电子废物拆解区河流沉积物中多溴二苯醚的污染水平、分布及来源

用GC-NCI-MS分析法测定了路桥河流表层沉积物中41种多溴二苯醚同类物的含量. 目的是了解该地区沉积物中PBDEs的污染水平、空间分布特征和来源. 结果表明,所有沉积物样品中₄₀PBDEs(不包括BDE209)的含量为0.177～161 ng·g^-1,平均值为22.5 ng·g^-1, BDE209的含量为0.36～958 ng·g^-1,平均值为148 ng·g^-1. 同族体组成特征表明多数样品中十溴二苯醚(BDE209)是最主要的同族体,占38.4%～96.0%, 平均值为74.4%,九溴PBDEs和七溴PBDEs次之, 分别占3.3%～25.8%和0.01%～14.1%. PBDEs同类物之间呈显著性相关,表明大多数PBDEs同类物有相似的输入途径.同族体组成和聚类分析表明,所有采样点均受到deca-BDE工业品的污染,另有一些采样点除受到deca-BDE工业品的污染外, octa-BDE工业品也有一定的贡献. 与国内外其它研究相比,研究区域内沉积物中的PBDEs污染处于中低水平,但个别样点受点源污染影响较大,值得关注.     

珠江河口水生生物中多溴联苯醚的分布

对珠江河口生物样品中多溴联苯醚(PBDEs)的含量进行了检测.所采集的鱼类(鱼、大黄鱼、银鲳、舌鳎、龙头鱼),虾类(刀额新对虾、近缘新对虾)及虾蛄类生物样品肌肉组织中10种PBDEs(BDE28,47,66,100,99,85,154,153,138,183)的含量分别为37.8～407.1 ng·g^-1(脂肪归一化浓度)、49.0～239.1 ng·g^-1和142～444.5 ng·g^-1.所有样品中,BDE47相对含量最高,其相对于∑<     

浙江省台州市电子垃圾拆解地多溴联苯醚浓度水平分布特征和迁移趋势

本研究分析了浙江省台州市电子垃圾拆解地及其周边表层土壤和大气中多溴联苯醚（PBDEs）的浓度水平.结果表明,台州市峰江和滨海的拆解园区、农田和居住区土壤中∑₁₂PBDEs含量（以dw计）范围分别为21.8~1310 ng ·g^-1和6.19~220 ng ·g^-1,PBDEs单体分布没有显著差异.峰江和滨海两地大气中∑₁₂PBDEs质量浓度范围分别为262~3240 pg ·m^-3和840~2990 pg ·m^-3,浓度中值分别为1410 pg ·m^-3和840 pg ·m^-3（冬季）、1590 pg ·m^-3和1960 pg ·m^-3（夏季）,除去BDE209外的11种PBDEs单体分布在冬夏两季呈现显著性差异.通过土-气交换逸度分析发现峰江和滨海PBDEs在土-气分布迁移趋势上呈现一定的差异性.峰江PBDEs的迁移趋势主要以土壤挥发为主,土壤是大气中3~5溴代BDEs的排放源,温度的升高可以促进这一过程,这说明峰江土壤中PBDEs已成为污染释放源,建议应对峰江电子垃圾拆解园区土壤和附近农田开展土壤修复.滨海PBDEs的迁移趋势则主要以大气沉降为主,土壤是PBDEs主要的汇,说明滨海的拆解园成为PBDEs的新排放源.     

上海市地表灰尘中PAHs季节变化与功能区差异

研究了上海市中心城区地表灰尘中多环芳烃（PAHs）的季节变化与功能区差异,并探讨了这种变化特征的原因.结果表明,上海市中心城区地表灰尘中PAHs累积水平具有显著的季节变化,PAHs总量和组分均表现出冬季含量高于夏季的特征.冬季样品中PAHs含量为9 176～32?573 ng·g^-1,平均值为20 648 ng·g^-1;而夏季PAHs含量为6?875～27?766 ng·g^-1,平均值仅为14?098 ng·g^-1.PAHs组分也表现出相似特征,冬季含量为50(二氢苊)～3 162 ng·g^-1 (茚并［1,2,3-c,d ］芘),夏季含量为3(苊)～1 485 ng·g^-1 (茚并［1,2,3-c,d ］芘).各个功能区地表灰尘PAHs含量的差异明显.冬季最高值出现在工业区（31 163 ng·g^-1）、商业区（24 932 ng·g^-1）和交通要道（18 815 ng·g^-1）,最低值出现在公园（7 885 ng·g^-1）和绿地（8 036 ng·g^-1）;夏季最低值出现在公园（7 942 ng·g^-1）,最高值出现在交通要道（14 528 ng·g^-1）、工业区（14 247 ng·g^-1）和商业区（11 523 ng·g^-1）.所有功能区样品中PAHs组分含量呈现出按环数或分子量的增加而逐渐升高的趋势.大城市地表灰尘中PAHs的季节变化与功能区差异与其来源密切相关,也受到各组分理化性质的影响.     

