Passive sampling of polar emerging contaminants in Irish...

PassivesamplingofpolaremergingcontaminantsinIrish

catchmentsLISAJONES,J. RONAN,B.MCHUGH,R.THOMAS,F.REGANDUBLINCITYUNIVERSITY

The 18th International Conference on Diffuse Pollution and EutrophicationLos Angeles, USA, August 13-17, 2017

Outline

• Passive Sampling– Analytes

• Approach– Rationale– Catchment study– Sampling sites

• Cork catchment• Conclusions

Lisa Jones

Dublin City University

Projectdescription• EPAfunded3yearproject• RoleofPSasascreeningandmonitoringtoolfornewandemergingchemicals

• RoleofPSasasurrogateforbiotamonitoring• Qualitative/quantitativescreeningofselectedsubstancesinanumberofIrishwatersrepresentativeofdifferentpressures

• Casestudiesonemergingcompoundsandpharmaceuticalsusingacatchmentapproach

Passive Sampling Lisa Jones


PassiveSampling

PassiveSampling• Freeflowofanalytemoleculesfromsampledmediumto

collectingmedium– onlydissolvedanalytes,noenergysource

Fig. 1 – Passive sampling mechanism

Fig. 2 – Passive sampling device

(interior)

Fig. 3 – Passive sampling devices



Fig.5– Adsorptionpassivesamplingmechanism

Fig.4– Absorptionpassivesamplingmechanism

Equilibriumisreachedandtime-weightedaverageisdetermined.Mainlyfornon-polarcompounds.

Kineticregimeismaintainedandcalculationsarebasedontime-integratedmeasurementsMainlyforpolaranalytes.

Ref: Smedes et al., 2010



• Greatersensitivitythancanbeachievedby“traditional”spot-sampling

• Applicabletoawidevarietyofcompounds• Time-integratedsamplingatlowdetectionlimitsandin-situextractionofanalytes

• Abilitytosamplelargevolumesofwater• Easeofdeploymentandprocessing• Noexternalpowerinputisrequired

AdvantagesofPassiveSamplingLisa Jones


TargetAnalytesPassive Sampling Lisa Jones


EPA Samplertype Water Biota

EDCsandpharmaceuticals

Compound

POCIS

Y Y17bestradiol(E2) Y Y17aethynylestradiol(EE2) Y YDiclofenac Y YAlkylphenols Y Y

Organohalogens

HCB

PDMS

Y YHeptachlor Y YHeptachlorepoxide Y YHBCDD Y YPCBs Y YPBDEs Y YHCBD Y YDioxinsanddioxin-likecompounds Y Y

PFOS PFOS POCIS Y Y

TargetAnalytesPassive Sampling Lisa Jones


Compoundgroup Compound Samplertype Water Biota

PAH

Naphthalene

PDMS

Y YAnthracene Y YFluoranthene Y YBenzo-a-pyrene Y YBenzo-b-fluoranthene Y YBenzo-k-fluoranthene Y YIndeno-1,2,3cd-pyrene Y YBenzo-g,h,i-perylene Y Y

Pesticides

Aclonifen

POCIS

Y YBifenox Y YCybutryn Y YTerbutryn Y YQuinoxyfen Y YDichlorvos PDMS Y YDicofol Y Y

Cypermethrin SPMD/PDMS Y N

Approach

CatchmentApproach• TheWFDintroducedacomprehensivecatchmentbasedapproachtowatermanagement

• Identifypointsourcesandpathwaysofpollution• Moretargetedapproachtomonitoringofemergingandprioritycompoundsinwater

• Potentialroleforthecombinationofcatchmentbasedapproachesandfocusedwaterandpassivesampleranalysisforthesurveillancemonitoring

Lisa Jones


PrioritypollutantsinWastewaterLisa Jones


• Relate emission factors to occurrence• Monitor priority pollutant levels in

wastewater treatment plant effluents

• Relate levels detected to emission factors• Population equivalents, rainfall, traffic, etc.

