL SAMPLE
(LFB/LCS): A known matrix spiked with compound(s) representative of the target
analytes. The LFB is analyzed exactly as a sample. This is used to determine whether the
methodology is in control, and whether the laboratory is capable of making accurate and
precise measurements.

4.7. MATRIX: The component or substrate (e.g., surface water, drinking water) which
contains the analyte of interest.

4.8. MATRIX SPIKE: An aliquot of sample spiked with a known concentration of target
analyte(s). The spiking occurs prior to sample preparation and analysis. A matrix spike is
used to document the bias of a method in a given sample matrix.

4.9. MATRIX SPIKE DUPLICATES: A second aliquot of the same sample used for matrix
spike spiked with identical concentrations of target analyte(s). The spiking occurs prior to
sample preparation and analysis. They are used to document the precision and bias of a
method in a given sample matrix.

4.10. METHOD BLANK: An analyte-free matrix to which all reagents are added in the same
volumes or proportions as used in sample processing. The method blank should be
carried through the complete sample preparation and analytical procedure. The method
blank is used to document contamination resulting from the analytical process. For a
method blank to be acceptable for use with the accompanying samples, the concentration
in the blank of any analyte of concern should not be higher than the method detection
limit

4.11. METHOD DETECTION LIMIT (MDL): The minimum concentration of a substance that
can be measured and reported with 99% confidence that the analyte concentration is
greater than zero and is determined from analysis of a sample in a given matrix type
containing the analyte. For operational purposes, when it is necessary to determine the
MDL in the matrix, the MDL should be determined by multiplying the appropriate one-
sided 99% t-statistic by the standard deviation obtained from a minimum of seven
analyses of a matrix spike containing the analyte of interest at a concentration one to five
times the estimated MDL.

4.12. ORGANIC-FREE REAGENT WATER: All references to water in the method refer to
water in which interference is not observed at the method detection limit of the
compounds of interest. Organic-free reagent water can be generated by passing tap water
through a carbon filter bed containing about 1 pound of activated carbon. A water
purification system may be used to generate organic-free deionized water.

4.13. PRECISION: The agreement among a set of replicate measurements without assumption
of knowledge of the true value. Precision is estimated by means of duplicate analyses.
These samples should contain concentrations of analyte above the MDL, and involve the
use of matrix spikes or laboratory fortified blanks. The estimates of precision are based
on the relative percent difference (RPD).

RPD =100 [2 ( X1 - X2 ) / ( X1 +X2 ) ]

where X1 and X2 are the two measurements

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4.14. QUALITY CONTROL CHECK STANDARD (QCS): A standard solution from a source,
other than normal calibration standards, that is certified and traceable. These standards
are used to check the accuracy of a calibration curve.

4.15. SPIKE SOLUTION (SS): A solution of method analytes of known concentrations that is
used to fortify an aliquot of laboratory reagent water or sample matrix.

4.16. STANDARD CURVE: A plot of concentrations of known analyte standards versus the
instrument response to the analyte. Calibration standards are prepared by successively
diluting a standard solution to produce working standards which cover the working range
of the instrument. Standards should be prepared at the frequency specified in section six
(6) of this SOP. The calibration standards should be prepared using the same type of
solvent as the final sample preparation solvent.

5. APPARATUS AND EQUIPMENT

5.1. Gas Chromatograph: Agilent 6890 or 7890 capable of four steps temperature
programming, with dual electron capture detectors, dual capillary split/splitless injectors
and a dual HP 7673 Automatic Sampler. The GC and GC Automatic Sampler operating
parameters are illustrated in Table 5 and Table 6 of the Appendix.

5.1.1. The first analytical column is a DB-5, J & W fused silica capillary, 30 m x 0.32
mm x 0.25 um or similar column.

5.1.2. The second column is a DB-608, J & W fused silica capillary, 30 m x 0.32 mm x
0.52 um or similar column.

5.1.3. Both columns can be used as primary or confirmatory based on the performance.

5.1.4. The column with the best performance, is chosen by the analyst to be
primary. The primary column is used to report the results. Important criteria
for choosing the primary column:
5.1.4.1. Stable retention time windows during the entire run sequence
5.1.4.2. The best chromatography (no tailing or fronting, no impurity
interference with surrogates of target components)
5.1.4.3. The best calibration curves especially for target positives
5.1.4.4. The best LCS/Matrix Spikes results
5.1.4.5. The smallest number of CCV failures
5.1.4.6. The best surrogates results
5.1.4.7. The lowest %decomposition for Endrin/DDT

5.2. Data system

5.2.1. A computer system is interfaced to the Chromatograph that allows the
continuous acquisition and storage on machine-readable media of all
chromatographic measurements obtained throughout the duration of the
chromatographic run sequence program.