泉州山美水库及入库河流沉积物中多溴二苯醚的时空分异和降解分析

为了解城市水源水库中多溴二苯醚（PBDEs）的时空分异和同系物的降解来源及其贡献,分析了泉州山美水库及入库河流表层沉积物中PBDEs的含量、污染程度、空间分布、水文期变化、赋存量、同系物组成及其降解来源的贡献.结果表明,入库河流沉积物中∑PBDEs中值（1072.1 ng ·g^-1）是山美水库（160.4 ng ·g^-1）的6.7倍,山美水库单位面积沉积物中∑PBDEs的赋存量（80.3 kg ·km^-2）是太湖的6.3倍,北美五大湖的188倍,其污染程度较国内外大多数湖库更严重,且以BDE-209为主（84.5%~99.2%）.水库大多数样点（r为0.564~0.994,P<0.034）及河流各点（r为0.953~1.0,P<0.000）间PBDEs组成相似度较高,入库区和入库河流样点间极显著正相关（r为0.779~0.964,P<0.005）且相关性强于其他功能区,显示入库河流是水库中PBDEs的主污染源.库尾区与入库河流相关性较低（r为0.454~0.915,P≤0.128）,受九都镇影响较大.各样点∑PBDEs水文期变化较一致（r为0.617~0.714,P≤0.077）,但水文期变化对∑PBDEs的影响统计不显著（P=0.178,Two-Way ANOVA）,而点位变化则对∑PBDEs有极显著影响（P=0.0001）,入库区和其他功能区有（近）显著差异（P为0.019~0.061）,表明PBDEs在水库沉积物中的空间分布变异大于水文期变化.PBDEs自然降解从河流到入库区再到库中区逐渐增加,且各级还原脱溴速率不同,部分BDE因其继续降解速率较慢而累积.丰度比值法研究表明,低溴BDE主要源自十溴二苯醚的逐级还原脱溴自然降解.Deca-BDE降解产生的Nona-BDE约70%以上可较快降解生成Octa-BDE,BDE-208约85%源自BDE-209的降解,从Octa-BDE到Penta-BDE的降解过程中,部分Octa-BDE和Hexa-BDE同系物因降解较慢而累积,Penta-BDE到Tri-BDE降解率在70%以上.     

珠江三角洲养殖水体中喹诺酮类药物残留分析

利用高效液相色谱分析了珠江三角洲地区淡水养殖区和海水养殖区7个不同采样点表层水体、沉积物以及8种养殖鱼类肌肉和肝脏2种组织中诺氟沙星、环丙沙星和恩诺沙星3种喹诺酮类药物残留含量.结果表明,养殖水体表层水中均未检出3种喹诺酮类药物;淡水养殖区沉积物中诺氟沙星、环丙沙星和恩诺沙星检出范围分别在5.03～13.28、3.64～9.32和0～7.13 ng·g^-1;海水养殖区沉积物分别为1.88～8.81、0～1.09 ng·g^-1,恩诺沙星在海水养殖区沉积物中未检出;3种喹诺酮类药物在鱼体肝脏组织中含量普遍高于肌肉组织,其中诺氟沙星、环丙沙星和恩诺沙星在鱼体肌肉组织中的含量分别为1.95～100.54、0.48～33.26和1.18～51.89 ng·g^-1.3种喹诺酮类药物在鱼体内的残留浓度大小顺序为：诺氟沙星>恩诺沙星>环丙沙星.淡水养殖鱼类喹诺酮药物残留普遍高于海水养殖鱼类.     

