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PBDEs: Will Our Sludge Burn. Karin Didriksen North City of Palo Alto 650-494-7629 Karin.North@cityofpaloalto.org. Polybrominated Diphenyl Ethers. What are PBDEs? Why are we concerned? Palo Alto’s sampling results. Polybrominated Diphenyl Ethers. 209 congeners 1 to 10 bromines

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pbdes will our sludge burn

PBDEs: Will Our Sludge Burn

Karin Didriksen North

City of Palo Alto

650-494-7629

Karin.North@cityofpaloalto.org

polybrominated diphenyl ethers
Polybrominated Diphenyl Ethers
  • What are PBDEs?
  • Why are we concerned?
  • Palo Alto’s sampling results
polybrominated diphenyl ethers1
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
Background
  • Added to many consumer products
  • Chemical fire retardant
  • Saves lives
  • On the Regional Board’s “watch list”
commercial uses
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)
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)

Plastic materials that contain PBDEs
commercial mixtures of pbdes
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
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 Use in the Americas

†Highly bioaccumulative

BSEF, 2003

environmental concerns
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 t4 and pcbs
Structural Similarity of PBDEs, Their Metabolites and Environmental Derivatives to T4 and PCBs
pbde concentrations on the rise
PBDE concentrations on the rise…

Organohalogen Compounds in Human Milk in Sweden

(Norén and Mieronyté, 1998)

pbdes in columbia river whitefish
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 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
PBDE Life Cycle

Deca-BDE

Penta-BDE

Cross- media issue

Consumer products

Polybrominated Dioxins and Furans

(Indoor/ outdoor)

Air/ Dust

Waste

(Urban runoff; Sewage sludge;E-waste)

Biota (fish)

Food (penta)

Hydroxy-PBDEsMethoxy-PBDEs

palo alto s study
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
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
Fate of PBDEs(wastewater treatment plant)

Stack emissions (PBDF /PBDD) <6.1 x 10-7 lbs/yr

wastewater treatment

Sludge 48 lbs/yr

Influent (~ 50 lbs/year)

Incinerator

Ash(not analyzed)

Effluent 2 lbs/yr

penta formulation
Penta Formulation

Br

Br

Br

Br

Br

Br

O

O

O

Br

Br

Br

Br

Br

Br

Br

Br

2,2',4,4',6-pentaBDE

2,2',4,4'-tetraBDE

2,2',4,4',5-pentaBDE

(PBDE-100)

(PBDE-47)

(PBDE-99)

Br

Br

Br

Br

O

O

Br

Br

Br

Br

Br

Br

Br

Br

2,2',4,4',5',5-hexaBDE

2,2',4,4',5,6'-hexaBDE

(PBDE-153)

(PBDE-154)

Accounts for >90 % of the PBDEs in most humans. However, minor congeners may be important.

comparison of sludge results ug kg dry weight
Comparison of Sludge Results (ug/kg dry weight)

*sum of “penta-like” congeners

correlation of pbdf with pbde in german sewage sludge used on crops
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
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)
potential sources to potw
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
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
text of california ban ab302
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.”

summary
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
general summary
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
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.pdf
  • Brominated Flame Retardants Information Clearinghouse funded by CalEPA http://www.greenstart.org/efc9/