5.2.2. This system currently uses EZChrom Elite Client/Server from Agilent
Technologies, Inc. to acquire chromatographic data and Target software from
ThermoFisher Scientific, Inc. to process and report the analysis results.

5.2.3. For reporting data, the system currently uses: DEP LIMS.
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5.3. Gases

5.3.1. Helium, UPC Grade, is used as the carrier gas. The helium is passed through an
oxygen and a hydrocarbon filter before it enters the GC.

5.3.2. Nitrogen, UPC Grade, is used as the make up gas for the ECD detectors. The N
2

is passed through an oxygen and a hydrocarbon filter before entering the GC.

5.4. Glassware

5.4.1. Sample Containers: 43.0 +/- 0.5 mL screw cap amber vials. (i.e, referred to as
40 mL vials). Each vial is equipped with a PTFE faced silicone septum. Dirty
vials may be soaked in acetone to remove the old label. Wash vials with hot
soapy water and allow to dry in an oven (120
o
C).

5.4.2. Autosampler Vials - Crimp top vials, suitable for the GC system being used.

5.4.3. Micro Syringes - 10 uL, 25 uL, 50 uL, and 250 uL.

5.4.4. Volumetric Flasks - 10 mL, 25 mL, and 50 mL.

5.4.5. Graduated Cylinder 10 mL, 50 mL.

5.4.6. Extraction Syringes - 5 mL, 2.5 mL glass, gas-tight syringes.

6. REAGENTS AND CHEMICALS

6.1. Reagents

n-Hexane - Fisher HPLC grade
Methanol - Pesticide grade.
Acetone - Pesticide grade.
Sodium Chloride, NaCl ACS reagent grade, for pretreatment before use, pulverize
a batch of NaCl and place in a muffle furnace at room temperature. Increase the
temperature to 400
0
C for 30 minutes. Place in a battle and cap.
Sodium thiosulfate, Na
2
S
2
O
3
ACS reagent grade. For preparation of solution (40
mg/mL), dissolve 1g of Na
2
S
2
O
3
in reagent water and bring to 25 mL volume in a
volumetric flask.

6.2. Neat Standards

1,2-Dibromoethane (EDB) - Neat standard (99+% purity).
1,2-Dibromo-3-chloropropane (DBCP) - Neat standard (99+% purity). Protect from
light.

6.3. Stock Standards Solution may be prepared in the DEP lab from neat standards or
purchased from a certified manufacturer (ISO 9000 or EPA certified).

1,2-Dibromoethane (EDB) - 2000 ug/mL Solution from Chem Service or
AccuStandard
1,2-Dibromo-3-chloropropane (DBCP) - 2000 ug/mL Solution from Chem Service
or AccuStandard.
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6.4. Deionized (D.I.) Water: Water determined by method analysis to be free of fumigants
and interference peaks.

6.5. Stock and Intermediate Standards

6.5.1. Stock standards mixtures are concentrated standards prepared from neat
standards (approximately 100% purity) once a year. Standards may be prepared
in the DEP lab or purchased from a certified manufacturer (ISO 9000 or EPA
certified).

6.5.2. Stock Solution (2 mg/mL)

6.5.2.1. This is 50.0 mg of EDB, and DBCP, in 25.0 mL of methanol. The
approximate volumes for these standards are 23.0 uL EDB, 23.9 uL
DBCP.

6.5.2.2. This solution is prepared by weighing a 25.0 mL volumetric flask
partially filled with methanol. A microsyringe is used to deliver the
standard below the neck of the flask and into the methanol. The new
weight of the flask is recorded. The flask is filled to 25.0 mL after both
fumigants have been added.

