FundamentalsFundamentals ooff PPassiveassive SamplerSamplerFundamentalsFundamentals ofof PassivePassive SamplerSampler Use at Superfund SitesUse at Superfund Sites
Robert M. Robert M. BurgessBurgessU.S. EPAU.S. EPA
OfficeOffice ofof ResearchResearch andand DevelopmentDevelopmentOfficeOffice ofof ResearchResearch andand DevelopmentDevelopmentNational Health and National Health and Environmental Effects Environmental Effects Research Laboratory Research Laboratory
(NHEERL)(NHEERL)Atlantic Ecology DivisionAtlantic Ecology Division
NarragansettNarragansett RRhodehode IslandIsland 0288202882NarragansettNarragansett, , RhodeRhode IslandIsland [email protected]@epa.gov
OutlineOutline
Introduction to Introduction to passive samplerspassive samplers
What What information can passive samplers provideinformation can passive samplers provide
CharacteristicsCharacteristics ooffCharacteristicsCharacteristics ofof passivepassive samplerssamplerspassivepassive samplerssamplers–– TTypes of passive samplersypes of passive samplers–– Passive sampler Passive sampler deploymentdeployment
PassivePassive samplersampler–– PassivePassive samplersampler ccostsostscostscosts–– Passive sampler Passive sampler theorytheory–– Technical issues Technical issues using passive using passive samplerssamplers
Passive sampler application at Passive sampler application at a a Superfund siteSuperfund site
SSSSummaryummary
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Conceptual Model of Conceptual Model of Relationship BetweenRelationship BetweenContaminated Sediments and Aquatic LifeContaminated Sediments and Aquatic Life
Atmosphere
Wildlife
WaterFishFish
Mussels
Interstitial WaterDissolved and Bioavailable
ConcentrationDissolved and Bioavailable
Concentration
Contaminated SedimentsBenthic Worms
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(Not to Scale)Diffusion/Advection
IntroductionIntroduction
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How How concentrationsconcentrations inin the water
to determine or measure dissolved to determine or measure dissolved and and bioavailablebioavailableconcentrations in the waterconcentrations in thethe waterwater columncolumn andand interstitialinterstitial waters?waters?columncolumn andand interstitialinterstitial waters?waters?
Why not use conventional Why not use conventional sampling sampling methods? Some methods? Some problems:problems:
–– Water ColumnWater Column
waterwater andandLogistically Logistically
extractextractand technically difficult to and technically difficult to collect large volumes of surface collect large volumes of surface
waterwater andand extractextractSeveral artifacts Several artifacts including losses to including losses to filters filters and contamination by and contamination by colloids colloids reduce accuracy of analysisreduce accuracy of analysisAnalytical Analytical detection limits are often not sufficiently lowdetection limits are often not sufficiently low
–– IInterstitial Waternterstitial Water
CentrifugeCentrifuge oror squeezesqueeze iinterstitialnterstitial wwateraterCentrifugeCentrifuge oror squeezesqueeze interstitialinterstitial waterwaterSimilar Similar artifacts as water columnartifacts as water columnCollecting Collecting large volumes of interstitial waters is challenginglarge volumes of interstitial waters is challenging
Are there other sampling Are there other sampling methods for collecting methods for collecting and and measuring measuring dissolved and bioavailabledissolved and bioavailable contaminants? contaminants?
PPassive samplersassive samplers
SSince late 1980s or soince late 1980s or so
ConsistConsistConsistConsist ooofofff aaanannn ooorganicorganicrganicrganic phasephasephasephase (i(i(i(i..eeee., ., simplesimplesimplesimple organicorganicorganicorganic filmfilmfilmfilm orororor polymer) which accumulates contaminants from the polymer) which accumulates contaminants from the dissolved phasedissolved phase
SemiSemi--permeable permeable membrane devices (SPMDs)membrane devices (SPMDs)
SolidSolidSolidSolid phasephasephasephase mmicromicromicroicro--extractionextractionextractionextraction (SPME)(SPME)(SPME)(SPME)
Polyethylene devices (PEDs) Polyethylene devices (PEDs)
PolyoxymethylenePolyoxymethylene (POM)(POM)
––
––
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IntroductionIntroduction
IntroductionIntroductionTypesTypes ofof contaminantscontaminants sampledsampledTypesTypes ofof contaminantscontaminants sampledsampled
–– Organic compoundsOrganic compounds
Low water Low water solubilitysolubility
KK s)s)Highly hydrophobic, lipiphillicHighly hydrophobic, lipiphillic and bioaccumulatingand bioaccumulating (medium to larg(medium to largKKOWOWs)s)
–– Many legacy contaminants (e.g., Many legacy contaminants (e.g., PCBs, PAHs, PCBs, PAHs, DDTs, DDTs, DieldrinDieldrin))
–– MetalsMetals
Passive samplers behave like aquatic organismsPassive samplers behave like aquatic organisms
–– Accumulate Accumulate contaminants from the dissolved contaminants from the dissolved phasephase