• Create index of priority substance emissions from wastewater treatment plants

EmergingsubstancesinIrishwatersEPA RBDs DAFF LAs Other(14Agencies)

Surfacewater ✓ ✓ ✓ 4others

Groundwater ✓ ✓ ✓ 4others

Landfill ✓ ✓

Mining ✓

Stormwater/runoff 1other

WWTPs ✓ ✓

Industry ✓ ✓ ✓

Agriculture ✓ ✓ 2others

Forestry ✓ 2others

Legislation ✓ ✓ ✓ ✓ 4others

Domestichouseholds 1other

Airports ✓

Aquaculture ✓ 2others

Lisa Jones


RiskIndex

IPPCLicenses(155)

WastewaterDischargeLicenseApplications

(9)

AnnualEnvironmentalReports(11)

TradeEffluentLicenses(872)

WasteDischargeLicenses(62)

ExperimentalData(>400)

TrafficData CensusData

Rainfalldata(102)

Lisa Jones


TargetMonitoringStationsPassive Sampling Lisa Jones


County Site Rationale POCIS PDMS Water Mussels Fish(IFI)

Cork

Inchigeelagh Upstreamriver ✓ ✓ ✓ ✓

Inniscarra Downstreamriver ✓ ✓ ✓ ✓

Shandon Riverine/transitional ✓ ✓ ✓ ✓

LoughMahon Riverine/transitional ✓ ✓ ✓ ✓

Outerbay Riverine/transitional ✓ ✓ ✓ ✓

Dublin

Poolbeg Highpressurecoastal ✓ ✓ ✓ ✓

Osberstown Riverine/transitional ✓ ✓ ✓ ✓

LucanBridge Downstreamriver ✓ ✓ ✓ ✓

KilcullenBridge Upstreamriver ✓ ✓ ✓ ✓

Galway KilkieranBay Coastalreference ✓ ✓ ✓ ✓

Mayo Burrishoole Upstreamriver ✓ ✓ ✓ ✓

DonegalGlenLackagh1 Cypermethrinstudy ✓ ✓ EPABenthickick

samplingGlenLackagh2 Cypermethrinstudy ✓ ✓

Lisa Jones


ProtocolforPassiveSamplerDeployment- POCIS

• EA lab/NLS guidelines for POCIS• Sent in sealed canisters• On site samplers and field blanksexposed to same conditions

• 4 week deployment time has beenoptimized

POCIScanister**



ProtocolforPassiveSamplerDeployment

• ICES TIMES no. 52* for PDMS• EA lab/NLS guidelines for POCIS

Record:• GPSco-ordinates• Dateandtimeofdeployment• Salinity• Watertemperature*ICESTIMESno.52.2012.Guidelinesforpassivesamplingofhydrophobiccontaminantsinwaterusingsiliconerubber

**EnvironmentalSamplingTechnologieslab:http://www.est-lab.com/pocis.php

PDMSsheetattachment*

POCIScanister**



AnalysisPassive Sampling Lisa Jones


• 1Lwatersamples(n=3)• Samplerdeployments4-6weeks(POCIS/PDMS)• SPE– Strata-XwithelutionusingDCM• HPLC-MS/MS

– AppliedBiosystems3200Q-TRAPwasused.Themobilephasesweredeionisedwater(A)and0.025%TEAin95:5CH3OH:acetone(B)flowingat300μLperminutewithagradientasfollows:0to0.5min(5to20%B),0.5to1min(20to40%B),1to12min(40to80%B),12to14min(80%B)and14to14.5min(80to5%B)withanalysisaspertheEnvironmentAgencyBlueBook220

CorkCatchment

TargetMonitoringStationsPassive Sampling Lisa Jones


County Site Rationale POCIS PDMS Water Mussels Fish(IFI)

