The significance of brominated flame retardants in the environment:current understanding,issues and challenges
Mehran Alaeetariff
a,*
,Richard J.Wenning
b
a
National Water Rearch Institute,867Lakeshore Road,P.O.Box 5050,Burlington,Ont.,Canada L7R 4A6
b
ENVIRON International Corporation,Marketplace Tower,6001Shellmound Street,Suite 700,Emeryville,CA 94608,USA
1.BFRs –yesterday and today
Fire has been a major cau of property damage and death throughout recorded history and to the prent day.In fact,in the United States,over 3million fires are reported annually,which result in 29000injuries,4500deaths,and direct property loss estimated in excess of US$8billion (Gann,1993).During the past veral de-cades,modern technology has responded to this chal-lenge by introducing heat resistant chemicals to reduce the chances of ignition and burning of a wide range of textiles,plastics,building materials,and electronic equipment ud in commerce and in residential homes.By some estimates,the u of flame retardant chemicals has saved annually many lives and hundreds of millions of dollars in property damage (Spiegelstein,2000).By the turn of this century,flame retardant chemicals had become the cond largest additive ud by the plastics industry,resulting,in part,to a market value for flame retardant chemicals estimated at nearly US$2.2billion (Tullo,2000).
The earliest flame retardant formulations date back to about 450BC,when the ancient Egyptians ud alum to reduce the flammability of wood (Hindersinn,1990).By about 200BC,the ancient Romans included vinegar with alum to further reduce fire hazards in wooden buildings (Hindersinn,1990).
Advancements of chemistry in modern times has re-sulted in the u of more than 175different flame
re-tardant chemicals,divided into four major groups:inorganic,halogenated organic,organophosphorus and nitrogen-bad compounds and mixtures (EHC,1997).
Halogenated organic flame retardants are generally classified as either chlorinated or brominated flame re-tardants (BFRs).BFRs are further classified as either reactive or additive materials.The reactive BFRs,which include compounds such as the tetrabromobisphenol A (TBBPA)and derivatives,are chemically bonded into plastics (EHC,1995).The additive BFRs,which include the polybrominated diphenyl ethers (PBDEs)and hexa-bromocylododecane (HBDD),are ud as additives in a wide variety of polymers and resins (EHC,1997).The additive BFRs generally are believed to be more easily relead to the environment than the reactive BFRs (Hutzinger et al.,1976;Hutzinger and Thoma,1987).
PBDEs were the first group of BFRs to be detected in the environment.In 1979,the prence of BDE-209(deca-BDE)was measured in soil and sludge samples collected from areas surrounding PBDE manufacturing facilities in the US (de Carlo,1979).Two years later,Anderson and Blomkist (1981)reported the prence of PBDEs in samples collected along the Visken River in Sweden.Jansson et al.(1987)first suggested that PBDEs were global contaminants by demonstrating their pres-ence in tissue samples of fish-eating birds and marine mammals collected from the Baltic
Sea,North Sea and Arctic Ocean.Similar reports confirmed the widespread distribution of PBDE congeners in marine fish,shellfish,and diments collected in the Pacific region and el-where (Watanabe et al.,1987).PBDEs were also re-ported in cod liver and herring from the North Sea (de Boer,1989),and in fresh water eels in the Netherlands (de Boer,1990).Stafford (1983)confirmed the prence of PBDEs in North America,reporting elevated con-centrations of veral congeners in the eggs and tissues of fish-eating birds from six US states and Ontario,Canada.Watanabe et al.(1992)were among the first to suggest a global long-range transport process for
involve
PBDEs
Chemosphere 46(2002)
579–582
/locate/chemosphere
*
Corresponding author.Tel.:+1-905-336-4752;fax:+1-905-336-6430.
E-mail address:********************(M.Alaee).
0045-6535/02/$-e front matter Ó2002Elvier Science Ltd.All rights rerved.PII:S 0045-6535(01)00224-7
bad,in part,on studies of air particulate samples collected from Japan and Taiwan.
In recent years,scientists and environmental regula-tory agencies in North America and Europe have raid new concerns about the prence of PBDEs in the en-vironment.Deep diment core samples collected from the Bornholm Deep located in the southern Baltic Sea and analyzed by Nylund et al.(1992)indicate,in con-trast to other persistent organic pollutants such as PCBs, dioxins,and DDT,that PBDE levels have incread exponentially since the late1970s.And,nearly ever
y environmental monitoring program conducted during the past decade has shown sharply increasing levels of PBDEs in wildlife,particularly in Nordic countries where this trend sharply contrasts with a general de-crea in the occurrence of dioxins,PCBs and some chlorinated pesticides in marine mammals and aquatic wildlife(Bergman,2000;Hooper and McDonald,2000). The obrvations are particularly troubling since PBDEs(BDE-47,-99,-100and-153,in particular), similar to the dioxins and PCBs,are highly lipophilic compounds and readily bioaccumulate through the food web(Sellstrom et al.,1993).
