得克隆的源、排放以及人体暴露评价研究
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摘要
我们调查了中国得克隆(Dechlorane Plus,简称为DP)制造工厂地区大气、土壤和底泥中的新型氯系阻燃剂得克隆的含量和分布。我们在大气、底泥和土壤样品中都检测到了DP,大气中总DP浓度范围是7738-2,6757 pg/m3,DP浓度的平均值是12,245 pg/m3,土壤中DP的浓度是1489±3583 ng/g。与工厂附近土壤中的DP浓度比较可以发现工厂附近运河底泥中的DP(4.9±4.3 ng／g)浓度较低。大部分大气样品的反式DP(anti-DP)异构体比例(fanti)值在已公布的商用DP的fanti值范围里面,而大部分土壤和底泥样品是大于商用DP的平均fanti值的,这表明土壤和底泥中的anti-DP发生了立体选择性富集。经评价,DP生产过程中的人体暴露的健康风险是比较高的。
2008年我们在中国东北的大连沿海地区采集了表层底泥样品并对DP进行了分析。底泥样品中DP的浓度分布在0.69 ng/g-7.00 ng/g之间,平均值为2.46 ng/g。大连沿海底泥中相对高的DP浓度表明我们可将大连作为一个DP源。大连湾工业区附近采样点的DP浓度近似两倍高于居民区和公园周围的采样点,这表明城市污水排放和工业源可能是大连市DP的重要来源。大连底泥的平均fanti值为0.78,略高于商用DP合成物的平均fanti值0.68,这表明底泥中的anti-DP发生了立体选择性富集。
Levels and distribution of new chlorinated flame retardant of Dechlorane Plus (DP) in air, soil, and sediment in the area of a DP production facility in China were investigated. DP was detected in air, soil, and sediment samples, total DP concentration in air was the range 7738-2,6757 pg/m3 with a median value of 12,245 pg/m3, DP concentrations in soil was 1489±3583 ng/g.Compared with the concentrations of DP in soil surrounding the facility, low concentrations of DP (4.9±4.3 ng/g) was found in sediment from the canal near the facility. The anti-DP fractional abundance (fanti) of most air samples were in the range of reported commercial DP, and most soil and sediment samples were above the mean of commercial DP, indicating a stereoselective enrichment of anti-DP in sediment and soil. Human exposures to DP in the manufacturing process are expected to be high.
Surficial sediment samples were collected in Dalian costal area, northeast China, in 2008 and analyzed for Dechlorane Plus (DP). The DP concentrations are ranging from 0.69 ng/g to 7.00 ng/g with a mean value of 2.46 ng/g. The relative high DP sediment concentrations in Dalian suggests we can make Dalian as a DP source. DP concentrations at the sites close to industrial zone in Dalian.Bay were approximately 2-fold higher than those in the sites around the residential and garden areas, implying urban sewage discharge and industrial sources may be an important source of DP.The anti-DP fractional abundance (fanti) of DP isomers in sediment with a mean value of 0.78 was higher than the commercial DP composition (0.68), indicating a stereoselective enrichment of anti-DP in sediments.
2008年我们在中国东北的大连沿海地区采集了表层底泥样品并对DP进行了分析。底泥样品中DP的浓度分布在0.69 ng/g-7.00 ng/g之间,平均值为2.46 ng/g。大连沿海底泥中相对高的DP浓度表明我们可将大连作为一个DP源。大连湾工业区附近采样点的DP浓度近似两倍高于居民区和公园周围的采样点,这表明城市污水排放和工业源可能是大连市DP的重要来源。大连底泥的平均fanti值为0.78,略高于商用DP合成物的平均fanti值0.68,这表明底泥中的anti-DP发生了立体选择性富集。
Levels and distribution of new chlorinated flame retardant of Dechlorane Plus (DP) in air, soil, and sediment in the area of a DP production facility in China were investigated. DP was detected in air, soil, and sediment samples, total DP concentration in air was the range 7738-2,6757 pg/m3 with a median value of 12,245 pg/m3, DP concentrations in soil was 1489±3583 ng/g.Compared with the concentrations of DP in soil surrounding the facility, low concentrations of DP (4.9±4.3 ng/g) was found in sediment from the canal near the facility. The anti-DP fractional abundance (fanti) of most air samples were in the range of reported commercial DP, and most soil and sediment samples were above the mean of commercial DP, indicating a stereoselective enrichment of anti-DP in sediment and soil. Human exposures to DP in the manufacturing process are expected to be high.
Surficial sediment samples were collected in Dalian costal area, northeast China, in 2008 and analyzed for Dechlorane Plus (DP). The DP concentrations are ranging from 0.69 ng/g to 7.00 ng/g with a mean value of 2.46 ng/g. The relative high DP sediment concentrations in Dalian suggests we can make Dalian as a DP source. DP concentrations at the sites close to industrial zone in Dalian.Bay were approximately 2-fold higher than those in the sites around the residential and garden areas, implying urban sewage discharge and industrial sources may be an important source of DP.The anti-DP fractional abundance (fanti) of DP isomers in sediment with a mean value of 0.78 was higher than the commercial DP composition (0.68), indicating a stereoselective enrichment of anti-DP in sediments.
引文
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[6]Gauthier, L. T., Letcher, R. J.. Isomers of Dechlorane Plus flame retardant in the eggs of herring gulls (Larus argentatus) from the Laurentian Great Lakes of North America:Temporal changes and spatial distribution. Chemosphere 2009,75:115-120.
[7]Tomy, G. T., Pleskach, K., Ismail, N. et al. Isomers of dechlorane plus in Lake Winnipeg and Lake Ontario food webs. Environ. Sci. Technol.2007,41:2249-2254.