Cork

Inchigeelagh Upstreamriver ✓ ✓ ✓ ✓

Inniscarra Downstreamriver ✓ ✓ ✓ ✓

Shandon Riverine/transitional ✓ ✓ ✓ ✓

LoughMahon Riverine/transitional ✓ ✓ ✓ ✓

Outerbay Riverine/transitional ✓ ✓ ✓ ✓

Dublin

Poolbeg Highpressurecoastal ✓ ✓ ✓ ✓

Osberstown Riverine/transitional ✓ ✓ ✓ ✓

LucanBridge Downstreamriver ✓ ✓ ✓ ✓

KilcullenBridge Upstreamriver ✓ ✓ ✓ ✓

Galway KilkieranBay Coastalreference ✓ ✓ ✓ ✓

Mayo Burrishoole Upstreamriver ✓ ✓ ✓ ✓

DonegalGlenLackagh1 Cypermethrinstudy SPMD ✓ ✓ EPABenthickick

samplingGlenLackagh2 Cypermethrinstudy SPMD ✓ ✓

Cork oestrogen results

Matrix LoughAlluaInchigeelagh Iniscarra Shandon Lough

MahonCorkOuterHarbour

Analyte Units 2013EE2

POCISngL-1 <0.04 0.06 <0.04 <0.04 <0.04

E2 ngL-1 <0.04 <0.04 <0.04 0.06 0.05EE2

WaterngL-1* nd nd nd nd nd

E2 ngL-1* nd nd nd nd ndAnalyte Units 2014EE2

POCISngL-1 <0.04 0.06 0.09 <0.04 <0.13

E2 ngL-1 <0.04 <0.04 0.07 <0.04 <0.12EE2

WaterngL-1* nd nd nd nd nd

E2 ngL-1* nd nd nd nd nd

*LODwatersamplesbyLC-MS/MS:E1:0.07ng L-1 E2:0.07ng L-1,EE2,0.11ng L-1.5Lsamplen=2EffectivesamplingratesPOCIS(ng/sampler/day)*:E1:0.39,E2:0.46,EE2:0.235EQS:EE2(0.007ngL-1)E2(0.08ng L-1)

Upstream Downstream



PesticidesOccurrenceinWaterPassive Sampling Lisa Jones


Pesticide TargetEQS Freq. MaxDetected

µg L-1 N=25Aclonifen 0.12 4 0.2 x 10-5

Bifenox 0.012 4 3.8 x 10-6

Cybutryn 0.0025 10 0.6 x 10-5

Dichlorvos 0.0006 12 3.2 x 10-6

Dicofol 0.0013 0 0Heptachlor

0.00000020 0

Heptachlor epoxide 0 0Quinoxyfen 0.15 15 6.4 x 10-6

Terbutryn 0.065 8 1.3 x 10-6

Cypermethrin Study

Cypermethrin study• Persistentpyrethroidinsecticide.• Cypermethrinkillsinvertebratesandalthoughithasashorthalf-life(<2weeks)itcanhavelastingeffects.

• Sitesselectedbasedonpressuresfromagriculture,forestryandaquaculture.

• Largedatasetofusageandoccurrencereportshasbeencompiled



• Aim tostudytheeffectsofupstreamactivityandtheoccurrenceofcypermethrin usingpassivesampling.

• NIEAandUKEAbegansurveillancemonitoringin2013.

• EPAadvisedonsiteselectioninDonegal:– UpstreamanddownstreamsitesinGlenLackagh

Cypermethrin studyPassive Sampling Lisa Jones




3Sensitive/potentiallyimpactedsites 2Controlsites

Glen Lackagh DownstreamWater: 3.4 – 1.4 ng L-1

PDMS: nd

Big BurnWater: 2.0 – <0.1 ng L-1

PDMS: nd

Glen Lackagh UpstreamWater: 2.9 – 0.2 ng L-1

PDMS: <0.06 ng L-1

OwenveaghWater: 0.6 – 0.8 ng L-1

PDMS: nd

Clogher FinnWater: 1.5 – 1.2 ng L-1

PDMS: nd

EQS: 0.08 ng L-1

Conclusions

Environmentalchallengesandsolutions

• PSaddresseschallengesofdetectingatlowEQS– Dissolvedvstotalwaterconcentrationremainsanissue

• Time-integratedmeasurements• Easytodeployandanalyse

– Simplermatrix– Lackofconfoundingbiologicalfactors– Suitablefor“temporal”trendmonitoring(andforsurveillance/screening)andforco-deploymentwithbiota

• Ongoingdevelopmentofmodellingandpartitioncoefficientswilldrivecapabilities



The Way Forward• Itisproposedthat:

– PSMcouldbecomepartofalargerstrategyformonitoring;

– ThereisaroleforPSinarisk-basedscreeningapproachtooperationalmonitoring;

– PSisapplicableintrendmonitoring(feedingintoriskbasedassessments);

– ThereisaneedtodevelopaplandefininghowtoimplementPSforthepurposesoftrendmonitoring.



ProjectMedia

• Twitter:@irishwaterstudy• Website:https://sites.google.com/site/irishpassivesampling/home



AcknowledgementsThis project is funded by the EPA as part of the Science,Technology, Research and Innovation for the Environment(STRIVE) Programme 2007–2013. This programme is financed bythe Irish Government under the National Development Plan2007–2013.

It is administered on behalf of the Department of theEnvironment, Heritage and Local Government by theEnvironmental Protection Agency, which has the statutoryfunction of co-ordinating and promoting environmentalresearch. Thanks to the Marine Institute for funding this travel.



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