FundamentalsFundamentals ooff PPassiveassive ... (POM) ... Carmen White (()RPM) Deep Deep water marine site (60 m) ... tion (pg/L) C oncentra Human Health AWQC 60 Station;

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

U.S. U.S. EPA NARPM 2011EPA NARPM 2011 22

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


(Not to Scale)Diffusion/Advection

IntroductionIntroduction

U.S. EPA NARPM 2011U.S. EPA NARPM 2011 44

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)

––

––


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


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)



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

99U.S. U.S. EPA NARPM 2011EPA NARPM 2011

Types of Passive SamplersTypes of Passive Samplers

Passive Sampler DeploymentPassive Sampler DeploymentWWaterater CColumnolumn

(NRMRL & Battelle)


(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)


Passive Sampler DeploymentPassive Sampler Deployment


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)


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


Passive Sampler TheoryPassive Sampler TheoryE ilib i S liEquilibrium Sampling


pler

)en

tratio

nsi

ve S

amp

Con

ceg/

mL

Pas

s

Deployment Time (days)

(n


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


(n Concentration KSampler-D is the passive sampler-dissolved partition coefficient



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


(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


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)


)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)


Passive Sampler ApplicationPassive Sampler Application

LAC

SD

Deployments

Water Column – PEDs(flow(flow mmetereter deployment)deployment)


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




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



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

Documents

FundamentalsFundamentals ooff PPassiveassive ... (POM) ... Carmen White (()RPM) Deep Deep water marine site (60 m) ... tion (pg/L) C oncentra Human Health AWQC 60 Station;