Welcome to the CLU-IN Internet Seminar

1. Welcome to the CLU-IN Internet Seminar Biological-based Assays - Indicators of Ecological Stress Sponsored by: National Institute of Environmental Health Sciences, Superfund Research Program Delivered: September 23, 2010, 2:00 PM - 4:00 PM, EDT (18:00-20:00 GMT) Instructors: Bruce Duncan, Senior Ecologist with EPA Region 10's Office of Environmental Assessment (duncan.bruce@epamail.epa.gov) Jim Shine, Associate Professor of Aquatic Chemistry, SRP Grantee (jshine@hsph.harvard.edu) Moderator: Beth Anderson, Program Analyst, Superfund Research Program (tainer@niehs.nih.gov) Visit the Clean Up Information Network online atwww.cluin.org 1

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3. Bioavailability of Sediment Contaminants1. NIEHS-sponsored Bioassay Network2. Relationships between sediment, water, mussels, SPMEs, & fish Bruce Duncan, EPA Region 10, Seattle, Office of Environmental Assessment Risk Evaluation Unit Session IV: Biological-based Assays – Indicators of Ecological Stress Ecological Risk: New Tools and Approaches – September 23, 2010

4. KC Donnelly

5. National Network to Investigate the Utility of Short-term Bioassays for Evaluating Sediment Quality Investigate the utility of using SRP-developed assays to characterize the toxicity of complex mixtures in sediment Hypothesis: SRP-developed assays will detect degraded sediment quality effectively and serve as an additional line of evidence if integrated into risk assessment

6. Background • Superfund Research Program • Created in 1986 under the Superfund Amendments and Reauthorization Act (SARA) • University-based grants program • Basic research • Complement EPA and ATSDR • Under National Institute of Environmental Health Sciences

7. Background Collaboration between 5 University based Superfund Research Programs Texas A&M University Duke University Michigan State University University of California – Davis University of California – San Diego

8. Summary Table – “calibration” testing single contaminants and mixtures BIOASSAY In vivo Fish embryo EROD teratogenicity GJIC CALUX Chemical (EC50) (EC10) (EC50) (EC50) 405 ppm BaP 1 ppb 200 ppb NA (EC40) Flu NA NA 4.4 ppm NA 422 ppm BaP+Flu 1 ppb 100 ppb 4.8 ppm (EC40) Coal - tar .06 ppm 5 ppb 2.87 ppm 341 ppb PCB 126 .03 ppb 0.1 ppb NA 49 ppt PCB 153 NA NA 4.34 ppm NA PCB mix -- -- -- --

9. Conclusions Calibration step was completed Assays were not always more sensitive but can serve as an additional line of evidence Improved specificity 2nd Phase of project anticipated Aliquots of homogenized sediment will be sent to Superfund Research Program investigators for analysis Study will attempt to “crosswalk” with biological effects data from sediment toxicity bioassays

10. Bioavailability of Sediment ContaminantsRelationships between sediment, water, mussels, SPMEs, & fish Bruce Duncan, EPA Region 10, Office of Environmental Assessment, Risk Evaluation Unit & Adjunct Professor, Texas A&M University, Health Science Center, School of Rural Public Health, Dept Environmental and Occupational Health In collaboration with Matt Kelley, Postdoctoral Fellow - Dugas Lab, LSU Health Sciences Center-Shreveport

11. Partners • EPA R10 – deployment, retrieval, design • Dive Team, Manchester Lab, Field support, Program volunteers • Texas A&M University – design,tissue, water, sediment analysis • KC Donnelly (dec); Matt Kelley; Thomas McDonald • Southern California Coastal Water Research Project – SPME design, analysis • Keith Maruya, David Tsukada, Wayne Lao • NMFS – juvenile salmon • Jim Meador • Applied Biomonitoring – mussel prep, measuring, design • Michael Salazar, Sandra Salazar

12. http://dnr.metrokc.gov/wlr/waterres/wqa/wqpage.htm Site History: Lower Duwamish Waterway