6.5.3. Intermediate (spike) solutions 1-6: Intermediate (spike) standard solutions are
mixture or individual standards used to prepare working standards. They are
prepared in our lab from stock standards by mixing / diluting with methanol or
can be purchased from a certified manufacturer (ISO 9000 or EPA certified).
The concentrations of the components in the intermediate standards are listed in
Table 2. Standards are replaced once per year. New standards are checked vs.
standards in house and vs. a second source (QC Standards), after diluting them
to one of the working standard level. The criterion of acceptance is +/- 10%
difference. All standard preparations and verifications have to be recorded in the
Standard Preparation Tracker located in DEP LIMS. A list containing all
standards with their serial numbers used in the analysis must be part of analysis
documentation folder. These solutions are used for the preparation of working
standards as well as matrix spikes and lab fortified blanks. Levels 2, 4, and 6 are
routinely prepared.

6.5.3.1. Spike solution 2: This is 25.0 uL of stock solution diluted to 25 mL
with methanol in a 25 mL volumetric flask.

6.5.3.2. Spike solution 4: This is 5 mL of stock solution 2 diluted to 25.0 mL
solution with methanol in 25.0 mL volumetric flask.

6.5.3.3. Spike solution 6: This is 2.50 mL of stock solution 4 diluted to a 25.0
mL solution with methanol in a 25.0 mL volumetric flask.

6.5.3.4. Solutions may be mixed slowly using a Pasteur pipet. According to the
EPA methods for volatile organics the volumetric flask may be inverted
2-3 times to mix without compromising sample integrity.

6.5.4. All solutions are stored in a refrigerator and allowed to warm to room
temperature before being used.

6.5.5. See Table 7 for routine standard preparation
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6.6. Working Standard Solutions (Calibration standards)

6.6.1. Working standard solutions are a series of diluted standards in hexane. They are
used for calibration and are prepared by spiking intermediate (spike) standard
solutions into vials containing 35 mL of water and are extracted with 2 mL of
hexane. These standards are freshly prepared with each new extraction batch.
A selected level (usually level 4) of second source (QCS) standard is also
prepared and checked against the corresponding primary source standard. The
acceptance criterion is +/-15% difference. The concentrations for each analyte in
35 mL water are presented in Table 3.

6.7. Quality Control Check Standards (QCS) are prepared from a source, other than
calibration standards, that is certified and traceable. These standards are used to check the
integrity of the calibration standards.

7. SAMPLE COLLECTION, PREPARATION AND STORAGE

7.1. Samples must be collected in 40 mL glass containers.

7.2. All samples must be iced or refrigerated at 4 degrees C from time of collection until
extraction.

7.3. All samples must be analyzed within 28 days of collection.

7.4. In case the samples were chlorinated, add to each empty 40 mL container 3 mg of sodium
thiosulfate crystals as dechlorination agent. Alternately, 75 uL of freshly prepared sodium
thiosulfate solution (40 mg/mL) may be added to empty 40 mL bottles just prior to
sample collection.

8. SAMPLE PREPARATION PROCEDURE

8.1. Allow samples to warm to room temperature prior to extraction.

8.2. Remove the container cap. Discard 8 mL, using a disposable pipette in a 10 mL
graduated cylinder. Replace the container cap and weigh the container with contents to
the nearest 0.1 g and record the weight for subsequent sample volume determination.

8.3. Remove the container cap and add 6 g NaCl to the sample. Recap the sample container
and dissolve the NaCl by shaking for about 20 seconds.

8.4. Prepare a D.I. water blank, calibration standards, check standards ( QCS, CCV, MDL
check) in 43 mL vials: add 35 mL DI water, measured using 50 mL graduated cylinder,
add 6 g NaCl and dissolve; add 20 uL of intermediate (spike) solution L4 QCS for the
spikes and QCS check standard; 20 uL L4 for CCVs, and 20 uL of L6 for MDL check.

8.5. Remove the container cap and add 2 mL hexane into each container using 5 mL syringe.
Recap and shake for about 80 seconds.

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8.6. Set the container down and allow hexane and water layers to separate completely (If
there is an emulsion, place vial in an ultrasonic water bath for several minutes to break up
the emulsion).

8.7. Remove the cap and carefully transfer the hexane extract using a disposable pipette. Fill
up the autosampler vial. Keep the rest hexane extract into another vial. Crimp the
autosampler vials. The sample is now ready for GC/ECD analysis.

8.8. Apply the same procedure to all samples, spikes, blanks and standards.

8.9. Determine the Sample Volume

8.9.1. Discard the remaining sample/hexane mixture. Shake off the remaining few
drops using short, brisk wrist movements.

8.9.2. Reweigh the empty container with original cap and calculate the net weight of
sample by difference to the nearest 0.1 g. This net weight (grams) is equivalent
to the volume of water (in mL) extracted.