北京东南郊化工区土壤和植物中氯苯类有机物的残留及分布特征

对2003-11采自北京东南郊化工区的土壤、植物样品中11种氯苯类有机物进行了分析测定. 结果表明,土壤（干重）中氯苯类有机物（CBs）的总量范围为0.232～51.15 ng·g^-1,均值为18.16 ng·g^-1,其中1,2-DCB、1,4-DCB和HCB分别占45.2％、15.3％和17.1％;植物（干重）中CBs的总量范围为5.635～31.99 ng·g^-1,均值为12.36 ng·g^-1,其中1,4-DCB和HCB分别占51.5％和14.9%. 土壤中∑CBsi>与土壤有机质含量的皮尔森（Pearson）相关系数为0.544（P≤0.05）,呈弱正相关关系. 此外,除1,4-DCB和1,2,4-TCB外,云杉针叶中CBs的土壤-植物富集因子（BCFs）随CBs挥发能力［lg(V_P/K_OW)的增强而降低,随CBs辛醇/空气分配系数（K_OA）的增大而升高.     

电子垃圾拆解地表层土壤中的多卤代芳烃及其潜在污染源

通过收集典型电子垃圾拆解区的电子垃圾碎屑以及拆解现场和对照区的表层土壤（0～5 cm深度）样品.采用GC/MS 5975B对样品中PHAHs进行分析.结果发现,在采集的三大类电子垃圾碎屑中电缆绝缘层含有最高浓度的PBBs（35.25 ng·g^-1）,其中以PBB2、PBB3和PBB15为主的低溴代联苯占到总量的38%.电子元件填充物中的∑PBDEs和PBDE209检出浓度最高,分别为29.71 ng·g^-1和4.19×103 ng·g^-1;PBDE153和PBDE183是最具支配地位的同族体,分别占PBDEs总量的43%和24%.电缆绝缘层中的PCBs浓度在所收集的电子垃圾碎屑中最高（680.02 ng·g^-1）.拆解现场表层土壤中PHAHs的污染特征与电子垃圾碎屑中PHAHs的污染特征相一致,而且其污染水平明显高于对照区土壤相应PHAHs的浓度水平.表明电子垃圾中PHAHs是当地土壤环境的重要污染源.     

典型电子垃圾拆解区大气中多溴联苯醚的污染

分别在典型电子垃圾拆解区(E)和其上风向参考点(S)采集了大气颗粒相和气相样品，以研究该区域大气中PBDEs的浓度水平、污染特征和气/固分布特点.分析过程中运用气相色谱-质谱联用仪，负化学离子源(GC-NCI-MS)检测了11种PBDEs.结果表明，电子垃圾拆解造成了比较严重的PBDEs污染，三溴～十溴联苯醚的浓度范围为51.1～2685 pg·m^-3(平均值830 pg·m^-3)，而对照区由于制衣行业的影响也造成了一定程度的PBDEs污染，三溴～十溴联苯醚的浓度范围为1.00～98.9 pg·m^-3(平均值28.7 pg·m^-3).在气/固分布的研究中发现，不同的PBDEs在气相和颗粒相的分布比例相差很大，从低溴至高溴PBDEs在气相中的比例呈降低趋势，而在颗粒相中的比例呈上升趋势.电子垃圾拆解区以五溴-联苯醚污染为主，占∑₁₁PBDEs总量的54.3%；而十溴-联苯醚污染次之，占∑₁₁PBDEs总量的23.8%，该污染特征进一步证实了该地区电子垃圾的来源，不仅来自亚洲国家，而且还来自欧美等国家.     