–– Concentrate contaminants into Concentrate contaminants into the the ppololyyp yp ymer like animals accumulate mer like animals accumulate contaminants into their lipids (analytically useful)contaminants into their lipids (analytically useful)
e e
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What information can passive samplers What information can passive samplers pprovide at rovide at a Sua Supperfund site?erfund site?p pp p
(1) Dissolved (1) Dissolved and bioavailableand bioavailable water column and water column and interstitialinterstitial waterwaterinterstitial water concentrationsconcentrations ooff manymany llegacyegacyinterstitial water chemicalschemicals
concentrationsconcentrations ofof manymany legacylegacy
Compare to Compare to Water Water Quality Criteria (WQC) or other Quality Criteria (WQC) or other standards standards oror toxicitytoxicity datadataoror toxicitytoxicity datadata
((22))( )( ) Accumulated Accumulated concentrations concentrations of manof manyyyy le leggggacacyy chemicalschemicals
yy
EEmulate uptake by aquatic organismsmulate uptake by aquatic organismsServeServe aass ssurrogatesurrogates forfor biomonitoring organismsorganismsServeServe biomonitoringasas surrogatessurrogates forfor biomonitoringbiomonitoring organismsorganisms
–– Especially in Especially in situations situations wwherhere e mussels mussels or fish cannot be or fish cannot be used (e.g., used (e.g., low low dissolved dissolved oxygen, toxicity, oxygen, toxicity, low/high low/high temperaturetemperature cconstraints)onstraints)temperaturetemperature constraints)constraints)
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Conceptual Model of Conceptual Model of Relationship BetweenRelationship BetweenContaminated Sediments and Aquatic LifeContaminated Sediments and Aquatic Life
Wildlife
WaterFish
MusselsFish
Dissolved and BioavailableConcentration
PassiveSamplers
Contaminated SedimentsBenthic Worms
(Not to Scale)
Atmosphere
SPME
fiber-optic cable
70 – 95 umthickthick
0.25
m
2.5 cm
SPMD (polyethylenetubing containing
triolien)
75 um thick
POM
PEDPED50 um thick
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Types of Passive SamplersTypes of Passive Samplers
Passive Sampler DeploymentPassive Sampler DeploymentWWaterater CColumnolumn
(NRMRL & Battelle)
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(NHEERL & Brown U)
SPME (in stainless steelmesh cover))
SPME (in coppermesh envelope)
PED
POM
SPMD
Passive Sampler DeploymentPassive Sampler DeploymentSediS diment
Copper tubingSPME (i Copper tubinghousing
SPME (in protective syringe)
(SCCWRP)( )
SPME (in protective syringe)
(MIT)
PED (in aluminum frame)
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Passive Sampler Costs ($/sampler)Passive Sampler Costs ($/sampler)a,ba,b
TypeType
MaterialsMaterials(samplers and (samplers and
deployment deployment equipment)equipment)
PP iiPreparationPreparationtt(dialysis)(dialysis)
Chemical Chemical AnalysesAnalyses TotalTotal
WWaater (5 L)ter (5 L) <5<5 -- 525525 530530
SPMDSPMD 350350 111155 350350 815815
SPMESPME ~35~35 -- 275275 ~310~310
PEDPED ~15~15 -- 375375 ~390~390
POMPOM ~50~50 -- 375375 ~425~425
a 2011 Battelle costs (L Lefkovitz, Duxbury,( , MA, USAy )b Assume 10 - 20 samples, GC/MS analysis of NOAA
, , ) PCB list (20 congeners)
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Water ColumnPCB molecule
Passive Sampler(e.g., PED or POM)Initial concentration of PCBs in
passive samplers = 0 ng/mL
Passive Sampler TheoryPassive Sampler Theory
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Passive Sampler TheoryPassive Sampler TheoryE ilib i S liEquilibrium Sampling
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pler
)en
tratio
nsi
ve S
amp
Con
ceg/
mL
Pas
s
Deployment Time (days)
(n
Deployment Time (days)
Passive Sampler TheoryPassive Sampler Theory
Apparent equilibriumC
pler
)
Apparent equilibrium
*C
CKD
Sampler
Sampler D
entra
tion
sive
Sam
p p
where, CD is the dissolved concentration
Con
ceg/
mL
Pas
s
Dissolved andBioavailable
C t ti
Dof a contaminant (ng/mL),CSampler is the passive samplerconcentration (ng/mL),K i h i l
Deployment Time (days)
(n Concentration KSampler-D is the passive sampler-dissolved partition coefficient
Deployment Time (days)
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Technical Issues using Passive Technical Issues using Passive SamplersSamplersEstablishingEstablishing whenwhen equilibriumequilibrium occursoccurs
on ampl
er) *
Con
cent
ratio
g/m
L P
assi
ve S
Deployment Time (days)
(ng
UnlessUnless deploymentdeployment timetime seriesseries datadata iiss aavailablevailable ((ii ee $$$)$$$)–– UnlessUnless deploymentdeployment timetime seriesseries datadata isis availableavailable (i(i..ee., ., $$$)$$$)
–– Challenge Challenge in all monitoring (including in all monitoring (including biomonitoringbiomonitoring))OftenOften aassumessume 2828 daysdays iiss ssufficientufficientOftenOften assumeassume 2828 daysdays isis sufficientsufficient
