0

100

200

300

400

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600

1981 1983 1987 1989 1991 1992 1994 1996 1998 1999

ng/g

wet

wei

ght

BDE 153

BDE 154

BDE 99

BDE 100

BDE 47

Polybrominated Diphenyl Ether Trends in the Great Lakes Ecosystem A new persistent contaminant of concern?

Frederick Luckey New York State Department of Environmental Conservation Division of Water, 625 Broadway, Albany, NY 12233-3508Fjluckey@gw.dec.state.ny.us

PBDE Trends in Lake Ontario Lake TroutDept. of Fisheries & Oceans, Canadian Centre for Inland WatersDept. of Fisheries & Oceans, Canadian Centre for Inland Waters

Alaee, M., Luross, J.M., Sergeant, D.B., Muir, D.C.G. Whittle, D.M.,and Solomon, K.R. 1999. Distribution of polybrominated diphenyl ethers in the Canadian environment. Organohalogen Compounds 40:347-350.

Bromine Science and Environmental Forum – www.bsef.com

de Boer, J., de Boer, K. and Boon J. P. Handbook Environmental Chemistry (Passivirta, J., ed.), Springer-Verlag, 2000, ch 4; 61-95.

Luckey, F.J., Fowler, B. and Litten, S. Establishing baseline levels of polybrominated diphenyl ethers in Lake Ontario surface waters. In Proc. 2nd International Workshop on Brominated Flame Retardants. pp 153-157, Stockholm University, Sweden.

Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June 2000.

Manchester-Neesvig, J.B., Valters K. and Sonzogni, W.C. 2001. Comparison of polybrominated Diophenyl Ethers (PBDEs) and Polychlorinated Biphenyls (PCBs) in Lake Michigan Salmonids. Environ. Sci. Technol., 35, pp.1072-1077.

Moisey, J., Simon, M. Wakeford, B., Weseloh, D.V. and Norstrum, R.J. 2001. Spatial and temporal trends of polybrominated diphenyl ethers in Great Lakes herring gulls, 1981 to 2000. In Proc. 2nd International Workshop on Brominated Flame Retardants. pp 153-157, Stockholm University, Sweden.

Meironyte, D., Noren, K., and Bergman Ake. 1999. Analysis of Polybrominated Diphenyl Ethers in Swedish human milk. A time trend study, 1972-1997. J. of Toxicology and Environmental Health, Part A, 58:329-341. pp. 329-341.

Noren, K. and Meironyte, D. Chemosphere, 2000, 40, 1111-1123.

Ryan, J. J. and Patry, B. Organohalogen Compounds, 2000, 47, 57-60.

Ryan, J.J. and B. Patry, Body burdens and exposure from food for polybrominated diphenyl ethers (BDEs) in Canada 3rd Annual Workshop on Brominated Flame Retardants in the Environment, 2001, Burlington, Ontario, Canada209.

Sjodin, A., Jakobsson, E., Kiergaard, A., Marsh, G. and Sellstrom, U. 1998. Gas chromatographic identification and quantification of polybrominated diphenyl ethers in a commercial product, Bromkal 70-5DE. J. of Chromatography A. 822, pp.83-89.

World Health Organization. 1994. Environmental Health Criteria 162: Brominated Diphenyl Ethers, WHO: Geneva, Switzerland.

PBDE Structure

4’

2’O3’

5’

2

4

3

66’

5

C12H10-nBrnO

Polybrominated diphenyl ethers (PBDEs) have been used for more than two decades as an effective flame retardant in a wide range of electrical applications, building materials, textiles, foams and plastics to reduce loss of life and property due to fire. Unfortunately it is now clear that PBDEs have joined the ranks of global persistent organic contaminants found in tissues of fish and wildlife even in remote corners of the earth.

The purpose of this poster paper is simply to highlight some of the initial work, completed and underway, that will help us better understand the behavior of PBDEs in the Great Lakes environment.

