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...     

电子废物拆解区农业土壤中多溴二苯醚的分布与来源

用GC-NCI-MS测定了浙江台州路桥表层农业土壤中41种多溴二苯醚(PBDEs)的含量, 并对其分布及来源进行了分析.结果表明:所有样品中Σ41PBDEs的含量为0.193~91.0ng/g,平均值为8.96ng/g,其中BDE209的含量为0.0452 ~ 61.5ng/g,平均值为5.41ng/g.在多数样品中十溴BDE及九溴BDEs是主要的同族体,四溴和七溴BDEs同族体次之.同族体组成特征和聚类分析表明,多数采样点主要受到deca-BDE工业品的污染,另有一些采样点受到octa-BDE和deca-BDE工业品的污染,个别采样点主要受到penta-BDE工业品污染.与国内外相关研究相比,研究区域内土壤中PBDEs的污染水平较低,但少数采样点受点源污染影响较大.     

中国东北主要河流沉积物中多溴二苯醚的含量状况及生态风险分析

为揭示多溴二苯醚(PBDEs)在东北主要河流流域内的污染现状,通过采集该地区流域内表层沉积物样品,采用GC-NCIMS技术对沉积物中41种PBDEs同类物进行分析.结果发现沉积物中BDE209含量低于检出限,其它40种PBDEs同类物总含量(不包含BDE209)范围(干重)为0.91~17.67 ng·g-1.其中第二松花江吉林市上游和下游沉积物样品中PBDEs的检出含量最高,分别为15.86 ng·g-1、17.67 ng·g-1,以BDE207和BDE47为主,分别占PBDEs总量的86.5%和76.6%;其它河流沉积物中各同族体含量差异并不明显.实验结果与国内外最近的文献报道值相比较,再结合生态风险分析显示,东北主要河流沉积物中PBDEs的含量处于低污染水平,目前不存在生态风险.     

三峡库区主要支流表层沉积物多溴联苯醚的分布特征

采用GC-MS(NCI)技术对三峡库区28个表层沉积物样品中的多溴联苯醚(PBDEs)进行分析,研究了其在三峡库区主要支流的污染现状与分布特征.实验发现三峡库区Σ26PBDEs和BDE209在沉积物中的检出含量分别为35.24 pg·g-1和11.92 pg·g-1,其中BDE28,47,77和99为Σ26PBDEs中最具支配地位的同族体.Σ26PBDEs和BDE209的最高检出含量在龙河河口采样点,分别为146.07 pg·g-1和502.63 pg·g-1.Σ26PBDEs和BDE209含量具有良好相关性,说明两者污染来源相同.实验结果与国内外水体沉积物中含量相比较,显示Σ26PBDEs和BDE209在三峡库区沉积物中含量处于较低污染水平,引起的潜在风险也相对较低.     

苏州、无锡和南通道路灰尘中的多溴联苯醚和多氯联苯

2009年7月在江苏省南部城市苏州、无锡和南通采集了58个城市道路灰尘样品,使用气相色谱质谱法测定了样品中的8种多溴联苯醚(PBDEs)和32种多氯联苯(PCBs).结果表明,样品中Σ8PBDEs含量范围为4.21~1 471μg·kg-1,Σ32PCBs含量范围为ND~14.1μg·kg-1,PBDEs的含量远远高于PCBs.和其他地区城市土壤样品比较,城市道路灰尘中的PBDEs含量较高,来自燃料燃烧过程和汽车尾气产生的PBDEs不容忽视.城市工业区和中心区样品中PBDEs和PCBs的含量水平没有显著性差异,而高于景观区.研究发现,在城市工业区存在PCBs非故意排放源.PBDEs同族体单体相对含量分析表明,BDE209是样品中检测出的最主要的PBDEs单体,占Σ8PBDEs含量的96.7%(64.1%~99.8%).样品中的PCBs同族体主要为四氯代PCBs和六氯代PCBs,道路灰尘中PCBs同族体的分布模式与PCBs产品和其他环境介质存在一定差异.     

