卤代阻燃剂不同含量水平及所致健 康效应的比较 -- 人和野生动植物 Susan D. Shaw, DrPH Director Marine Environmental Research Institute Center for Marine Studies USA The Fire Retardant Dilemna in China: Exposure and Epidemiology Issues Green Science Policy Symposium, Western Academy of Beijing, China August 22, 2009
溴化阻燃剂 持久性, 生物蓄积性, 毒性 O 209 congeners Br 4-10 多溴联苯醚 (PBDEs) Br Br Br 3 isomers Br Br Br 六溴环十二烷 (HBCD) Br HO H 3 C CH 3 Br Br Br OH 四溴双酚 A (TBBPA)
2001 年溴化阻燃剂全球消耗量 Deca-BDE Octa-BDE Asia Other World (mt) 56,150 3,790 Penta-BDE HBCD TBBPA Americas Europe 0% 50% 100% 7,500 16,700 119,600 Data: BSEF 2003, Watanabe & Sakai, 2003
美国人体内 PBDEs 含量 71 ng/g lipid 400 64 62 440 20 ng/g lw blood/serum milk cord serum adipose
不同国家地区间妇女母乳中 PBDE 含量的比较 Asia ng/g lipid Payatas, Philippines Australia Europe North America Mexico Massachusetts, US Massachusetts, US Texas, US 0 10 20 30 40 ng/g lw Pacific NW (50 ng/g)
亚洲地区妇女母乳中 PBDEs 含量的比较 <10 ng/g lipid Korea Japan China India Vietnam Cambodia Philippines Malaysia 2 ng/g lipid wt Indonesia Fig. 2. Geographical distribution of PBDEs in milk from Asia. Slide: S. Tanabe
不同国家地区间人群血液中 PBDE 含量的比较 Asia Europe ng/g lipid Haojiang, South China (190 ng/g) North America Quebec, Canada California, US Tenn/Washington, US Central America Urban site, Nicaragua Rural site, Nicaragua 0 20 40 60 80 100
美国加州家庭各成员血清中 PBDE 含量比较 ng/g lipid wt 500 450 400 350 300 250 200 150 100 50 0 ng/g lipid Father Mother Child Toddler Fisher et al. EHP 2006
广东省环境废弃物回收利用 高暴露人群
环境废弃物处置场所相关暴露人员血中 PBDE 水平比较 600 500 400 Children living & working onsite Sum PBDE BDE-209 ng/g lw 300 200 100 0 Children working onsite e-waste reference WDS WDS reference Guiyu, China Haojiang, China Managua, Nicaragua (non e-waste site) Data: Bi et al. ES&T 2007, Athanasiadou et al. EHP 2007
中国南方城市 Guiyu and Haojiang 人群血液 中 PBDE 同系物含量比较 Deca-BDE 59% 68% 30 25 Guiyu Haojiang % of total PBDE. 20 15 10 5 0 28 47 85 99 100 153 154 183 196 197 203 206 207 208 209 BDE Congener Data: Bi et al 2007
各类猛禽 ( 肉食鸟 ) 体内溴化阻燃剂含量研究 Peregrine Falcon (Falco peregrinus) Potter et al. ET&C 2009, Johansson et al. ET&C 2009 Bald Eagle (H. leucocephalus) McKinney et al. 2006, ES&T, Gooddale 2008, BRDI Osprey (Pandion haliaetus) Goodale BDRI 2008, Rattner et al. Arch Env Cont Tox 2004, Toschik et al. ET&C 2005 Sparrow Hawk (Accipiter nisus) Chen et al. ES&T 2007, Voorspoels et al. ES&T 2007 Buzzard (Buteo buteo) Chen et al. ES&T 2007, Voorspoels et al. ES&T 2007 Common Kestrel (Falco tinnunculus) Chen et al. ES&T 2007
溴化阻燃剂在各国猛禽 ( 肉食鸟 ) 体内含量比较 China Sparrowhawk, Beijing Japanese Sparrowhawk, Beijing Little Owl, Beijing Kestrel, Beijing (12300) ng/g lipid muscle Europe Greenland US Peregrine falcon, Sweden Peregrine falcon, Sweden Peregrine falcon Osprey, Maine eggs Bald eagle, Maine (8600) Peregrine falcon, CA (7850) 0 1000 2000 3000 4000 5000 6000 7000 8000