9. GENERAL DESCRIPTION OF GC/ECD ANALYSIS

9.1. Pre-Run GC Maintenance

9.1.1. Before starting an analysis run sequence, an initial checking and maintenance of
the instrument has to be performed.

9.2. Summary of GC/ECD Analysis

9.2.1. The analysis of samples is accomplished by using two dissimilar fused silica
capillary columns, usually a DB-5 and a DB-608 or similar column (usually
0.32mm ID/30m/0.25-0.50 um).

9.2.2. Analysis is accomplished in two steps: identification of positives and
quantification of the positives.

9.2.3. Identification of positives requires all of the following QA/QC criteria to be
meet:

9.2.3.1. Use of an updated multipoint calibration (updated Retention Times and
Response Factors).

9.2.3.2. Stable retention time windows (all calibration check standards are
within the calibration windows).

9.2.3.3. Recoveries for LFB(s) and matrix spikes are within the control limits.

9.2.3.4. Continuing calibration check standard responses in both columns are
not to be below 15% of initial calibration.

9.2.4. All the samples are analyzed in two columns for confirmation of the target
analyte hits. The LFB(s) and Matrix Spikes results, target analyte reported hits,
are all based on one (the primary) column results. If for some analytes, QC
criteria in the primary column are out of control limits, due to matrix
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interference or other problems, the result will be reported from the confirmatory
column if QC criteria are met.

9.2.5. A target component is identified as positive if its peak is detected within its
appropriate retention time window in both columns. The amount of the
prospective hit found in one column has to be confirmed in the other column.
Criterion for the amount confirmation is equal to or less than +/- 30% difference
between the two columns responses. If besides retention time, there is other
evidence that the target analyte is a positive, and the amount in two columns
does not match, the result will be reported based on the smallest value found in
the two columns, and will be qualified as estimated (J ).

9.2.6. Quantitative analysis of Fumigants is accomplished by the external calibration
method. All target component positives found have to be quantified using at
least a three point calibration curve. The linearity of the calibration curve is
defined by an RSD of =/<20% of the response factors if the calibration curve is
through origin, or by a correlation coefficient not lower than 0.995 if calibration
is not through origin (minimum of 3 levels for linear, 5 levels for quadratic).
Other fit than linear can be used if appropriate for the calibration curve.
Identified positives are quantified. If needed, the samples are diluted or re-run
with a multilevel calibration curve. The amount reported in FDEP LIMS is
based on one column response assigned by the chemist as primary.

9.2.7. Absolute Retention time windows are used for the identification of target
analytes. The absolute retention time window is assessed during initial
calibration as +/- 0.035 minute of the mean RT of the analyte.

9.2.8. In the event a positive identification is found in both the sample(s) and the
instrument blank, the instrument must be cleaned and the sample(s)
rerun/reanalyzed.

9.2.9. In the event a positive identification is found in both the sample(s) and the
extraction blank then the sample set has to be re-extracted and reanalyzed. If
samples are beyond holding time, than:

9.2.9.1. Elevate the MDL to two times the amount found in the blank.

9.2.9.2. Report as a positive hit if that amount is equal or higher than the new
MDL. If the amount reported is less than or equal to ten times the new
MDL, include the qualifier J (estimated value).

9.3. Instrument Initial Calibration

9.3.1. Quantitation of every hit at PQL or higher level for all target components has to
be accomplished by using a calibration curve with a minimum of three levels.

9.3.2. To create an initial calibration curve using external standard procedure, inject at
least three concentration levels of the calibration standard. One of them should
be at a concentration near the MDL level. The other concentrations should
correspond to the expected range of concentrations in the real samples. The
Target will calculate the ratio of response to the amount injected (calibration
factor). Concentrations used in the calibration are calculated to 35 mL of water
sample.

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9.3.3. The system is considered to be in initial linear calibration if the Relative
Standard Deviation (%RSD) or the analyte calibration factors (using peak area
calculation) is less than or equal to 20% (through origin) or the correlation
coefficient is not lower than 0.995 if the calibration curve is not through origin.
Use another curve fit if more appropriate

9.4. Continuing Calibration

9.4.1. After initial calibration, the GC/ECD response is checked on a continuing basis
(every 7-10 samples) by using continuing calibration check standards, usually
L4. Criterion of acceptance for continuing calibration check is +/- 15% of initial
calibration. If a continuing calibration check standard fails high (exceeds 15%)
in both channels, all the samples bracketed by this standard have to be re-run for
all hits more concentrated than PQL level. If the samples have exceeded the
analysis holding time then all hits must be flagged as estimated.