13. 2008 stations 13

14. 2009 stations

15. Sediment - 2008

16. Pore water & Surface Water - 2008

17. Sediment PAH bioavailability • Design from the sediment up: • Surface Water • Mussels & SPMEs - top of cages • Fish in cages • Mussels & SPMEs - bottom of cages • Sediment • Porewater

18. Sediment Sampling

19. Pore Water Collection

20. SPMEs – inside cages and in sediment 2008, top and bottom of cages in 2009

21. New for 2009Mussels – top and bottom of cages, matched to SPMEs

22. NOAA Field Facility - Mukilteo Fish – juvenile salmonids

23. Fish Transport

24. Cage Deployment

25. Cage Retrieval

26. Fish retrieval/processing

27. Water Sampling

28. Sediment PAH bioavailability • How well do SPMEs concord with fish and mussel tissue? • What are relationships between biotic and abiotic media both in/on and above the sediment? • Status on other analyses

29. Some Expectations • Fish tissue PAHs – have seen before, but not often • Sediment/Water – expect higher tPAH concentrations in sediment porewater, perhaps different mix of individual PAHs • Mussels – challenges with mussels in contact with sediment • SPMEs – could show reduced variablity and concordance with mussel tissue

30. Any PAHs in the fish? • Fish tissue PAHs – previous & new work

31. Sediments any different?

32. LDW 2008 SPME tPAHs (ng/L) SPMEs differ?

33. How did mussels do? growth/survival

34. Mussel Growth – closer look

35. How about relationships among parameters?

36. Sediment–water tPAH relationshipwater at hatchery = 48.25 water at hatchery = 48.25

37. PAH patterns - Sediment, water and tissue Sediment Mussels Fish Water

38. PAH patterns - SPMEs

39. Mussels (tPAH)Sediment, water and SPMEs relationships

40. Summary of overall relationships • puzzling in some respects • recall the loss of the B site samples which had highest sediment PAHs

41. Summary -mixed relationships

42. Summary -mixed relationships–note scale for sediment concentration (missing data from 3400 mg/kg dw sediment)

43. Summary of variability (SEs) for different measures

44. Summary: Reducing variability

45. Summary: Next stepsPCBsPorewaterQuestions

46. Tools to Assess Metal Bioavailability in Aquatic Ecosystems Jim Shine Department of Environmental Health Harvard School of Public Health Funding: NIEHS Superfund Research Program

47. Outline • Introduction: Why Care About Metal Speciation? • The ‘Gellyfish’: Measurement of Metal Speciation in Aquatic Ecosystems • Design/Testing • Field Application I: Metal Speciation in Boston Harbor • Field Application II: Sensor of Metal Uptake in Mussels • - Concluding Remarks

48. Importance of Metal Speciation: • - Free Metal Ion: A Key Metal Species • - Allows understanding of distribution of metals in a system • Predictive of transport, fate, biological uptake • - Not a constant fraction of total metal in space and time • - Water quality criteria based on total metals awkward • - Biotic Ligand Model: New generation of WQC • - Based on free metal ion interacting with biota

49. Current Speciation Analytical Techniques • -Difficult, time consuming, expensive, require specialized training • Can only be done for one metal at a time • Limit scope of speciation studies (space and time) • - Modeling approaches? Cu2+ = f(Cutotal, DOC) • - Problem: How to generate large enough data sets to be useful • - What is the spatial, temporal variability in speciation? • - What environmental factors affect speciation? • - Need: Simple, inexpensive tool to measure speciation

50. Equilibrium Sampler (Gellyfish) : Design Criteria - Metal binding resin held within a polyacrylamide wafer - binding sites: Iminodiacetate (IDA) - IDA sites equilibrate with free metal ions in the surrounding solution - Metals back extracted into 5% Nitric Acid - Metal analysis by ICP-MS - Knowledge of IDA affinity for metal allows calculation of free metal ion in surrounding solution