Steering meeting presentation april 15 2014

The Role of Passive Sampling in the Screening and Monitoring of New and Emerging Chemicals

April 15th, 2014

Outline •  Work Package (WP) 1 – Desk study and literature review •  WP 2 – Analytical method development and optimisation •  WP 3 – Passive sampling, pilot monitors and spot sampling •  WP 4 – Biota sampling and testing for selected substances •  WP 5 – Upland activity: Cypermethrin study •  WP 6 – WWTP outfall receiving waters •  WP 7 – Integration and assessment of datasets •  WP 8 – Project management

Work Package 1

Target Monitoring Sites

•  Dublin sites have been changed and an extra site has been included: – Lucan Bridge, Malahide, Kilcullen Bridge and Poobeg

•  This sampling will be taking place from May 2014.

•  Historical data from MI and DCU is available for these sites.

Target Monitoring Sites

•  Upstream site added to cypermethrin study. •  SPMD, POCIS, grab samples and biota to be collected.

•  Patricia McCreesh and Ray Thomas supplied informaNon on historic data and site selecNon for Donegal.

Protocol for Biota Sampling •  50 My#lus edulis mussels •  4 – 6 cm, 4 – 5 cm •  Depurate for 24 hours •  Dissect (shell weight, Nssue weight)

•  Homogenise •  Store at -‐30C

Literature Review

•  ‘Passive Sampling of Emerging Compounds’ – Environmental PolluNon (IF 3.730)

Deliverables Work Package 1 Status

Desk study and literature review Complete

SelecNon of target monitoring staNons Complete

Develop protocols and select locaNons for biota monitoring Complete

Develop detailed protocols for passive sampler deployments Complete

Final Report: Desk study with protocols for deployment, biota sampling

Work Package 2

Work Package 2 : •  Method development ongoing for:

–  Organohalogen pesticides by GCMS –  HBCD and BFRs by LCMS –  PFOS by LCMS –  Pharmaceuticals and endocrine disrupting compounds

•  Extraction by soxhlet/solid phase extraction (SPE) •  Analysis by gas and liquid chromatography with

tandem mass spectrometric or UV detection


Method selecNon and opNmisaNon Methods in place for 24 of 27 analytes

Methods for: Organohalogen pesNcides, HBCD. Transfer of BFR method to LC-‐MS/MS

Ongoing

Methods for: EDCs Ongoing

Methods for: PharmaceuNcals Ongoing

Methods for: PFOS Ongoing

Note: All methods to be operational by month 26.

Work Package 3

Work Package 3:

•  Catchment approach has been taken in Cork

•  Deployment of POCIS and PDMS samplers in July 2013

•  POCIS collected after 4 weeks •  PDMS and water samples collected after 2

months

Sampling •  Second sampling regime in Cork underway for PDMS and POCIS.

•  POCIS trial to Ne-‐in with WP 3 in Cork – 2, 4, 6 week collecNons to evaluate uptake

•  Samplers deployed in Kilkieran (March 2014), POCIS and grab samples collected.

Results: POCIS and Grab Samples Shandon Lough Mahon Cork Outer Harbour Iniscarra Inchigeelagh

Analyte Units 17alpha ethynyloestradiol (EE2)

ng <0.2 <0.2 <0.2 1.39 <0.2

17beta oestradiol (E2) ng <0.5 2.36 1.98 <0.5 <0.5

17alpha ethynyloestradiol (EE2)

ng/L* nd nd nd nd nd

17beta oestradiol (E2) ng/L* nd nd nd nd nd


Prepare equipment (PDMS & POCIS) for deployment Complete

Deployment of samplers Phase two complete

CollecNon and screening analysis Ongoing

Spot sampling as compliance measure Phase two complete

Work Package 4

Biota sampling •  Fish samples supplied by IFI for Cork catchment (2013) – Trout (Upper Lee catchment) – Whole fish

•  Analysed for organic pollutants at the MI – Ongoing

•  IFI to supply more samples in 2014 •  Mussels collected from marine sites


Sampling programme for biota at all locaNons Ongoing

Sample collecNon & preparaNon Ongoing

Analysis of shellfish and fish samples Ongoing

RecommendaNons Cork PDMS redeployed

Work Package 5

StaQons and sampling plan

County Site RaNonale POCIS PDMS Water Mussels Fish (IFI)

Cork Inchigeelagh Upstream river staNon ✓ ✓ ✓ ✓

Inniscarra Downstream river staNon ✓ ✓ ✓ ✓

Shandon Riverine/transiNonal ✓ ✓ ✓ ✓

Lough Mahon Riverine/transiNonal staNon ✓ ✓ ✓ ✓

Outer bay Riverine/transiNonal staNon ✓ ✓ ✓ ✓ Dublin Malahide High pressure coastal ✓ ✓ ✓ ✓