9.4.2. When acceptance criteria for the continuing calibration verification are exceeded
low, i.e., low bias, those sample results (including non-detects) may be reported
if they exceed a maximum regulatory limit/decision level. Otherwise the
samples affected by the unacceptable verification shall be reanalyzed after a new
calibration curve has been established, evaluated and accepted. If the samples
have exceeded the analysis holding time then all detects and non-detects results
must be flagged as estimated.

9.4.3. In order to quantify positives in the re-run samples, the calibration curve has to
be re-made by re-running calibration set together with the samples to be
quantified. The GC-ECD system is also subjected to any maintenance that is
deemed necessary to correct the calibration problem.

9.5. Analysis Run Sequence.

9.5.1. The analyst will set up an analysis run sequence by placing the GC vials
containing the sample extracts and standards on the autosampler tray in the
following order or similar:

n-hexane blank (equipment blank)
FUM-L2
FUM-L4
FUM-L6
FUM-QCS
laboratory fortified blank ( LFB/LCS )
sample matrix spike (MS)
sample matrix spike duplicate (MSD)
extraction blank
samples #1 to #9
FUM-L4
FUM-L6
samples #10 to #19
FUM-L4
FUM-L6

9.6. Data Processing/Reporting

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9.6.1. Analytes are identified by matching retention times with those in the standard
chromatograms. Typical retention times are listed in Table 4. Retention times
will vary depending on the length of the column, but the elution sequence will
be the same.

9.6.2. The concentration found in the sample extract (Cx) for an identified positive hit,
expressed in concentration in the 35 mL of theoretically extracted sample
volume in ug/L, and corrected for real extracted volume of sample, is
quantitated on the initial calibration curve. However, the analyst must ensure
that all identification criteria are fulfilled and the peak area integration was
correctly done. If not, the integration has to be re-done by choosing a new set of
integration parameters or by manual integration. Target software will complete
the calculation to determine the concentration of the analyte in the water sample
(C
sample
) for the measured extracted volume V
sample
. This is done using the
formula:

C
sample
(ug/L) =(C
x
) DF 35/ V
sample

Where :
C
x
- The concentration determined in the sample extract (ug/L)
DF - The appropriate dilution recorded in the dilution report
V
sample
- Determined sample volume taken in extraction (usually close to
35 mLs)

9.7. Reporting results in DEP LIMS.

9.7.1. QA/QC results, MDLs, and positives are reported in the DEP LIMS using the
QC Manager Program, instrument GC Pesticides: Target.

10. QUALITY CONTROL

10.1. For QA/QC see the Lab SOP GC-001-2.

10.2. QC criteria pertaining to this SOP are summarized in Table 6.

10.3. All data generated by a chemistry analyst are subjected to supervisory review and
authorization. The supervisor is assessing the validity of data generated by assuring that
all QA/QC criteria are met by checking the following review/authorization checklist:
Check sample preparation report
Procedure
Spiking solutions
Preparation holding time
Check project log-in folder for special requests
Check initial calibration for linearity
Check continuing calibration check standards
Check the QCS (Second source) report
Check accuracy and precision for LFB and Matrix Spikes
Check retention time drift
Check for Blanks contamination
Check for positives:
Proper integration of the peaks (baseline)
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Retention time confirmation
Amount confirmation
If response is within the calibration range
Calculations
Qualifiers
Check information in the Target Report Header:
SOP #
Instrument ID
Column ID
Evaluate the data against any field information
Check LIMS report:
Preparation and analysis dates
MDLs.
Amounts reported for positives
Qualifiers
Comments

11. METHOD PERFORMANCE

1.1. The MDLs are determined by using EPA recommended procedure (40 CFR Pt 136 Appx. B)
Ref. 16.3 by analyzing at least 7 spikes in DEP D.I. water close to MDL levels. The spikes are
run and analyzed in DB-5 and DB- 608. The Reported MDLs are chosen based on the highest
value measured in any of the two columns. The equation used to calculate the MDL is as
follows:

MDL =S t
(n-1, 1-a=0.99)

Where: t
(n-1, 1-a=0.99)
is Student coeficient value for the 99% confidence level with
n=number of replicates
S=standard deviation

1.2. Run and analyze in the end of each analysis run sequence a L6 standard for MDL verification.
If the check does not pass, samples and standards must be re-run. If samples expired qualify the
MDL reported for the failing parameters as estimated (J ).

