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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
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Outline
• Passive Sampling– Analytes
• Approach– Rationale– Catchment study– Sampling sites
• Cork catchment• Conclusions
Lisa Jones
Dublin City University
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Projectdescription• EPAfunded3yearproject• RoleofPSasascreeningandmonitoringtoolfornewandemergingchemicals
• RoleofPSasasurrogateforbiotamonitoring• Qualitative/quantitativescreeningofselectedsubstancesinanumberofIrishwatersrepresentativeofdifferentpressures
• Casestudiesonemergingcompoundsandpharmaceuticalsusingacatchmentapproach
Passive Sampling Lisa Jones
Dublin City University
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PassiveSampling• Freeflowofanalytemoleculesfromsampledmediumto
collectingmedium– onlydissolvedanalytes,noenergysource
Fig. 1 – Passive sampling mechanism
Fig. 2 – Passive sampling device
(interior)
Fig. 3 – Passive sampling devices
Passive Sampling Lisa Jones
Dublin City University
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Fig.5– Adsorptionpassivesamplingmechanism
Fig.4– Absorptionpassivesamplingmechanism
Equilibriumisreachedandtime-weightedaverageisdetermined.Mainlyfornon-polarcompounds.
Kineticregimeismaintainedandcalculationsarebasedontime-integratedmeasurementsMainlyforpolaranalytes.
Ref: Smedes et al., 2010
Passive Sampling Lisa Jones
Dublin City University
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• Greatersensitivitythancanbeachievedby“traditional”spot-sampling
• Applicabletoawidevarietyofcompounds• Time-integratedsamplingatlowdetectionlimitsandin-situextractionofanalytes
• Abilitytosamplelargevolumesofwater• Easeofdeploymentandprocessing• Noexternalpowerinputisrequired
AdvantagesofPassiveSamplingLisa Jones
Dublin City University
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TargetAnalytesPassive Sampling Lisa Jones
Dublin City University
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
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TargetAnalytesPassive Sampling Lisa Jones
Dublin City University
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
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CatchmentApproach• TheWFDintroducedacomprehensivecatchmentbasedapproachtowatermanagement
• Identifypointsourcesandpathwaysofpollution• Moretargetedapproachtomonitoringofemergingandprioritycompoundsinwater
• Potentialroleforthecombinationofcatchmentbasedapproachesandfocusedwaterandpassivesampleranalysisforthesurveillancemonitoring
Lisa Jones
Dublin City University
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PrioritypollutantsinWastewaterLisa Jones
Dublin City University
• 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
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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
Dublin City University
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RiskIndex
IPPCLicenses(155)
WastewaterDischargeLicenseApplications
(9)
AnnualEnvironmentalReports(11)
TradeEffluentLicenses(872)
WasteDischargeLicenses(62)
ExperimentalData(>400)
TrafficData CensusData
Rainfalldata(102)
Lisa Jones
Dublin City University
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TargetMonitoringStationsPassive Sampling Lisa Jones
Dublin City University
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 ✓ ✓
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Lisa Jones
Dublin City University
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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**
Passive Sampling Lisa Jones
Dublin City University
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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**
Passive Sampling Lisa Jones
Dublin City University
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AnalysisPassive Sampling Lisa Jones
Dublin City University
• 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
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TargetMonitoringStationsPassive Sampling Lisa Jones
Dublin City University
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 ✓ ✓
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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
Passive Sampling Lisa Jones
Dublin City University
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PesticidesOccurrenceinWaterPassive Sampling Lisa Jones
Dublin City University
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
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Cypermethrin Study
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Cypermethrin study• Persistentpyrethroidinsecticide.• Cypermethrinkillsinvertebratesandalthoughithasashorthalf-life(<2weeks)itcanhavelastingeffects.
• Sitesselectedbasedonpressuresfromagriculture,forestryandaquaculture.
• Largedatasetofusageandoccurrencereportshasbeencompiled
Passive Sampling Lisa Jones
Dublin City University
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• Aim tostudytheeffectsofupstreamactivityandtheoccurrenceofcypermethrin usingpassivesampling.
• NIEAandUKEAbegansurveillancemonitoringin2013.
• EPAadvisedonsiteselectioninDonegal:– UpstreamanddownstreamsitesinGlenLackagh
Cypermethrin studyPassive Sampling Lisa Jones
Dublin City University
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Passive Sampling Lisa Jones
Dublin City University
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
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Environmentalchallengesandsolutions
• PSaddresseschallengesofdetectingatlowEQS– Dissolvedvstotalwaterconcentrationremainsanissue
• Time-integratedmeasurements• Easytodeployandanalyse
– Simplermatrix– Lackofconfoundingbiologicalfactors– Suitablefor“temporal”trendmonitoring(andforsurveillance/screening)andforco-deploymentwithbiota
• Ongoingdevelopmentofmodellingandpartitioncoefficientswilldrivecapabilities
Passive Sampling Lisa Jones
Dublin City University
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The Way Forward• Itisproposedthat:
– PSMcouldbecomepartofalargerstrategyformonitoring;
– ThereisaroleforPSinarisk-basedscreeningapproachtooperationalmonitoring;
– PSisapplicableintrendmonitoring(feedingintoriskbasedassessments);
– ThereisaneedtodevelopaplandefininghowtoimplementPSforthepurposesoftrendmonitoring.
Passive Sampling Lisa Jones
Dublin City University
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ProjectMedia
• Twitter:@irishwaterstudy• Website:https://sites.google.com/site/irishpassivesampling/home
Passive Sampling Lisa Jones
Dublin City University
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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.
Passive Sampling Lisa Jones
Dublin City University
Thankyouforyourattention!