Application Note

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MercuryDeterminationinIndustrialSludge,SRM2782,ModifiedEPA
Method245.5,usingtheCETACQuickTraceM8000CVAFSSGTA
JeffForsberg,ProductManager,BrianCook,MercuryProductSpecialist,CETACTechnologies,Omaha,NE

freesample batchanalysis.The QuickTrace M8000has

INTRODUCTION
a fourchannel peristaltic pump that ensures consistent
Industrial sludge is the byproduct of wastewater
sample uptake into the analyzer and allows for
treatment processes and may contain mercury or other
sample/reagent reduction online in a closed system. The
heavymetals.Thepurposeofthisstudyistovalidatethe
reduced sample then flows into the nonfoaming Gas
capabilitiesoftheCETACQuickTraceM8000ColdVapor
Liquid Separator (GLS), and argon is purged through the
Atomic Fluorescence Analyzer in the subg/L range in
sampleaselementalmercuryisliberatedandentersinto
single gold trap amalgamation (SGTA) mode. This was
the system. The mercury is then passed onto a gold trap
carriedoutbyquantitationofmercuryinindustrialsludge.
whereitformsanamalgam.Thegoldtrapisthenheated
TheQuickTraceM8000MercuryAnalyzerwasvalidated
to release mercury from the amalgam. The sample then
by developing a modified method following US EPA
passes into a filtered photomultiplier fluorescence
Method 245.5, Mercury in Sediment (Manual Cold Vapor
detector, and is measured at a wavelength of 253.7nm,
Technique).
where it is recorded in a realtime chart recorder in the
INSTRUMENTATION
QuickTrace software. Software instrument controls
The working range for include, but are not limited to, argon flow, lamp,
the
QuickTrace photomultiplier automatic voltage select, pump control,
M8000MercuryAnalyz and smart rinse threshold. Optimizing these parameters
erisfrom<0.05ng/Lto allowsforincreasedordecreasedsensitivity.
>400g/L.Thesedetec
tion limits allow for ex
tremely lowlevel quan
titationoftotalmercury.
Minimal detector drift
provides stability for
larger sample batch
analysis,
which requires

longeranalysisruntime.
Figure 1. QuickTrace M8000 The QuickTrace M
MercuryAnalyzer
8000 is an independent
standalone analyzer that uses Cold Vapor Atomic
Fluorescence (CVAF) spectrometry for obtaining reliable
quantitative data. The QuickTrace M8000 is
accompaniedbyanautosampler,whichallowsforhands

EXPERIMENTAL
TheQuickTraceM8000isoperatedbytheQuickTrace
software and provides method specific control of the
system. Parameter optimization allows for the
quantitationofmercuryinthesubg/Lrange.Thegoalof
this application is to optimize instrument parameters
usingEPAMethod245.5toquantitatemercuryatthesub
g/LlevelusingtheCETACQuickTraceM8000Mercury
Analyzer. Industrial sludge samples were digested from
standardreferencematerial2782,industrialsludge,which
was purchased from the National Institute of Standards
and Technology. The certified reference material was
collected from a site in northern New Jersey that does
pharmaceuticalresearchaseffluentbeforeitwastreated.
The reference material was stored in an amber glass

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bottle and shaken for approximately one minute to re

homogenize thesample priortosamplepreparation.The
outside of the bottle was rinsed with mercuryfree ultra
pure deionized water to remove any particles that may
have adhered to the outer surface. The digestion tubes
were precleaned using a detergent wash, 20% nitric acid
wash and two ultrapure deionized water rinses. The
samples were digested and analyzed in 50mL
polypropylenecopolymercentrifugetubes.

Figure3.MethodGoldTrapHeaterParameters

Initial calibration verification and initial calibration blank

wereanalyzedtovalidatetheaccuracyofthecalibration.
Calibration standards and control standards were
prepared in aqua regia, potassium permanganate, ultra
puredeionizedwater,andhydroxylamine.Aliquotsof100
g/L working standard were used to prepare the
calibrationcurvethatconsistedofoneblankandfivenon
zero standards that ranged from 0.2 g/L to 10 g/L.
Mercury is detected at wavelength 253.7 nm. SRM2782
total mercury is certified at 1.10 mg/kg with an
uncertaintyof0.19mg/kg.

Figure2.MethodParameters
Samplesweretreatedinthesamplevialswithaquaregia
and digested with 5% potassium permanganate solution,
followedbyreductionwith12%hydroxylamine.Reduction
of the inorganic mercury to elemental mercury was
carried out by excess online addition of 10% stannous
chloride,in7%hydrochloricacid,atarateof1.8mL/min
at50%pumpspeed.Sevenreplicateswereanalyzedalong
withtheappropriatequalitycontrolcheckstovalidatethe
instrument. Total analysis time was approximately 124
minutes, with each sample analysis lasting approximately
340 seconds. A sixpoint calibration curve was analyzed,
whichincludedfivenonzerostandardsandoneblank.