12. DATA ARCHIVAL

12.1. All raw data are retained in electronic or hard copy format. All paper formats are
maintained either in the laboratory office or in a State warehouse for at least ten years.
Electronic chromatographic raw data are archived by analysis file ID on optical disk in
the DEP backup system. They are archived on optical disk approximately 6 months after
data collection.

13. SAFETY

13.1. The toxicity or carcinogenicity of each reagent used in this method has not been precisely
defined; however, each chemical compound should be treated as a potential health
hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest
possible level by whatever means available. The laboratory is responsible for maintaining
a current awareness file of OSHA regulations regarding the safe handling of the
GC-018-3.15

Page 15 of 18
chemicals specified in this method. A reference file of material data handling sheets
should also be made available to all personnel involved in the chemical analysis. The
following parameters covered by this method have been tentatively classified as known
or suspected, human or mammalian carcinogens: EDB and DBCP. Primary standards of
these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic
gas respirator should be worn when the analyst handles high concentrations of these toxic
compounds.

13.2. Lab clothing

13.2.1. Lab coats and safety eyeglasses must be worn at all times when in any
laboratory.

13.2.2. Use gloves when handling samples, standards, or solvents, or when washing
glassware.

13.3. Chemicals involved

13.3.1. Even though the toxicity or carcinogeneity of some of the reagents used in this
method have not been precisely defined, each of them should be treated as a
potential health hazard. From this point of view exposure to these chemicals
must be reduced to the lowest possible level by whatever means available.

13.3.2. A reference file of Material Safety Data Sheets for each reagents used, is kept in
the GC room for documentation. Refer to this folder for any materials you are
handling. Update this folder upon receiving new chemicals or reagents.

13.3.3. Primary standards of these toxic compounds should be prepared in a hood (See
Hood Usage). A NIOSH/MESA approved toxic gas respirator should be worn
when handling highly concentrated solutions of these compounds.

13.4. Waste disposal (see Lab Manual Laboratory Waste Management J anuary 2007)

13.4.1. Neat standards should be sealed and labeled.

13.4.2. All stock standards, working standards, and un-used sample extracts must be
emptied into two separate waste containers for Pesticides and PCBs. The
container must be labeled properly with hazard warning labels indicating the
containers contents.

13.4.3. Chlorinated and non-chlorinated solvents must be stored separately and labeled
properly.

13.4.4. GC vials containing, standards, and sample extracts, must be stored in two
separate waste containers for Pesticides and PCBs. These containers should be
labeled properly as to there contents and stored in the hood.

13.5. Flammable solvents must be stored in a flammables cabinet.

13.6. Hood Usage

13.6.1. Handle all sample extraction solvent transfers, concentrations, sample preps, and
cleanups in the hood at all times.

13.6.2. At any time, no more than two people can work at each hood.
GC-018-3.15

Page 16 of 18

13.6.3. Turn the hood on and wait for adequate airflow. If there is no flow, DO NOT
USE THE HOOD!

13.7. Glassware

13.7.1. Inspect every piece of glassware to be used. Do not use any that are chipped,
cracked, etched, or scratched.

13.7.2. Dispose of all unwanted, broken glassware in the blue GLASS box. One
should discriminate between unwanted, broken glassware and that which is
only slightly damaged and reasonably easily repairable.

14. POLLUTION PREVENTION

14.1. Method requires using only 2 mL hexane solvent per sample, so no pollution of the
environment will occur. Very little solvent will escape the fume hood. This small amount
of solvent poses no threat to the environment.

