1. Developing Baseline Information on PBDEs in Lake Ontario Surface Water Frederick Luckey, New York State DEC Simon Litten, New York State DEC Brian Fowler, AXYS Analytical Services

2. Problem Statement Levels of PBDE, a widely used flame retardant are increasing in wildlife and human tissue around the world. In the Great Lakes, Lake Ontario lake trout appear to have some of the highest PBDE levels. Although a considerable amount of data is now available on PBDE levels in biota, there were no measurements of PBDE in surface waters in North America. Objective Develop baseline measurements of PBDE in Lake Ontario surface water. Identify dominant PBDE congeners.

3. PolybrominatedDiphenyl Ethers (PBDEs) (PBDEs) Flame retardant widely used in plastics, polymers, foams, electrical equipment, and building materials Global production > 150,000 tons /year 209 congeners / 8 homolog groups like PCBs Highly bioaccumulative (K ows 5 to 6); No US Federal environmental criteria /standards No EPA approved analytical methods Levels increasing in wildlife and human tissue.

4. C 12 H 10-n Br n O 2,2’,4,4’- tetrabromodiphenyl ether IUPAC BDE- 47 2’3’ 5’ 2 4 3 66’ 4’ 5 Polybrominated Diphenyl Ethers (PBDEs)

5. Polybrominated Diphenyl Ethers (PBDEs) Congener – One of 209 possible configurations of the number and position of bromines on the two phenyl rings. Homolog – Set of congeners having the same number of bromines. bromodiphenyl ether Mono- bromodiphenyl ether 1 Bromine bromodiphenyl ether Di - bromodiphenyl ether 2 Bromines bromodiphenyl ether Tri- bromodiphenyl ether 3 Bromines bromodiphenyl ether Tetra - bromodiphenyl ether 4 Bromines bromodiphenyl ether Penta - bromodiphenyl ether 5 Bromines bromodiphenyl ether 6 Bromines Hexa- bromodiphenyl ether 6 Bromines bromodiphenyl ether 7 Bromines Hepta- bromodiphenyl ether 7 Bromines bromodiphenyl ether 8 Bromines Octa- bromodiphenyl ether 8 Bromines Nona- bromodiphenyl ether Nona- bromodiphenyl ether 9 Bromines bromodiphenyl ether Deca - bromodiphenyl ether 10 Bromines

6. Adapted from: Luross et al. 1999. Determining a spatial distribution of BDPE in Lake Trout from the Great Lakes. Poster Session, SETAC 20th Annual Meeting. Nov. 1999 Philadelphia. 20th Annual Meeting. Nov. 1999 Philadelphia. PBDE in Great Lakes Lake Trout Dept. of Fisheries & Oceans, Canadian Centre for Inland Waters Ng/g Wet Weight

7. PBDE trends in Human Breast Milk (Sweden) Adapted from D. Meironyte Guvenius and K.Noren. 2001. Proceedings of The 2 nd Intl Workshop on BFRs, pp 303-5. Ng/gLipids Sweden Bans PBDE

8. 2,2’,4,4’-tetra BDE (BDE-47) - dominant PBDE reported in: 2,2’,4,4’-tetra BDE (BDE-47) - dominant PBDE reported in: Great Lakes Trout Baltic Salmon Baltic Salmon Arctic Ringed Seals Faroe Island Pilot Whales Human Breast Milk Human Breast Milk 2,2’,4,4’,5-penta BDE (BDE-99) - often 2nd highest 2,2’,4,4’,5-penta BDE (BDE-99) - often 2nd highest Dominant PBDE Congeners Reported in Biota BDE -47 & BDE-99 together makeup ~70% of the flame retardant formulation - Bromkal 70-5DE. BDE -47 & BDE-99 together makeup ~70% of the flame retardant formulation - Bromkal 70-5DE.

9. Great Lakes Basin

10. Research Vessel Lake Guardian EPA Great Lakes National Program Office Lake Ontario Surface Water Large Volume Sampling Western sampling area Eastern Central Lake Ontario Province of Ontario Fall 1999

11. spatially, temporally integrated spatially, temporally integrated large volume water samples large volume water samples 24 hour continuous sampling 24 hour continuous sampling 1 m depth, isothermal 1 m depth, isothermal Lake Ontario Open Water Sampling duplicate samples duplicate samples water depths >75 m water depths >75 m Fall 1999

12. Nytex Netting XAD Resin #1 Glass Fiber Filter Surface Water Intake 1 um Total Organics Platform Sampler (TOPS) XAD Resin #2 ~I m deep filter out large zooplankton & debris capture solids capture dissolved Lake Large Volume Sampler capture break thru

13. Glass Fiber Filter Second XAD Column First XAD Column Large Volume Sampler Total Organics Platform Sampler (TOPS)

14. Calculating PBDE Water Concentrations PBDE mass per sample (picograms) TOPS Sample Volume (L) = Water Conc. (pg/L) is inversely proportional to Sample Specific Detection Limit Sample Volume

15. Lake Ontario Surface Water Sample Volumes (Liters) Fall 1999

16. PBDE Analytical Methods Extraction & clean-up for Filters and XAD resin same as EPA Method 1668A for PCB congeners; Extraction & clean-up for Filters and XAD resin same as EPA Method 1668A for PCB congeners; Samples spiked with 13 C 12 -labelled BDE-77 & 126; Samples spiked with 13 C 12 -labelled BDE-77 & 126; Solvent extracted & cleaned with liquid chromatography; Solvent extracted & cleaned with liquid chromatography; High resolution GC/HRMS (Micromass Ultima); High resolution GC/HRMS (Micromass Ultima); Selected ion method similar to EPA 1668A; Selected ion method similar to EPA 1668A; EI mode at 10000 resolution. EI mode at 10000 resolution.