各类海鸟体内溴化阻燃剂含量研究 Caspian Tern (Sterna caspia) She et al. Chemosphere 2008 Least Tern (Sterna antillarum) She et al. Chemosphere 2008, Gooddale BRDI 2008 Forster s Tern (Sterna forsteri) She et al. Chemosphere 2008 Herring Gull (Larus argentatus) Gooddale BRDI 2008, Helgason et al. ET&C 2009 Chinese Pond Heron (Ardeola bacchus) Luo et al. ES&T 2008 Glaucous Gull (Larus hyberboreus) Vander Pol et al. Env Poll 2009, Verreault et al. ES&T 2005
溴化阻燃剂在各国海鸟体内含量比较 China Europe Pond heron, Pearl River delta (e waste region) ng/g lipid muscle eggs Greenland Canada US Herring gull, Maine coast South Africa Caspian tern, WA Caspian tern, CA Forster s tern, CA Least tern, CA 0 1000 2000 3000 4000 5000 6000
各类鳍足类动物体内溴化阻燃剂含量研究 Harbor seal (Phoca vitulina ) Shaw et al. 2008, Meng et al. 2009, Law et al. 2003 Sea lion (Zalophus californianus) Meng et al. 2009, Stapleton et al. 2006 Gray seal (Halichoerus grypus) Ikonomou & Addison 2008 Ringed seal (Pusa hispida ) Riget et al. 2006, Johansen et al. 2004 No. elephant seal (M. angustirostris) Meng et al. 2009 Harp seal (P. groenlandica) Johansen et al. 2004
溴化阻燃剂在各国鳍足类动物体内含量比较 Asia Europe No. Fur Seal, Japan coast Harbor Seal, Wadden Sea ng/g lipid Blubber Canada Harbor Seal, St Lawrence Estuary Canada US Greenland Ringed Seal Harbor Seal, SF Bay, CA Harbor Seal (3700 ng/g) NW Atlantic CA Sea Lion (55000 ng/g) CA Sea Lion (5800 ng/g) 0 500 1000 1500 2000 2500 Sum PBDE (ng/g lw)
PBDEs 在北美鳍足类动物体内含量 55000 California sea lion (range 3430-194000) Ringed seal Greenland 5800 California sea lion 3700 NW Atlantic harbor seal Pacific harbor seal Hooded seal Gray seal So. California sea lion Pacific harbor seal No. elephant seal 2000 ng/g lipid wt
各类鲸类动物体内溴化阻燃剂含量研究 Beluga whale (Delphinapterus leucas) Law et al. 2003, Lebeuf et al. 2004 Harbor porpoise (Phocoena phocoena) Law et al. 2002, Beineke et al. 2005 Killer whale (Orinicus orca) Rayne et al. 2002, Krahn et al. 2007 Bottlenose dolphin (T. truncatus) Fair et al. 2007, Johnson-Restrepo et al. 2005 White-sided dolphin (L. obliquidens) Tuerk et al. 2005 Striped dolphin (S. coeruleoalba) Isobe et al. 2009
溴化阻燃剂在各国鳍足类动物体内含量比较 Asia Humpback Dolphin, Hong Kong ng/g lipid Blubber Europe Australia Canada Harbor porpoise, UK Beluga Whale, St. Lawrence Estuary Bottlenose Dolphin UK (7700 ng/g) US Brazil (liver) Killer Whale, Alaska Bottlenose dolphin, Florida Bottlenose dolphin, Texas Gulf of Mexico Killer Whale, CA coast (13000 ng/g) Killer Whale, Puget Sd (6800 ng/g) Bottlenose Dolphin SC (6800 ng/g) 0 1000 2000 3000 4000 5000 Sum PBDE (ng/g lw)