练江沉积物中多溴联苯醚的污染特征、来源和潜在生态风险研究

为考察贵屿电子垃圾拆解区污染沿水体向下游的迁移行为和影响,本文对练江贵屿段及其上下游表层沉积物进行了系统采样和多溴联苯醚（PBDEs）分析,并对其污染来源和潜在生态风险进行了探讨.结果表明：PBDEs在练江上下游沉积物中普遍存在（检出率100%）,在贵屿上游浓度较低（10.2~2120 ng·g^-1）,进入贵屿段急剧升高（7470~193000 ng·g^-1）,至贵屿下游后有所起伏但整体下降（734~11300 ng·g^-1）.练江的PBDEs污染主要来自于沿途排放,贵屿电子垃圾拆解业是其中最大的污染排放源.贵屿下游沉积物的PBDEs浓度比上游高约一个数量级,说明贵屿高浓度的PBDEs污染可沿水体迁移至下游.主因子分析结果表明练江沉积物中的PBDEs污染存在3种模式,上游和下游主要支流（贵屿支流除外）呈现Deca-BDE污染模式（BDE-209为绝对优势单体）,这是我国沉积物中PBDEs的典型污染模式,可视为练江沉积物中PBDEs污染的背景模式;贵屿则呈现出两种特异模式：Penta-BDE模式（优势单体BDE-47&-99）和Deca-BDE脱溴降解模式（以BDE-197为主,其次是-209）,这分别与贵屿地区的电路板拆解和塑料的高温处理方式（烘烤、焚烧、熔融等）有关;贵屿下游支流和主干道样品中的PBDEs呈现与贵屿相似但多种模式共存的特征,进一步证实贵屿的PBDEs污染已沿水体迁移至下游并影响其PBDEs组成特征.练江上游和下游主要支流（贵屿支流除外）PBDEs的风险商值（HQ）均<1,表明生态风险可接受;贵屿段PBDEs的HQ值均>1,最高达63.9,存在严重生态风险;受贵屿污染迁移影响,贵屿下游支流及部分练江主干道样品的HQ值也>1,为PBDEs污染高风险区;Penta-BDEs（三-五溴代BDEs）为HQ值主要贡献污染物,其次是Hexa-BDEs和Deca-BDE.鉴于PBDEs具有环境持久性且在贵屿段的沉积通量高达（477±648）t（贵屿下游为（152±169）t）,其在贵屿及其下游20 km以内的污染急需开展进一步调查并采取相应的污染治理和修复措施.     

广州市室内尘土中多溴联苯醚的分布特点及来源

随机采集了广州市46个家庭和12个办公室内尘土样品,同时采集了17个室外尘土样品、2个电视机和2个电脑尘土样品并分析了室内尘土中多溴联苯醚(PBDEs)的含量、单体分布及来源.结果表明,家庭尘土中∑10PBDEs(BDE28,47,66,85,99,100,153,154,183,209之和)的含量为 564.3~9654ng/g,中值和均值分别为 2686,3407ng/g;办公室尘土中∑10PBDEs 的含量为 1737~4408ng/g,中值和均值分别为3133,3179ng/g.室内尘土中PBDEs的最主要单体为BDE209,分别占家庭尘土和办公室尘土∑10PBDEs的97.4%和99.0%.BDE47、99和183在室内尘土中含量也较高.大多数室内尘土中∑10PBDEs的含量高于室外,说明室内可能有重要的PBDEs释放源.室内尘土中PBDEs的主要工业品来源为十溴联苯醚,五溴联苯醚次之,八溴联苯醚较少.     

生产源区人血中多溴联苯醚水平与甲状腺激素相关性研究

采用气相色谱/负化学电离源-质谱法对莱州湾南岸地区十溴联苯醚生产源区36位居民血清中的5种多溴联苯醚浓度进行了检测,同时测定了样品中的甲状腺激素水平.血清中Σ5PBDEs（BDE-28、-47、-153、-183、-209）的质量浓度范围（以脂重计算,下同）为130.3～4 478.4 ng.g-1,平均值为529.9 ng.g-1.5种同族体中,BDE-209对Σ5PBDEs的平均贡献率达到了69.8%.在与甲状腺激素水平的相关性研究中,计算了两者的Spearman秩相关系数,结果显示BDE-28、-47、-153、-183与TSH水平呈高度负相关,BDE-183与fT4水平呈现显著性负相关,而BDE-28、-47与T3,BDE-28、-153、-183与fT3之间均呈现显著性正相关.本研究中,生产源区人体血清中PBDEs水平处于较高的暴露水平,主要同类物为BDE-209,人体对PBDEs的暴露会影响上述4种甲状腺激素的水平,PBDEs对人体的影响不容忽视,有关PBDEs暴露水平与甲状腺激素水平之间的相关性,应进一步深入研究.     

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach (Misgurnus anguillicaudatus)

To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept into net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied in this e-wastes recycling site, the mean concentrations of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach （Misgurnus anguiUicaudatus）

To understand potential ecotoxicological e ects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept in net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant di erence of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological e ects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied, the mean concentration of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE 209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE 209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

江苏经济高速发展城市香樟树皮中的多溴联苯醚

2009年7月在江苏省南部城市苏州,南通和无锡采集了40组香樟树皮样品,用加速溶剂萃取、气相色谱质谱法测定了样品中8种多溴联苯醚（PBDEs）.结果表明,所有样品中都检出了PBDEs,Σ8 PBDEs（BDE28、47、100、99、153、154、183、209）平均含量为835μg/kg脂重（112～7 460μg...     