Introduction

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1978 1982 1986 1990 1994 1998

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Ng/g Lipid

• 209 congeners / 8 homolog groups like PCBs

• PBDE congeners identified by the same IUPAC numbering system used for PCBs (e.g., BDE-47)

• bioaccumulative (Kows 5 to 6)

• can form brominated dioxins and furans when burned

• used in manufacture of additive brominated flame retardants widely used in plastics, polymers, foams, electrical equipment, textiles, TVs, computers, furniture and building materials.

• additive flame retardants do not bond well to polymers and other materials.

• PBDE flame retardant mixtures are classified by their degree of bromination: penta bromodiphenyl ether (BDE) (five bromines); octa-BDE (eight bromines); and deca-BDE (ten bromines).

• No current US Federal environmental criteria / standards

• No EPA approved analytical methods

• Some studies indicate that PBDE levels exponentially increasing in wildlife & human tissues.

PBDE Background

  Americas Europe Asia Total

Deca-BDE 24,300 7,500 23,000 54,800

Octa-BDE 1,375 450 2,000 3,825

Penta-BDE 8,290 210 -- 8,500

1999 PBDE Global Demand Estimates (Tons) Bromine Science & Environmental ForumBromine Science & Environmental Forum

PBDE Trends in Gull Eggs from Eastern Lake Ontario

Canadian National Wildlife Research Center & Canadian Wildlife ServiceCanadian National Wildlife Research Center & Canadian Wildlife Service

• 2,2’,4,4’-tetra BDE (BDE-47) - dominant PBDE reported in:

Great Lakes Trout & Gulls Baltic Salmon

Arctic Ringed SealsFaroe Island Pilot Whales

Human Breast Milk • 2,2’,4,4’,5-penta BDE (BDE-99) - often 2nd highest

• Preliminary results indicate BDE-47 & BDE-99 are dominant In Lake Ontario surface water.

Dominant PBDE Congeners in Biota

• BDE -47 & BDE-99 together makeup ~70% of theCommercial flame retardant formulation “Bromkal 70-5DE” leading some to speculate that use of this product may be one source of these congeners.

0

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1975 1980 1985 1990 1995 2000

References

1999 PBDE Conc. in Lake Ontario Surface WatersNew York State Dept. of Environmental. ConservationNew York State Dept. of Environmental. Conservation

Ng/g Lipid

PBDE trends in North American Breast MilkData compiled by Environment CanadaData compiled by Environment CanadaPBDE Lab / Field Contamination Issues

• Considering that PBDEs are widely used in many materials and there are no controls on its use, researchers need to take extra precautions to prevent field or lab contamination of environmental samples. In one instance PBDE lab method blank levels dramatically increased following the installation of new lab air ducts. It was discovered that the ducting material contained percent levels of brominated flame retardants levels. Method blank levels decreased after the ducts were replaced with PBDE-free ducts.

Canadian Milk Bank

Samples collected in New York State

Samples collected in Austin & Denver

Data sources: Canadian Milk Bank and New York state data: Ryan & Patry, Health Canada; Denver Colo. & Austin, Tex. Data: Papke

Data complied by Mehran Alaee, Environment Canada

Figure adapted from ES&T 02/01/02 Environmental News p. 50.

Large volume sample, XAD resin. Cartridge glass fiber filter, HRGC/MS EPA Method 1668A

Six-year old lake trout , HRGC/MS

Adapted from: Luross, J.M.; Alaee, M.; Sergeant, D.; Whittle, D.M.; Solomon, K.R, 2ND Annual Workshop on Brominated Flame Retardants in the Environment, 2000, Burlington, Ontario, Canada, June 2000.

Adapted from: Moisey, J., Simon, M. Wakeford, B., Weseloh, D.V. and Norstrum, R.J. 2001. Spatial and temporal trends of polybrominated diphenyl ethers in Great Lakes herring gulls, 1981 to 2000. In Proc. 2nd International Workshop on Brominated Flame Retardants. pp 153-157, Stockholm University, Sweden.

0 1 2 3 4 5 6 7

Western Basin - B

Eastern Basin - A

pg/ L

SuspendedSolids

Dissolved