15. REFERENCES

15.1. EPA 504 1,2-Dibromoethane (EDB), 1,2Dibromo-3-chloro-propane (DBCP), and 1,2,3-
Trichloropropane (123TCP) in water by microextraction and gas chromatography (1993).
15.2. DEP SOP GC-001-2, Quality Assurance/Quality Control in the GC Pesticides
Laboratory

16. APPENDIX

TABLE 1. MDL/PQL List for Fumigants

Compound MDL PQL Boiling Pt.
(ug/L) (ug/L) C
1,2-Dibromoethane (EDB) 0.010 0.040 131
1,2-Dibromo-3-chloropropane (DBCP) 0.010 0.040 196

TABLE 2. Concentration Levels for Intermediate (spike) Standards

Level

Concentration of intermediate spiking solution (ug/mL)
EDB DBCP

2 2 2

4 0.4 0.4

6 0.04 0.04

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TABLE 3. Concentration Levels for Fumigants in 35 mL water sample for 20 uL of spiking solution

Level Concentration of working standards (ug/L)
EDB DBCP

2 1.15 1.15

4 0.23 0.23

6 0.023 0.023

TABLE 4. GC Operating Parameters for GC/ECD Analysis

GC Parameter Setting GC Parameter Setting
GC Mode Const pressure
Temperature 1 35
0
C Injector Temperature 90
0
C
Time 1 1 minute Detector Temperature 325
0
C
Ramp 1 2
0
C /minute Carrier Gas Helium
Temperature 2 56
0
C Column Head Pressure 18/14 psi
Time 2 0 minute Total Flow Rate 36 mL per
minute
Ramp 2 12
0
C/minute Septum Purge Flow
Rate
4 mL per
minute
Temperature 3 128
0
C Make up Gas Nitrogen
Time 3 2 minutes Make up Gas Flow
Rate
55 mL per
minute
Ramp 3 30
0
C/minute Injection Mode Splitless for 1
minute
Temperature 4 220
0
C Injection Volume 2.0 uL
Time 4 8 minutes R T Window 0.08/0.1 minute
(NOTE: The operating parameters for both columns are the same).

TABLE 5. GC Operating Parameters for GC/ECD Analysis

Autosampler Parameter Setting Autosampler Parameter Setting

Inj/Bottle 1 Volume (5 uL Syringe) 4
First Bottle 1 #of Solvent A washes 4 (Acetone)
Last Bottle 99 #of solvent B washes 4 (Iso-Octane)
#of Sample washes 2 Priority Sample (1=Yes) No
#of Pumps 6 Capillary On-Column (1=Yes) No
Viscosity 1

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TABLE 6. QC Measurements, Acceptance Criteria and Corrective Actions

# QC MEASUREMENT
ACCEPTANCE
CRITERION
CORRECTIVE ACTION
1 LFB recoveries 60-140 % Reanalyze/Re-extract/Flag
2
Matrix Spike
- recoveries
- precision
60-140%
=/<30%
Reanalyze/Re-extract/Flag
3 CCV +/- 15%(w) Re-run and recalibrate/Flag
4 QCS verification +/- 15% Re-run and recalibrate/Flag
6 MDL Instrument performance 80% -120% Maintain and re-run
7 Linearity criterion
20% RSD or
0.995 CC
Use appropriate cal fit / Re-run/ Recalibrate

TABLE 7. Standard Preparation

#
Standard
Name
Parent Standard
Name

Conc

Add
Final
Standard
vol (ml)

conc
Final
Solvent
1 STOCK STD
FUM STK. EDB QCS NEAT 99% 23.0 uL 25 2000 ppm methanol
DBCP NEAT 99% 23.9 uL 25 2000 ppm methanol
2 FUM L2
EDB FUM STK. A 2000 ppm 25 uL 25 2.0 ppm methanol
DBCP FUM STK. A 2000 ppm 25 uL 2.0 ppm methanol
3 FUM L4
EDB FUM L2 2.0 ppm 5 mL 25 0.4 ppm methanol
DBCP 2.0 ppm 0.4 ppm methanol
4 FUM L6
EDB FUM L4 0.4 ppm 2.5mL 25 .04 ppm methanol
DBCP 0.4 ppm .04 ppm methanol
5 FUM QCS
STK. QCS EDB QCS NEAT 99% 23.0 uL 25 2000 ppm methanol
DBCP NEAT 99% 23.9 uL 25 2000 ppm methanol
6 FUM L2 QCS
EDB FUM STK.A QCS 2000 ppm 25 uL 25 2.0 ppm methanol
DBCP 2000 ppm 25 uL 2.0 ppm methanol
7 FUM L4 QCS
EDB FUM L2 QCS 2.0 ppm 5 mL 25 0.4 ppm methanol
DBCP 2.0 ppm 0.4 ppm methanol

Analysis of Selected Fumigants in Water by Microextraction and GC-ECD

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Effective Date: 10/25/2010

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