[8]Shen, L.,Reiner, E.,Mac, P. et al. New halogenated norbornene flame retardants in the Laurentian Great Lakes:Dechloranes 602,603 and 604 Organohalogen Compd.2009, 77:2309-2314.
[9]Hoh, E., Zhu; Hites, R. A.. Dechlorane plus, a chlorinated flame retardant, in the Great Lakes. Environ. Sci. Technol.2006,40:1184-1189.
[10]Zhu, J., Feng, Y.-1., Shoeib, M.. Detection of dechlorane plus in residential indoor dust in the city of Ottawa, Canada. Environ. Sci. Technol.2007,41:7694-7698.
[11]Sverko, E.,Tomy, G. T., Marvin, C. H. et al. Dechlorane plus levels in sediment of the lower Great Lakes. Environ. Sci. Technol.2008,42:361-366.
[12]Shen, L., Reiner, E. J., MacPherson, K. A. et al. Identification and screening analysis of halogenated norbornene flame retardants in the Laurentian Great Lakes: Dechloranes 602,603, and 604. Environ. Sci. Technol.2009.
[13]童孟良,周芝兰,许沅沅.无机阻燃剂的研究进展[J].化工文摘,2008,2：45-48.
[14]钱伯章.全球对阻燃剂的需求持续增长[J].World Plastics,2008,26 (3).
[15]褚劲松.新型磷氮系阻燃剂的合成及阻燃性能研究[D]：硕士论文.武汉：华中师范大学,2006.
[16]郭卫红,汪济奎,张德震等.聚烯烃阻燃剂及膨胀型阻燃剂的研究进展与展望[J].材料导报.2002,16(3)：56.
[17]Demir H, Balkose D, Ulku S. Influence of surface modifieation of fillers and polymer on flammability and tensile behaviour of polypropylene~composites [J]. Polymer Degradation and Stability.2006,91(5):1079.
[18]De mir H, Arkis E, Balkose D et al. Synergistic effect of natural zeolites on flame retardant additives [J]. Polymer Degradation and Stability.2005,89(3):478.
[19]陆云.卤系阻燃剂在防火材料中的应用及前景.消防技术与产品信息.2009,10：41-42.
[20]王晓英,毕成良,李俐俐等.新型环保阻燃剂的研究进展[J].天津化工.2009,23(1)：8-11.
[21]杨丽,周逸潇,韩新宇等.阻燃剂阻燃机理的探讨[J].天津化工.2010,24(1)：1-4.
[22]梁诚.阻燃剂生产现状与发展趋势[J].中国石油和化工.2003,(9)：22.
[23]任淑英.阻燃剂及其发展方向[J].聚合物与助剂.2008,(6)：25-29.
[24]TROITZSCH J H. Overview of flame retardants, fire and fire safety,markets and applications, mode of action and main families, role in fire gases and residues[J]. ChemToday.1998,16(1):18-24.
[25]HIRAI Y, SAKAI S. Brominated flame retardants in recycled plastic products[Z]. Amsterdam:4th International Workshop on Brominated Flame Retardants,2007.
[26]FONSECAL V M, FERNANDES V J, ARAUJO A S et al. Effect of halogenated flame-retarda-nt additives in the pyrolysis and thermal degradation of polyester/sisal composites[J].J Thermal Analy& Calorim.2005,79:429-433.
[27]姜玉起.溴系阻燃剂的现状及其发展趋势[J].化工技术经济.2006,24(9)：14-18.
[28]MCPHERSON A, THORPE B, BLAKE A. Brominated flame retardants in dust on computers: The case for safer chemicals and better computer design[R]. Massachusetts:Clean Production Action, Computer Take Back Campaign,2004.
[29]BARONTINI F, COZZANI V. Form ation of hydrogen bromide and organobrominated compounds in the thermal degradation of electronic boards [J]. J Analytic and Applied Pyrolysis.2006,77(1):41-55.
[30]DAW SON R B, LANDRY S D. Brominated flame retardantst:Issues surrounding their use in electrical and electronic equipment[z]. Boston:IEEE International Symposium on'Electronics and the Environment,2003.
[31]BIRNBAUM L S,STASKAL D F. Brominated flame retardants:cause for concern [J]. Environ Health Perspect.2004,112(1):9-17.
[32]纪巍,王鉴,董群等.阻燃剂在塑料中的应用及发展趋势[J].化学工业与工程.2008,25(2)：177-182.
[33]徐启杰,李伟,时文中.溴系反应型阻燃剂的研究进展[J].天中学刊.2007,22(2)：25-28.
[34]欧育湘.实用阻燃技术.北京：化学工业出版社,2002.
[35]欧育湘,阻燃剂-制造、性能及应用,北京：兵器工业出版社,1997.
[36]薛铮然,李海静.山东化工.2002,31：31-32.
[37]US Department of Health and Human Services. National Toxicology Program.1986.
[38]WHO. Environmental Health Criteria:Brominated Diphenyl Ethers. World Health Organization.1994:162.
[39]Thoma H, Hauschulz G, Knorr E, Hutzinger 0. Chemosphere.1987,16:277-285.
[40]SEderstrEm G, SellstrEm U, de Wit C, Tysklind M. Environ. Sci. Technol..2004, 38:127-132.
[41]Ohta S, Nishimura H, Nakao T. et alOrganohalog. Compd..2001,52:321-324.
[42]刘汉霞,张庆华,江桂斌.多溴联苯醚及其环境问题[J].化学进展.2005,17(3)：554-562.
[43]刘宗峰,朗印海,曹正梅等.环境中多溴联苯醚(PBDEs)分布特征研究进展[J].土壤通报.2007,38(6)：1227-1233.
[44]Sellstrom U, Kierkegaard A, de Wit C, Jansson B. Environ. Toxicol. Chem..1998, 17:1065-1072.
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