Poolbeg Riverine/transiNonal ✓ ✓ ✓ ✓

Lucan Bridge Downstream river staNon ✓ ✓ ✓ ✓

Kilcullen Bridge Upstream river staNon ✓ ✓ ✓ ✓ Galway Kilkieran Bay Coastal reference staNon ✓ ✓ ✓ ✓ Mayo Burrishoole Upstream river staNon ✓ ✓ ✓ ✓

Donegal Glen Lackagh 1 Cypermethrin study SPMD ✓ ✓ EPA Benthic kick

sampling Glen Lackagh 2 Cypermethrin study SPMD ✓ ✓

Work Package 5 : •  Cypermethrin study beginning April 2014 •  Analysis by Ray Thomas, NIEA

•  Site (s): –  Glen Lackagh sites 38G040900 and 38G040700

upstream of Glen Lough, Donegal –  Pre- and post- application study

Cypermethrin Data River Q-‐Value Date X Y Remarks from fieldsheets

GLEN (LACKAGH)

2-‐3 28/09/2012 212685 431467 InvesNgaNve. Toxic signs at 0900. Worse here. Sheep suspected – cypermethrin EffecNvely a dead river here. Some forestry u/s. Also one field that looks ''burned'' possible herbicide? Lots of heather u/s. didn''t see sheep on open land. Okay at 0400

GLEN (LACKAGH)

3/0 26/09/2012 211832 431043 Something wrong here. Two samples taken. Very sparse. Sheep dip?

Cypermethrin Assessment •  Large dataset of usage and occurrence reports has been compiled. –  Proposed desk study on this data

•  InformaNon from census of agriculture, department of veterinary medicine, Coilte, Teagasc, DEFRA, department of Agriculture, etc.

•  Ray Thomas, Patricia McCreesh and Danielle Ashton have assisted the project team in the collecNon of this data.


Site selecNon and sampler deployment Sites selected, deployment ongoing

Spot sample collecNon Ongoing

Analysis of samples for cypermethrin May/June 2014

Passive sampler extracNon and analysis for cypermethrin June 2014

Assessment of upland acNvity Ongoing

Work Package 6

Work Package 6 : •  WWTP outfall study-EDCs and pharmaceuticals •  Methods

–  In place for E2 in water and biota –  Optimising method for EE2 to detect below EQS –  Diclofenac method under development

•  POCIS devices suitable –  Issue with sampling rates

•  MI experience with integrated study-historical data for E2 and EE2 in Dublin


Site selecNon and sampler deployment Ongoing

Spot sample collecNon Ongoing

Analysis of samples for EDCs and PharmaceuNcals Ongoing

Passive sampler extracNon and analysis for EDCs and PharmaceuNcals Ongoing

CollecNon of background data on WWTP efficiency Ongoing

Work Package 7

PS and biota •  Biota EQS set for 11 compounds •  EU guidance document currently being developed

–  SelecNon of target organism differs between MS –  Human health vs secondary poisoning –  Require consistency and comparability to assess compliance against

the EQSbiota and in interpretation of data

•  PS and biota –  Similar drivers for uptake –  Environmental factors can be modelled –  Metabolism and health status can be complicaNng factors –  Suitable where no biota are present

White PhD thesis: Relationship between BAFs (dry weight) calculated from mussels and PS at the Kilkieran reference site vs. parameter LogKpw.

1

2

3

4

5

6

7

3 3.5 4 4.5 5 5.5 6 6.5 7 7.5

Log BA

F (dry weight)

Log Kpw

PAH BAFdw

PCB BAFdw

OC BAFdw

PBDE BAFdw

Log BAFdw = 0.80 (Log Kpw) + 0.13 R2= 0.75

BAF model for PDMS and biota (mussels): Kilkieran

Work Package 8

Project Management

•  Monthly and weekly meetings and conference calls have continued for the project team.

•  Monthly analytical reports have been introduced to facilitate the final STRIVE report deliverable due at project completion.

Funding OpportuniQes

PublicaQons in PreparaQon

•  JPI Water call

•  Passive sampling review (submitted) •  Book (August 2014) •  Review chapter (May/June 2014)


Kick-‐off meeNng Complete

Workshops 1/3

Project meeNngs Ongoing

Financial and Technical reports ( EPA Deadlines) Ongoing

Monthly communicaNons Ongoing

Final Report 2016

Acknowledgements This 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 by the Irish Government under the National Development Plan 2007–2013. It is administered on behalf of the Department of the Environment, Heritage and Local Government by the Environmental Protection Agency, which has the statutory function of co-ordinating and promoting environmental research.