PBDEs 在北美各类鲸类动物体内含量 Residents Killer whales 13000 6800 Offshore Killer whale Harbor porpoise Transients Residents 6800 Beluga whale 2000 ng/g lipid wt 3100 Bottlenose dolphin White-sided dolphin
PBDE 在亚洲各类鲸类动物体内含量 Finless porpoise Porpoise Kajiwara et al. (2006) 6000 2600 Striped dolphin Coastal species Offshore species 200 ng/g lipid weight Melon-headed Whale JAPAN Dall s porpoise HONG KONG INDIA PHILIPPINES
溴化阻燃剂含量时间变化趋势 北方海豹
1970-2005 年北美 PBDEs 含量变化线图 10000 1000 Sum PBDE (ng/g lw).. 100 10 1 0 Doubling time~2-5 years US Human Blood Figure: Shaw and Kannan Rev Env Health 2009 dungeness crab whitefish bull shark cormorant great blue heron beluga whale bottlenose dolphin harbor seal-ca harbor seal-canada harbor seal-ne US human-us 1970 1975 1980 1985 1990 1995 2000 2005 Data: Schecter et al. 2005, Ikonomou et al 2002, 2006, Rayne et al 2003, Johnson-Restrepo et al 2005, Elliott et al 2005, Lebeuf et al 2004, She et al 2002, Shaw et al 2008
1970 2000 年日本海豹体内 PBDEs, HBCDs 含量变化趋势 120 PBDEs 80 HBCD (ng/g lipid weight) 80 40 60 40 20 0 1970 1975 1980 1985 1990 1995 2000 0 nd 1970 1975 1980 1985 1990 1995 2000 Data: Kajiwara et al. 2004, 2006
中国南海海豚体内溴化阻燃剂含量变化趋势 10000000 HBCDs PBDEs PCBs DDTs CHLs HCHs HCB 1000000 :1990 :2000/01 100000 *** (ng/g lipid wt) 10000 1000 100 10 *** 1 0.1 ***: p < 0.001 Data: Kajiwara et al. 2006
Penta-BDE 所致野生动植物毒理学效应 貂类动物完全的生殖失败 (Complete reproductive failure in mink) 鹰 隼 游隼, 鱼鹰蛋壳变薄, 不易孵化 海豹体内甲状腺激素含量发生变化, 生存率降低 Data: Zhang et al. Env Tox Chem 2008, Martin et al. Env Tox Chem 2007, Fernie et al. ES&T 2009, McKernan et al. Env Toxicol Chem 2009, Johnansson et al. Environ Toxicol Chem 2009, Hall et al. Env Poll 2003, Hall and Thomas Env Tox Chem 2007, Hall et al. Env Sci Technol 2009
Summary BFRs are ubiquitous global contaminants; levels increasing in humans and wildlife Large reservoirs of penta-bde (foam products); deca- BDE still in use E-waste recycling sites = highest human exposure Highly exposed children at risk for neurotoxicity, immune and thyroid effects Need for safe alternatives for the environment and human health
总结 溴化阻燃剂是独特的全球污染物 ; 人和野生动植物体内含量呈增高趋势 大量的溴化阻燃剂如 penta-bde( 泡沫产物 ),deca- BDE 仍在使用中 废品回收场所 = 人类最大剂量暴露地方 高暴露儿童神经 免疫毒性及甲状腺异常等不良健康效应的风险明显增加 基于人类和环境保护的迫切需要, 必须寻找安全的替代物
致谢 Arlene Blum, Green Science Policy Institute, U. of California, Berkeley, CA Linda Birnbaum, National Institute of Environmental Health Sciences, USA Olaf Paepke, Eurofins-ERGO, Hamburg, Germany Kurunthachalam Kannan, State U. of New York, Albany NY Shinsuke Tanabe, Tomohiko Isobe, Karri Ramu, Ehime University, Japan Susan Klosterhaus, San Francisco Estuary Institute, CA Michelle Berger, Isabelle Richardson, Marine Environmental Research Institute, Maine ---and my colleagues worldwide