Polybrominated diphenyl ether (PBDE) in blood from children (age 9–12) in Taizhou, China

Polybrominated diphenyl ethers (PBDEs) as ubiquitous persistent organic pollutants have attracted much attention in recent years. Exposure to PBDEs could induce a high health risk for children. The aim of this study was to investigate the PBDEs exposure of children (9–12 years) from Taizhou, China. Fifty-eight blood samples were collected in one school in a mountainous area in Taizhou. The concentrations of Σ9PBDEs (sum of BDE-28, -47, -99, -100, -153, -154, -183, -197 and -209) ranged from 2.66 to 33.9 ng/g lipid wet (lw) with a median of 7.22 ng/g lw. These concentrations were lower than those of children in USA, but close to European and Asian general population levels. The results showed that children in Taizhou countryside were at a low level of PBDEs exposure. The predominant congener was BDE-209, followed by BDE-28, -47, -197 and -153. High abundance of BDE-209 was consistent with the pollution background of PBDEs in China characterized by high brominated congeners as main pollutants.     

Debrominated and methoxylated polybrominated diphenyl ether metabolites in rainbow trout (Oncorhynchus mykiss) after exposure to decabromodiphenyl ether

Decabromodiphenyl ether (BDE209) is the primary component in a commonly used flame retardant. Previous studies had proved that BDE209 itself was not toxic, while its metabolites including debrominated diphenyl ethers (De-BDEs) and methoxylated brominated diphenyl ethers (MeO-BDEs) posed a potential threat to organisms. Many studies had indicated that BDE209 could metabolize quickly in mammals, but lacking in the basic data about the metabolism of BDE209 in fish. In the present study, two replicate treatment groups of rainbow trout (Oncorhynchus mykiss) were exposed to BDE209 via a single intraperitoneal injection approximately 100 and 500 ng/g, respectively. Muscle, liver and blood samples were collected to analyze the specific metabolites on day 1 and day 28 post injection. The highest concentration of BDE209 was detected in muscle tissues, from 796.1 ng/g wet weight (day 1) to 687.1 ng/g wet weight (day 28) in high dose group, suggesting that BDE209 could accumulate slightly in muscle tissues. However, BDE209 was not detected in the blood for all treatments. Most congeners of De-BDEs were found in muscle and liver tissues, with the highest concentration in the liver. The main De-BDEs were nona-, octa-, hepta- and penta-De-BDEs. A total of seven MeO-BDE metabolites were observed among di erent fish tissues. Blood had the highest contribution of the MeO-BDE metabolites. Each MeO-BDE congener increased over the 28 days. These results in contrast to other studies suggested possible species-specific di erences in metabolic abilities.     

有机氯农药和多溴联苯醚在白洋淀鸭子组织中分布特征研究

利用气相色谱-质谱(GC/MS)方法定量分析了白洋淀鸭子肌肉、肝脏、脑组织中HCHs、DDTs和PBDEs的分布特征.结果表明,3种组织中HCHs和DDTs的含量范围分别为0.9～5.0 ng/g(以湿重计,下同)和0.3～2.8 ng/g,而PBDEs的含量范围是0.03～0.65 ng/g.统计分析鸭子不同组织中持久性卤代烃的含量差异,结果显示,DDTs和PBDEs的含量水平有较大差异(p0.05);而HCHs在3种组织中的含量差异不明显(p0.05).肝脏中DDTs和PBDEs的平均含量较高,分别为2.3和0.37 ng/g.在HCHs和DDTs同系物(代谢物)组成中,β-HCH在肝脏和脑组织中占主要地位,p,p′-DDE是DDTs的主要代谢产物;在PBDEs同系物中,BDE47和BDE99是鸭子组织中主要的组成部分.鸭子不同组织中HCHs、DDTs和PBDEs的组成模式反映了白洋淀仍然受到历史残留的有机氯农药污染;同时,来自白洋淀上游的工业污染很可能输入新型持久性有机污染物(PBDEs).