–– Solution: Solution: Use Use of performance reference compounds of performance reference compounds (PRCs) (PRCs) to to establishestablish equilibriumequilibriumestablishestablish equilibriumequilibrium
SPMDs, PED, POMSPMDs, PED, POM
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Technical Issues using Passive Technical Issues using Passive SamplersSamplersRelating passive sampler accumulation to Relating passive sampler accumulation to animal animal bioaccumulationbioaccumulation Friedman et al. (2009)
–– CCritiritic
rnteeal for cal for determining how to determining how to interpret interpret passive samplpassive sampler dataer data
––bioabioaDataData Cset set 1000comparing passive comparing passive sampler accumulation to sampler accumulation to aanimal nimal
mr
–– SoluSolu 100tion: Generate tion: Generate general linear modelsgeneral linear models
Animal CAnimal Conconcententrratatioionn ((ngng // mLmL)) * SamplSampleerr CConconcententrratatioionn (ng / mL)(ng / mL)
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)gng
/ 100000P iPassive SS (( ampller ((e.g., PEDPED or POM)POM)
=
n Mussels
10000001 1 Li
?1:1 Line
10000atio
ccumulation is being rapidly establishedccumulation is being rapidly establishedoon
c
r2 = 0.88
100 1000 10000 100000 1000000
W
PED C t ti ( / )PED Concentration (ng/g)
Passive Sampler ApplicationPassive Sampler ApplicationPalos Verdes Superfund SitePalos Verdes Superfund Site
WaterWater CColumnolumn andand SedimentSediment DeploymentsDeployments–– WaterWater ColumnColumn andand SedimentSediment DeploymentsDeployments
Los Angeles (CA)Los Angeles (CA)Carmen White Carmen White ((RPMRPM))( )( )Deep Deep water marine site (60 m)water marine site (60 m)DDTs & PCBsDDTs & PCBsSeven Seven water column stations and five sediment stationswater column stations and five sediment stations
–– OObjectivesbjectives
DetermineDetermine waterwater ccolumnolumn cconcentrationsoncentrationsDetermineDetermine waterwater columncolumn concentrationsconcentrations ofof contaminantscontaminants rresultingesulting fromfromofof contaminantscontaminants resultingresulting fromfrom remediation remediation activity (before, during, after)activity (before, during, after)Determine Determine magnitude magnitude of flux of contaminants of flux of contaminants into the water column from into the water column from sedimentssedimentsCompare different types of Compare different types of passive samplers (PED, POM, passive samplers (PED, POM, SPME)SPME)
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Passive Sampler ApplicationPassive Sampler Application
LAC
SD
Deployments
Water Column – PEDs(flow(flow mmetereter deployment)deployment)
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Sediments – PEDs, POMs & SPME(flux platform deployment)
Passive Sampler ApplicationPassive Sampler ApplicationAquatic Life
AWQC
30,000
)tio
n (p
g/L)
Con
cent
ra Human HealthAWQC
C
60
StationU.S. U.S. EPA NARPM 2011EPA NARPM 2011 2121
Passive Sampler ApplicationPassive Sampler Application
Office of Superfund Remediation and Technology InnovationandOffice of Research and Development
Guidance for the Application ofPassive Samplers at Superfund Sites
Sediment Assessment and Monitoring Sheet (SAMS)
Passive Samplers at Superfund Sites
Atmosphere
W t
Wildlife
Mussels WaterFish
Mussels
Dissolved and BioavailableConcentration
PassiveSamplers
OSWER Directive 9200 1 96FS
Contaminated Sediments
(Not to Scale)Benthic Worms
OSWER Directive 9200.1-96FS
February 2012
SAMS guidance SAMS guidance
titi ffdocument in document in preparapreparatition on ffor or using passive using passive samplerssamplers atatsamplerssamplers atat Superfund sitesSuperfund sites
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SummarySummaryPassive sampling a Passive sampling a scientifically sound and costscientifically sound and cost--effective approach effective approach for monitoring for monitoring contaminant contaminant concentrations in the water column and sediment concentrations in the water column and sediment interstitial watersinterstitial waters
Passive samPassive sampplers lers ppp pp provide information on:rovide information on:–– Dissolved and Dissolved and bioavailablebioavailable concentrations of contaminantsconcentrations of contaminants–– SSampler uptake may serve as a surrogate for ampler uptake may serve as a surrogate for animal animal
bioaccumulationbioaccumulation
Applications include:Applications include:–– M
remediationremediationMonitoring water column concentrations onitoring water column concentrations before, before, during and after during and after remediationremediation
–– Determining Determining sources of contaminants released sources of contaminants released from sediments from sediments to the water column to the water column (e.g., (e.g., site model site model development)development)
–– SAMSSAMS guidanceguidance documentdocument inin preparationpreparationSAMSSAMS guidanceguidance documentdocument inin preparationpreparation