17. Standards prepared by Cambridge Isotope Labs (CIL) Standards prepared by Cambridge Isotope Labs (CIL) PBDE Analytical Standards Calibration standard of 17 PBDE congeners (mono to hepta); Allows for identification & quantification of 41 congeners. Calibration standard of 17 PBDE congeners (mono to hepta); Allows for identification & quantification of 41 congeners. Same standards used by researchers in Canada & Europe. Same standards used by researchers in Canada & Europe. Method would recognize presence of non-target congeners. None were seen. Method would recognize presence of non-target congeners. None were seen.

18. Data Handling Levels of PBDE congeners seen in method blanks subtracted from field sample results Levels of PBDE congeners seen in method blanks subtracted from field sample results Non-detects treated as zero Non-detects treated as zero

19. Older Lab Newly Refurbished Lab Percent levels PBDE found in new ventilation system ducts! Lab to Lab Differences in Levels of PBDE Method Blank Contamination

20. Lab to Lab Differences in Levels of Major PBDE Congeners in Method Blanks PBDE Congener ID# “New” “Old”

21. BDE-47BDE-99 Comparison of Batch Specific Method Blanks with Field Sample Results for BDE-47 & BDE-99. Field Sample Results for BDE-47 & BDE-99. BDE-99BDE-47 “Old Lab” “New Lab” Picograms/sample

22. Calculated Water Concentrations for BDE-47 & BDE-99 Before & After Correcting for Method Blanks Before After pg/L Dissolved Phase

23. Lake Ontario Western Basin Comparison of PBDE Captured on 1 st & 2 nd XAD Columns PBDE Congener ID# Fall 1999 XAD #1XAD #2 pg/L

24. PBDE in Method Blanks in Old lab, Newly Built Lab and After Removal of BFR Treated Materials After removal of BFR insulation

25. R/V Lake Guardian Cruise Lake Ontario 1999

26. Lake Ontario Surface Water Total PBDE Concentrations Fall 1999 Picograms / Liter

27. Lake Ontario Surface Water Average Total PCB & PBDE Concentrations (pg/L) pg/L (1997) (1999)

28. Lake Ontario Surface Water PBDE Homolog Patterns Total (Dissolved + Suspended Solids) Total (Dissolved + Suspended Solids) Fall 1999 PBDE Homolog Group Central West East %

29. Lake Ontario Surface Water PBDE Homolog Patterns Dissolved Phase - Percent Abundance Dissolved Phase - Percent Abundance Fall 1999 PBDE Homolog Group % Central West East

30. Lake Ontario Surface Water PBDE Homolog Patterns Suspended Solids - Percent Abundance Suspended Solids - Percent Abundance Fall 1999 PBDE Homolog Group Central West East %

31. Lake Ontario Surface Water PBDE Congener Conc. Eastern Basin - A Comparison of Dissolved & Solids Conc. Fall 1999 PBDE Congener ID# pg/L

32. Lake Ontario Surface Water Major PBDE Congeners Total (Dissolved + Solids) – Relative Percent PBDE Congener ID# Fall 1999 Central West East %

33. Lake Ontario Surface Water Concentration of Major PBDE Congeners (pg/L) Total (Dissolved + Solids) PBDE Congener ID# pg/L Fall 1999 Central West East

34. PBDE’s in Lake Ontario Surface Water Preliminary Conclusions Total PBDEs are ~ 4 to 6 pg/L in open waters; Total PBDEs are ~ 4 to 6 pg/L in open waters; BDE-47 (tetra) & BDE-99 (penta) are the dominant BDE-47 (tetra) & BDE-99 (penta) are the dominant PBDE congeners, making up >70% total PBDEs; ~80% of PBDEs are dissolved; ~80% of PBDEs are dissolved; Little difference between Eastern, Central and Western Basin PBDE concentrations or congener patterns. Little difference between Eastern, Central and Western Basin PBDE concentrations or congener patterns.

35. Suggestions for PBDE Surface Water Researchers Carefully check labs for potential sources of PBDEs. New construction should be given special attention. Carefully check labs for potential sources of PBDEs. New construction should be given special attention. Collect XAD resin samples in series and analyze separately as a check on significance of lab contamination. Collect XAD resin samples in series and analyze separately as a check on significance of lab contamination. Two or three lab method blanks per sample batch should allow better characterization of lab background PBDE conc. Correct field sample results by subtracting levels of congeners measured in batch-specific method blanks. Consider slow injection of isotopically labelled PBDE surrogates into sample intake line in order to quantify how well XAD captures PBDE. Consider slow injection of isotopically labelled PBDE surrogates into sample intake line in order to quantify how well XAD captures PBDE.

36. Acknowledgements Thanks for the support provided by: USEPA Region 2 USEPA Great Lakes National Program Office Captain & Crew of the R/V Lake Guardian The Staff at AXYS Analytical Services

39. C 12 H 10-n Cl n 2,2’,4,4’- tetrachlorobiphenyl IUPAC # PCB- 47 2’3’5’24366’ 4’ 5 Polychlorinated Biphenyls (PCBs)

40. Glass Fiber Filter Surface Water Intake Flow Meter #1 Dissolved Phase Sample Volume = Meter #2 Flow Solids Phase Sample Volume = Meter #1 + #2 Flow Lake Lake Lake Ontario TOPS Sample Volumes Fall 1999 Flow Meter #2 XAD Resin #2 XAD Resin #1

41. Calculated Surface Water Concentrations for Congeners BDE-47 & BDE-99 After Correcting for Method Blanks pg/L

42. Adapted From: 2 Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2 ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June 2000. PBDE in Trends in Lake Ontario Lake Trout Dept. of Fisheries & Oceans, Canadian Centre for Inland Waters Ng/g Lipid