Figure4.PeakProfileof10g/LStandard

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The vials were sealed and inverted to homogenize. The
sampleswereplacedonthedryblockfor30minutesat95
Censuringthatthesolutionremainedpurpleandthatall
organics were oxidized. The sample was then reduced by
manuallyadding2.2mLof12%hydroxylamine,sealedand
inverted,andthenfilledto50mLwithultrapureDIwater.
The sample vials were then placed on the autosampler
trayandanalyzed.Inorganicmercurywasreducedtoele
mental mercury with online excess addition of 10% stan
nous chloride in 7% hydrochloric acid at 1.8 mL/min at
50%pumpspeed.Peakareaofeachsamplewasintegrat
ed for 120 seconds. Initial calibration verification, initial
calibration blank, continuing calibration verification, lab
fortifiedblank,labreagentblank,matrixspike,andmatrix
spikeduplicatewereanalyzedtovalidatetheinstrument.
Initial calibration verification was prepared with a2.5 mL
aliquot of the 100 g/L working standard into a matrix
matchedsolutiontogiveaconcentrationof5.0g/L.The
recovery was 91.2% on the initial calibration verification.
Each quality control was prepared in the same manner.
Continuingcalibrationverificationhadrecoveriesof97.4%
and 107.4%. The lab fortified blank had a recovery of
89.0%. Matrix spike and matrix spike duplicate were all
prepared with 1.25 mL aliquots of 100 g/L working
standard to give a concentration of 2.5 g/L. (Recoveries
wereMS=83.0%;MSD=96.2%withRPDat5.0%).

CALIBRATIONSTANDARDIZATION
Calibration standards were prepared using aliquots of a
100g/Lworkingstandardthatwaspreparedfromserial
dilutions of a 1000 mg/mL certified standard. Standards
were prepared using a final volume of 50 mL. Aliquot
volumesof0.1mL,0.5mL,1.25mL,2.5mL,and5.0mLof
100 g/L working standard were added to the ultrapure
deionized water. Calibration standard concentrations
were 0.2, 1.0, 2.5, 5.0, and 10.0 g/L. The calibration
standardswerematrixmatchedbytheadditionof1.8mL
of aqua regia prepared from trace metal grade
hydrochloric acid and nitric acid in a 3:1 ratio, 5.3 mL of
5% potassium permanganate solution and 2.2 mL of 12%
hydroxylamine. Calibration standards were analyzed
beginningwithonematrixblankandthenproceededfrom
lowest concentration standard to the highest
concentrationstandard;peakareawasintegratedfor120
seconds. The concentration and the calibration were
calculated.

RESULTS

Figure5.245.5Calibration

PROCEDURE
Afterthoroughlyshakingthesamplebottle,~0.2gramof
SRM2782, industrial sludge was weighed directly into a
50mLpolypropylenecentrifugetube,1.8mLofultrapure
water was added to the sample and shaken to put the
sludge into solution. Second, 1.8 mL of aqua regia was
added to the sample vial and swirled to mix. The sample
vials were placed in a dry block digestion system set to
95Cfor2min.Thevialswereallowedto coolandfilled
to25mLwithultrapureDIwater,whichwasfollowedby
the addition of 5.3 mL of 5% potassium permanganate.

Using the QuickTrace M8000 for measurement of low

levelmercuryisaneffectiveanalyticaltechniqueusedfor
obtainingreliablequantitativedata.Optimizingcarriergas
flow, pump speed, sample uptake, and rinse time allows
foranalysisofacalibration,qualitycontrols,andsamples
overabroaddynamicrange.Minimalsampleanalysistime
reduces laboratory costs, analyst time, and effort, along
withminimizinginstrumentmaintenance,whilegivingre
liable,quantitativedata.Totalmercuryinindustrialsludge
attheg/Llevelwaseasilyrecoveredbyutilizingthevari
ousinstrumentsettingsoftheQuickTraceM8000Mer
cury Analyzer. Method development using QuickTrace
software included calibration, quality controls, and spike
recovery.Asaresult,totalmercurywasaccuratelyquanti
tated.Sevenreplicatesofthedigestedstandardreference
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material were analyzed and total mercury concentration

wasrecordedandmeanconcentrationandstandarddevi
ationwerecalculated.Theresultsof1.12mg/kg0.13are
showninFigures5and6.

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REFERENCES
USEPA.Method245.5,MercuryinSediment(ManualCold
VaporTechnique).

SRM2782 has a certified concentration of 1.10 mg/kg

with an uncertainty of 0.19 mg/kg. Uncertainty values
correspondtoalevelofconfidenceat95%,andwascalcu
latedforsevenreplicatesofthestandardreferencemate
rialthatwereanalyzedontheQuickTraceM8000using
peakareareadingsforeachofthesevensamples.

IndustrialSludge,SRM2782,1.1mg/Kg0.19
Digest
1
2
3
4
5
6
7

mg/Kg
1.04
1.11
1.15
1.22
1.03
1.14
1.12
Mean= 1.12
Uncertainty= 0.128
n=7Replicates STDEV= 0.066

RSD%= 5.874

Figure6.Results

Figure7.ResultswithUncertainties
Contamination at the low level can present many
problems and can lead to inaccurate results. Therefore
careful attention was given to minimize contamination in
reagents, acids, and deionized water. Through method
development, parameter optimization, and sample
preparation, the QuickTrace M8000 Mercury Analyzer
quantitates total mercury at the subg/L level, giving
reliablequantitativedata.

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