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PBDEs: Will Our Sludge Burn Karin Didriksen North City of Palo Alto 650 -494 PBDEs: Will Our Sludge Burn Karin Didriksen North City of Palo Alto 650 -494 -7629 Karin. [email protected] org

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

Polybrominated Diphenyl Ethers • • • 209 congeners 1 to 10 bromines Mono smallest 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

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

Commercial Uses · High-impact plastic; other plastics, rubbers and resins · 1 to 10 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)

Plastic materials that contain PBDEs – – – – ABS polyacrylonitrile (PAN) polyamide (PA) Plastic 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)

Commercial Mixtures of PBDEs • Penta-BDE (used in foam) – Polyurethane foam in seat 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

Commercial Mixtures of PBDEs (cont) • Octa-BDE (used in plastics, textiles) – Electrical connectors 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

PBDE Use in the Americas PBDE Technical Mixture Penta. BDE† Octa-BDE Deca-BDE † Million PBDE Use in the Americas PBDE Technical Mixture Penta. BDE† Octa-BDE Deca-BDE † Million % of lbs/yr World’s Use (2001) 15. 7 95 3. 3 40 54. 0 44 Highly bioaccumulative Product Uses Furniture (foam cushions) Electronics (ABS plastic, cable) Electronics (HIPS plastic) and textiles BSEF, 2003

Environmental Concerns • Endocrine Disruption • Persistent Organic Pollutants (POP)/ Persistent Bioaccumulative Toxicants (PBT) 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

Structural Similarity of PBDEs, Their Metabolites and Environmental Derivatives to T 4 and PCBs Structural Similarity of PBDEs, Their Metabolites and Environmental Derivatives to T 4 and PCBs

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

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

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

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

PBDEs Have Become Ubiquitous Environment Contaminants PBDEs are measured in – Indoor and outdoor 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)

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

Palo Alto’s Study • August 2002 • 3 days of sampling, composite samples • 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)

Palo Alto’s Loading Data • 96% of PBDEs sorb onto biosolids • 4% of 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

Fate of PBDEs (wastewater treatment plant) Influent (~ 50 lbs/year) Sludge 48 lbs/yr Effluent Fate of PBDEs (wastewater treatment plant) Influent (~ 50 lbs/year) Sludge 48 lbs/yr Effluent 2 lbs/yr Stack emissions (PBDF /PBDD) <6. 1 x 10 -7 lbs/yr Incinerator Ash (not analyzed)

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

Mass of PBDEs in Effluent and Biosolids Penta-Formulation Deca-BDE Mass of PBDEs in Effluent and Biosolids Penta-Formulation Deca-BDE

Comparison of Sludge Results (ug/kg dry weight) Source Penta Formulation* Deca- BDE City of Comparison of Sludge Results (ug/kg dry weight) Source Penta Formulation* Deca- BDE City of Palo Alto 1, 918 -2, 086 1, 010 -1, 440 Hale’s study (Throughout U. S. ) 1, 100 -2, 290 85 -4, 890 European Studies 0. 4 -239 140 -350 *sum of “penta-like” congeners

Correlation of PBDF with PBDE in German Sewage Sludge Used on Crops Hagenmaier et 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).

Overview of Results • PBDE concentration in US Sludge is 10 to 100 x Overview of Results • PBDE concentration in US Sludge is 10 to 100 x 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)

Potential Sources to POTW • Unclear direct source since it is found everywhere in 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

Penta and Octa-BDE are now Banned • Banned in California starting 2008 – AB Penta and Octa-BDE are now Banned • Banned in California starting 2008 – AB 302 (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

Text of California Ban (AB 302) “ On and after January 1, 2008, a Text of California Ban (AB 302) “ 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 penta. BDE or octa. BDE, by mass. ”

Summary • 96% of PBDEs that enter the plant end up in the sludge 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 100 x greater than Europe • Unclear if 2 lbs/year is a significant contribution to the Bay

General Summary • PBDEs in consumer products are escaping into the environment – now 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.

Key Sources for PBDEs • “Tracking the Fate of Polybrominated Diphenyl Ethers (PBDEs) at 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. paloalto. ca. us/cleanbay/pdf/PBDE 04. pdf • Brominated Flame Retardants Information Clearinghouse funded by Cal. EPA http: //www. greenstart. org/efc 9/