Identification of hydroxylated octa- and nona-bromodiphenyl ethers in human serum from electronic waste dismantling workers.

Previous studies have reported high serum concentrations of polybrominated diphenyl ethers, especially decabromodiphenyl ether (BDE-209), in the residents of an electronic waste (e-waste) dismantling site in Guiyu town, South China. In the present study, human serum samples in this region were collected and pooled for the identification of hydroxylated diphenyl ethers (OH-PBDEs). Three OH-PBDEs, including two hydroxylated octabromodiphenyl ethers (OH-octaBDEs, 6-OH-BDE196 and 6-OH-BDE199) and one hydroxylated nonabromodiphenyl ether (OH-nonaBDE, 6'-OH-BDE206), were first structurally identified. Identification was done by coeluting a mixture of synthetic authentic standards with the methylated OH-PBDEs from the pooled samples using two gas chromatography columns with different polarities. The results were supported by full scan mass spectrometric data in electron capture negative ionization mode. All three OH-PBDE metabolites had hydroxy groups substituted in the ortho position. These results indicate that hydroxylated higher brominated diphenyl ethers such as OH-octaBDEs and OH-nonaBDEs can accumulate in human blood. The results suggest that higher brominated diphenyl ethers could be oxidatively metabolized into OH-PBDEs in humans. Because low brominated OH-PBDEs can also be detected in abiotic media, further investigations are needed to determine the presence of higher brominated OH-PBDEs in the environment in this region.

[1]  A. Bergman,et al.  Brominated flame retardants in serum from U.S. blood donors. , 2001, Environmental science & technology.

[2]  R. Hites,et al.  Measurement of Polybrominated Diphenyl Ethers and Metabolites in Mouse Plasma after Exposure to a Commercial Pentabromodiphenyl Ether Mixture , 2007, Environmental health perspectives.

[3]  Xiaojun Luo,et al.  Polybrominated diphenyl ethers in birds of prey from Northern China. , 2007, Environmental science & technology.

[4]  R. Hites Electron impact and electron capture negative ionization mass spectra of polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers. , 2008, Environmental science & technology.

[5]  L. Burka,et al.  Metabolism and disposition of 2,2′,4,4′,5-pentabromodiphenyl ether (BDE99) following a single or repeated administration to rats or mice , 2006, Xenobiotica; the fate of foreign compounds in biological systems.

[6]  G. Marsh,et al.  Identification of hydroxylated metabolites in 2,2',4,4'-tetrabromodiphenyl ether exposed rats. , 2006, Chemosphere.

[7]  Xiong Fu,et al.  Enzyme inhibitors: new and known polybrominated phenols and diphenyl ethers from four Indo-Pacific Dysidea sponges. , 1995, Journal of natural products.

[8]  Daisuke Ueno,et al.  Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in the abiotic environment: surface water and precipitation from Ontario, Canada. , 2008, Environmental science & technology.

[9]  G. Gabrielsen,et al.  Flame retardants and methoxylated and hydroxylated polybrominated diphenyl ethers in two Norwegian Arctic top predators: glaucous gulls and polar bears. , 2005, Environmental science & technology.

[10]  R. Macdonald,et al.  Persistent organic pollutants in British Columbia grizzly bears: consequence of divergent diets. , 2005, Environmental science & technology.

[11]  Yawei Wang,et al.  Development of quantitative structure gas chromatographic relative retention time models on seven stationary phases for 209 polybrominated diphenyl ether congeners. , 2006, Journal of chromatography. A.

[12]  A. Covaci,et al.  Remarkable findings concerning PBDEs in the terrestrial top-predator red fox (Vulpes vulpes). , 2006, Environmental science & technology.

[13]  Francis L Martin,et al.  Exposure of electronics dismantling workers to polybrominated diphenyl ethers, polychlorinated biphenyls, and organochlorine pesticides in South China. , 2007, Environmental science & technology.

[14]  D. Zalko,et al.  Disposition and metabolic profiling of [14C]-decabromodiphenyl ether in pregnant Wistar rats. , 2008, Environment international.

[15]  E. Braekevelt,et al.  Bioaccumulation, biotransformation, and biochemical effects of brominated diphenyl ethers in juvenile lake trout (Salvelinus namaycush). , 2004, Environmental science & technology.