A cond concern among scientists and regulatory authorities,raid most recently,is prompted by evi-dence suggesting high levels of PBDEs in humans. PBDEs have been detected in human adipo tissue, blood rum,and in human breast milk(Stanley et al., 1991;Klasson Wehler et al.,1997;Nor e n and Meir-onyt e,1998).Studies of nursing Swedish women by Meironyt e et al.(1999)suggest that the concentrations of veral PBDE congeners in breast milk have doubled every5years over the past25years.The major route of exposure appears to be through the diet,although data on this and other routes of exposure are limited at this time.A related concern is the increasing exposure of infants and young children to PBDEs and the uncer-tainties associated with the risk of adver effects during early developmental stages.
At prent,much remains uncertain regarding the toxicity of PBDEs in humans(Darnerud et al.,2001). There is limited evidence,both supporting and negating, the carcinogenicity of deca-brominated BDE(Kociba et al.,1975;NTP,1986).There is general agreement within the scientific community that data are insufficient to fully evaluate deca-and other PBDE congeners as human carcinogens(IARC,1990).The most nsitive end points of PBDE toxicity obrved in animal bioas-says appear to be effects on thyroid function,and par-ticularly induction of thyroid hyperplasia and alteration of thyroid hormone production(Fowles et al.,1994). The and relatedfindings are consistent with adver effects reported for other organohalogens such as PCBs (Brucker-Davis,1998).Recent studies by Meerts et al. (1998,2001)rai new concerns regarding the estroge-nicity of PBDEs.Several pure di-to hepta-brominated PBDEs have been shown to act via a dioxin-like Ah-receptor mediated pathway in vitro as either agonists or antagonists,prompting speculation that in vivo metab-olism of certain PBDEs may produce more potent pudoestrogens(Meerts et al.,2001).The and other effects and their significance should be the focus of ur-gently needed future toxicological studies with PBDEs.
2.Overview of this special issue
The manuscripts found in this special issue of Che-mosphere provide a state-of-the-science underst
anding of the occurrence and significance to human health and wildlife pod by PBDEs in the environment.This issue is mainly dedicated to the technical ssion on BFRs held in August2000in Monterey,CA,USA as part of the20th Annual International Symposium on Halo-genated Environmental Organic Pollutants and POPs. The work prented herein reflects the evolution of the scientific understanding of BFRs by scientists working in North America,Europe,and Japan during the past decade.The Annual International Dioxin Symposium and Periodic Technical Workshops and symposia hosted by Environment Canada and by Stockholm University have been important venues in this regard.
Manuscripts are organized intofive ctions:Intro-duction;Analytical;Environmental levels;Environ-mental fate and sources;and Toxicology and risk asssment.In the Introduction ction,de Wit provides an extensive overview of BFRs in the environment,re-flecting the considerable effort undertaken by the Swedish Environmental Protection Authority in1999–2000(de Wit,2000).
The three manuscripts included in the Analytical ction describe the challenges pod by efforts to ac-curately measure PBDEs at trace levels in different en-vironmental compartments.No longer regarded as an undesirable interference in gas chromatography analysis for other organohalogens,considerable effort is under-way to establish an analytical protocol for PBDEs.
Seven manuscripts are included in the Environmental levels ction,reflecting a broadening of our under-standing of the occurrence of PBDEs in various geo-graphical regions and environmental compartments. The studies address the occurrence of BFRs in aquatic birds,fish,marine mammals,and wildlife,as well as in human tissues(blood rum and breast milk)from Ja-pan,Europe and North America.The results,which highlight the similarities and differences in PBDE levels in biota and humans,support the hypothesis that long-range transport and inputs from local and regional sources are both important in the evaluation of PBDEs in the environment.
echoThree manuscripts are included in the Environmental fate and sources ction.On-going work in thisfield of
580M.Alaee,R.J.Wenning/Chemosphere46(2002)579–582
study is focud on resolving two important areas of uncertainty,the source(s)of releas to the environment and mechanisms for long-range global transport of PBDEs.
This special issue concludes with three manuscripts in the Toxicology and risk asssment ction.Two papers, one by Hardy and the cond by McDonald,frame the opposing viewpoints in the current debate concerning the toxicological significance to humans pod by ex-posure to PBDE学会宽容
全民情敌s.The third paper by Wenning is one of only a few risk asssment studies conducted thus far; and identifies the uncertainties and limitations in our current understanding of human exposure to the three predominant PBDE products sold commercially in North America and Europe.
3.Closing
As co-editors of this special issue of Chemosphere,we are especially grateful to the scientists and peer-review-ers located in North America,Europe,and the Asia-Pacific region who participated in the preparation and review of the manuscripts prented here.We owe a special acknowledgement to Dr.Kim Hooper at Cali-fornia EPA(Berkeley,CA)who initiated this process at the Dioxin2000meeting held in Monterey,California last August.Dr.Hooper,like many scientists involved in environmental monitoring and rearch,identified the need for a forum to communicate the complex issues and common themes associated with understanding chemical behavior in the environment and its signifi-cance to both human and ecological health.We trust this special issue of Chemosphere contributes to that goal.
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