1. PBDEs: Will Our Sludge Burn Karin Didriksen North City of Palo Alto 650-494-7629 Karin.North@cityofpaloalto.org

2. Polybrominated Diphenyl Ethers What are PBDEs? Why are we concerned? Palo Alto’s sampling results

3. Polybrominated Diphenyl Ethers 209 congeners 1 to 10 bromines Mono smallest congener Deca largest congener Similar to PCBs and Dioxins in regards to number of congeners

4. Background Added to many consumer products Chemical fire retardant Saves lives On the Regional Board’s “watch list”

5. Commercial Uses  High-impact plastic; other plastics, rubbers and resins  1 to 10 % by weight of TV and computer casings  Polyurethane foam (30% by weight) (furniture)  Textile coatings (drapes, carpet backings)

6. P lastic materials that contain PBDEs –ABS –polyacrylonitrile (PAN) –polyamide (PA) –polybutylene terephthalate (PBT) –polyethylene (PE) –polyvinyl chloride (PVC) –polyurethane (PUR) (foam) –unsaturated polyester (UPE). –cross-linked polyethylene (XPE) –polyethylene terephthalate (PET) –polypropylene (PP) –polystyrene (PS) –high-impact polystyrene (HIPS)

7. Commercial Mixtures of PBDEs Penta-BDE (used in foam) –Polyurethane foam in seat cushions and carpet padding –Printed circuit boards –All congeners highly bioaccumulative –86 to 99% of congeners found in human tissues

8. Commercial Mixtures of PBDEs (cont) Octa-BDE (used in plastics, textiles) –Electrical connectors –Automotive interior parts Deca-BDE (plastics, textiles) –Computer cases –Carpet backing and textiles

9. PBDE Use in the Americas PBDE Technical Mixture Million lbs/yr (2001) % of World’s Use Product Uses Penta- BDE † 15.7 95 Furniture (foam cushions) Octa-BDE3.340Electronics (ABS plastic, cable) Deca-BDE54.044Electronics (HIPS plastic) and textiles † Highly bioaccumulative BSEF, 2003

10. Environmental Concerns Endocrine Disruption Persistent Organic Pollutants (POP)/ Persistent Bioaccumulative Toxicants (PBT) –Structurally similar to PCBs and DDT –Lower brominated congeners bioaccumulate Emerging Environmental Challenge High Production Volume (HPV) Chemical

11. Structural Similarity of PBDEs, Their Metabolites and Environmental Derivatives to T4 and PCBs

12. PBDE concentrations on the rise… Organohalogen Compounds in Human Milk in Sweden (Norén and Mieronyté, 1998)

13. Figure courtesy of Dr. John Ryan of Health Canada and Dr. Mehran Alaee of Environment Canada:

14. Time-trend: PBDEs in Blubber of California Seals N=11 (She et al., 2002)

15. PBDEs in Columbia River Whitefish From Genelle, British Columbia Rayne et al. (2003) Environ Sci Technol 37(13):2847-54.

16. PBDEs Have Become Ubiquitous Environment Contaminants PBDEs are measured in –Indoor and outdoor air –Remote Arctic regions (i.e., long-range transport) –House and office dust –Rivers and lakes and sediments –Sewage sludge –Foods –Biota (terrestrial and marine mammals, fish, humans)

17. PBDE Life Cycle Penta-BDE Deca-BDE Consumer products Polybrominated Dioxins and Furans Air/ DustWaste Food (penta) (Urban runoff; Sewage sludge; E-waste) Biota (fish) Hydroxy-PBDEs Methoxy-PBDEs Cross- media issue (Indoor/ outdoor)

18. Palo Alto’s Study August 2002 3 days of sampling, composite samples Effluent and biosolids tested for 41 PBDE congeners Incinerator emissions tested for brominated furans and brominated dioxins Concentration levels at ppt (ng/L or ng/kg)

19. Palo Alto’s Loading Data 96% of PBDEs sorb onto biosolids 4% of PBDEs are discharged to Bay Incinerator transforms PBDEs to brominated furans and brominated dioxins Air pollution control device destroys 99.9% of dioxins and furans

20. Fate of PBDEs ( wastewater treatment plant) Influent (~ 50 lbs/year) Stack emissions (PBDF /PBDD) <6.1 x 10 -7 lbs/yr Effluent 2 lbs/yr Sludge 48 lbs/yr Incinerator Ash (not analyzed)

21. Penta Formulation Accounts for >90 % of the PBDEs in most humans. However, minor congeners may be important. Br O 2,2',4,4',6-pentaBDE (PBDE-100) 2,2',4,4'-tetraBDE (PBDE-47) 2,2',4,4',5-pentaBDE (PBDE-99) 2,2',4,4',5',5-hexaBDE (PBDE-153) 2,2',4,4',5,6'-hexaBDE (PBDE-154) Br O O O O

22. Mass of PBDEs in Effluent and Biosolids Penta-FormulationDeca-BDE

23. Comparison of Sludge Results (ug/kg dry weight) Source Penta Formulation* Deca- BDE City of Palo Alto1,918-2,0861,010-1,440 Hale’s study (Throughout U.S.) 1,100-2,29085-4,890 European Studies0.4-239140-350 *sum of “penta-like” congeners

24. Correlation of PBDF with PBDE in German Sewage Sludge Used on Crops. Hagenmaier et al. (1992) Chemosphere 25:1457-62 PBDE levels in U.S. sludge are 10- to 100-fold higher than European samples (Hale et al., 2001 Nature 412:140-1).

25. Overview of Results PBDE concentration in US Sludge is 10 to 100x greater than Europe Deca-BDE largest concentration in biosolids (~1,183 ppb) –Renewed concern over Deca (new data on debromination by UV and biota) BDE-99 (part of penta-formulation) largest concentration in effluent (~0.01 ppb)

26. Potential Sources to POTW Unclear direct source since it is found everywhere in the environment Some possible sources include: –Rinsing of cleaning rags –Carpet cleaning –Laundry and shower gray water –Human waste

27. Penta and Octa-BDE are now Banned Banned in California starting 2008 –AB302 (Chan et al.) signed into law August, 2002 US manufacturer announced it will voluntarily cease production by end of 2004 Banned in European Union starting 2005 Already voluntarily phased out in Japan

28. Text of California Ban (AB302) “ On and after January 1, 2008, a person may not manufacture, process, or distribute in commerce a product, or a flame-retarded part of a product, containing more than one-tenth of 1 percent of pentaBDE or octaBDE, by mass.”

29. Summary 96% of PBDEs that enter the plant end up in the sludge High concentration of PBDEs in sewage sludge US PBDE sludge concentrations 10 to 100x greater than Europe Unclear if 2 lbs/year is a significant contribution to the Bay

30. General Summary PBDEs in consumer products are escaping into the environment – now everywhere PBDE levels rising rapidly in fish, other wildlife and people in North America Penta- and Octa-PBDE banned in CA and the EU; not used in Japan.

31. Key Sources for PBDEs “Tracking the Fate of Polybrominated Diphenyl Ethers (PBDEs) at the Regional Water Quality Control Plant, Palo Alto, Ca http://www.city.palo- alto.ca.us/cleanbay/pdf/PBDE04.pdfhttp://www.city.palo- alto.ca.us/cleanbay/pdf/PBDE04.pdf Brominated Flame Retardants Information Clearinghouse funded by CalEPA http://www.greenstart.org/efc9/ http://www.greenstart.org/efc9/