[16]  Heather M Stapleton,et al.  Debromination of the flame retardant decabromodiphenyl ether by juvenile carp (Cyprinus carpio) following dietary exposure. , 2004, Environmental science & technology.

[17]  G. Marsh,et al.  Identification of hydroxylated polybrominated diphenyl ether metabolites in blood plasma from polybrominated diphenyl ether exposed rats. , 2005, Environmental science & technology.

[18]  G. Marsh,et al.  Identification of hydroxylated and methoxylated polybrominated diphenyl ethers in Baltic Sea salmon (Salmo salar) blood. , 2004, Environmental science & technology.

[19]  L. Kautsky,et al.  Hydroxylated and methoxylated brominated diphenyl ethers in the red algae Ceramium tenuicorne and blue mussels from the Baltic Sea. , 2005, Environmental science & technology.

[20]  Kevin C Jones,et al.  Organohalogen chemicals in human blood from the United Kingdom. , 2006, Environmental pollution.

[21]  H. Hakk,et al.  Decabromodiphenyl ether in the rat: absorption, distribution, metabolism, and excretion. , 2003, Drug metabolism and disposition: the biological fate of chemicals.

[22]  R. Hites,et al.  Hydroxylated Metabolites of Polybrominated Diphenyl Ethers in Human Blood Samples from the United States , 2008, Environmental health perspectives.

[23]  G. Marsh,et al.  Synthesis of octabrominated diphenyl ethers from aminodiphenyl ethers. , 2007, Environmental science & technology.

[24]  P. Darnerud,et al.  Plasma PBDE and thyroxine levels in rats exposed to Bromkal or BDE-47. , 2007, Chemosphere.

[25]  Guoying Sheng,et al.  Exposure to polybrominated diphenyl ethers among workers at an electronic waste dismantling region in Guangdong, China. , 2007, Environment international.

[26]  G. O. Thomas,et al.  Fate of higher brominated PBDEs in lactating cows. , 2007, Environmental science & technology.

[27]  F. Gobas,et al.  Hydroxylated and methoxylated polybrominated diphenyl ethers in a Canadian Arctic marine food web. , 2008, Environmental science & technology.

[28]  G. Marsh,et al.  Gas chromatography and mass spectrometry of methoxylated polybrominated diphenyl ethers (MeO-PBDEs). , 2006, Journal of mass spectrometry : JMS.

[29]  G. Marsh,et al.  Polybrominated Diphenyl Ethers (PBDEs) and Bioaccumulative Hydroxylated PBDE Metabolites in Young Humans from Managua, Nicaragua , 2007, Environmental health perspectives.

[30]  R. Letcher,et al.  Metabolism of Polybrominated Diphenyl Ethers (PBDEs) by Human Hepatocytes in Vitro , 2008, Environmental health perspectives.

[31]  Mehran Alaee,et al.  Polybrominated diphenyl ethers and hydroxylated and methoxylated brominated and chlorinated analogues in the plasma of fish from the Detroit River. , 2005, Environmental science & technology.

[32]  H. Stapleton,et al.  In vivo and in vitro debromination of decabromodiphenyl ether (BDE 209) by juvenile rainbow trout and common carp. , 2006, Environmental science & technology.

[33]  Peter Höglund,et al.  Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as Determined in Occupationally Exposed Workers , 2005, Environmental health perspectives.

[34]  Zhiqiang Yu,et al.  Determination of Dechlorane Plus in serum from electronics dismantling workers in South China. , 2009, Environmental science & technology.

[35]  K. Thuresson Occupational exposure to brominated flame retardants : With emphasis on polybrominated diphenyl ethers , 2004 .

[36]  E. Wehler,et al.  Bioavailability and half-life of decabromodiphenyl ether (BDE-209) in rat , 2003, Xenobiotica; the fate of foreign compounds in biological systems.

[37]  J. Huwe,et al.  Accumulation, whole-body depletion, and debromination of decabromodiphenyl ether in male sprague-dawley rats following dietary exposure. , 2007, Environmental science & technology.

[38]  A. Bergman,et al.  Synthesis of Hydroxylated and Methoxylated Polybrominated Diphenyl Ethers − Natural Products and Potential Polybrominated Diphenyl Ether Metabolites , 2003 .

[39]  M. van den Berg,et al.  Inhibition of human placental aromatase activity by hydroxylated polybrominated diphenyl ethers (OH-PBDEs). , 2008, Toxicology and applied pharmacology.