济南市夏季环境空气中PBDEs的浓度分布及潜在风险分析

为准确评估济南市夏季环境空气中PBDEs（多溴联苯醚）的污染情况,利用气相色谱-负化学离子源-质谱（GC-NCI-MS）方法,对采集到的大气颗粒物滤膜和气相样品进行了分析,得到不同粒径颗粒相和气相PBDEs在济南市夏季环境空气中的质量浓度.结果表明:观测期间,济南市环境空气中TSP（总悬浮颗粒物）、PM₁₀和PM_2.5中的ρ（PBDEs）分别为（224.1±14.0）（156.5±43.7）（110.2±27.4）pg/m3,质量浓度较高的3种PBDEs单体分别为BDE209、BDE99、BDE183;气相中ρ（PBDEs）为（54.8±13.2）pg/m3,其中,质量浓度较高的单体分别为BDE209、BDE47、BDE99.通过主因子分析发现,不同粒径颗粒物上吸附的PBDEs特征单体不同,TSP中以五溴联苯醚为主,PM₁₀中以八溴联苯醚和五溴联苯醚为主,PM_2.5中则以五溴联苯醚、八溴联苯醚、十溴联苯醚为主.通过将2种模型的预测值和实测值进行比较发现,稳衡态模型比K_OA（辛醇-空气分配系数）模型更好地模拟了PBDEs的气-粒分配情况.在稳衡态模型下,PBDEs在气-粒分配中接近于平衡状态.高溴代PBDEs主要分布于颗粒相中,而低溴代PBDEs的真实情况不同于理论预测结果,BDE99及BDE47在颗粒相的分配比高于50%,说明济南市低溴代PBDEs也容易吸附在颗粒相中.根据计算的PBDEs呼吸暴露水平可知,PM_2.5上PBDEs呼吸暴露量占TSP呼吸暴露量的49.1%,儿童约是成人的1.5倍.济南市普通儿童和成人对BDE99最高总摄入量分别为234.78和169.57 pg/（kg·d）,均低于BDE99最大允许摄入量260 pg/（kg·d）.根据US EPA（美国环境保护局）发布的PBDEs健康风险评价方法（EPA/540/R/070/002）,利用国内外相关参数分别计算空气吸入致癌风险指数发现,济南市夏季环境空气中PBDEs的致癌风险处于较低水平.研究显示,济南市夏季环境空气中不同粒径颗粒物PBDEs的质量浓度处于较低污染水平,其产生的潜在健康风险也较低.      

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.     

GC/MS法测定生物样品中多溴联苯醚类化合物

本研究建立了多溴联苯醚（PBDEs）生物样品分析方法,获得了优化的前处理条件、气相色谱和质谱检测条件.对定性定量方法及实验条件必须满足的要求进行了评价.通过质量控制（quality control, QC）对整个方法进行了验证.结果证明,本研究所建立的分析方法满足生物样品PBDEs测定的要求,回收率在50.5%～112.3%之间,回收率相对标准偏差在5.3%～9.9%之间,方法检测限在7.1～161.8 pg/g之间.在建立的方法基础上,测定了部分养殖和野生鱼类样品,测得的野生鳜鱼和鲫鱼以及2个养殖鲈鱼样品的结果分别为1.53、1.11、5.31和6.15 ng/g(干重),其中主要的同族体为BDE47.     

环渤海沉积物中多溴联苯醚(PBDEs)的研究

采用同位紊稀释高分辨气相色谱-质谱法,对环渤海海域的16个表层沉积物样品中的PBDEs进行了研究.研究结果表明环渤海区域ΣPBDEs含量水平差异较大,西部海域污染较其它区域严重.但与世界其它地区相比,总体的含量水平较低,与中国南海北部海域以及韩国近海海域基本相当.沉积物中PBDEs的污染模式以BDE209为主,反映了十溴联苯醚是我国目前使用最多的溴代阻燃剂.     

ASE-气相色谱/质谱法测定土壤硝基苯类化合物

该文通过优化土壤中硝基苯类化合物加速溶剂萃取/净化方法的最佳条件。结果表明:采用丙酮-二氯甲烷混合溶剂(1∶1,V/V)为萃取溶剂,萃取温度80℃,循环2次;经硅酸镁柱净化,气相色谱/质谱法进行分析。该法对土壤中20种硝基苯类化合物有良好的分离效果,选择不同浓度基体加标得到的回收率为73.0%～108%,相对标准偏差在1.8%～8.4%之间,方法检出限为2～10μg/kg。     

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.     

昆明市大气总悬浮颗粒物和PM2.5上多溴联苯醚的分布特征和潜在风险

为探究PBDEs（多溴联苯醚）在昆明大气中的环境行为,于2014年3月对昆明8个采样点大气TSP（总悬浮颗粒物）和PM_2.5样本进行了收集并利用GC-MS技术对其上附着的PBDEs的13种同系物进行了测定,进而对TSP和PM_2.5上PBDEs的分布特征和潜在风险进行了分析.结果表明:附着在TSP上的∑PBDE浓度（多溴联苯醚的总质量浓度）的范围为21.10~175.00 pg/m3.而附着在PM_2.5上的∑PBDE浓度范围为17.50~149.00 pg/m3,约占TSP中∑PBDE浓度的35.31%~85.14%,并且高溴化的同系物（BDE-138~BDE-209）比低溴化的同系物（BDE-17~BDE-99）更容易附着在PM_2.5上,约占∑PBDE浓度的8.50%~61.60%.对大气颗粒物中PBDEs的潜在影响和空气吸入暴露剂量评估结果表明,成人和儿童对PBDEs的DED_air（呼吸日暴露量）分别在5.28~43.75和6.90~57.23 pg/（kg·d）之间,TDI（每日总摄入量）分别在114.78~951.09和150.00~1 244.13 pg/（kg·d）之间,远低于最低无害水平[1 mg/（kg·d）].BDE-99的TDI分别为11.09~72.39和14.35~94.57 pg/（kg·d）,均低于最低摄入水平[260 pg/（kg·d）].研究显示,昆明市大气TSP和PM_2.5上的PBDEs对人体不存在健康风险.      

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.     

渤海湾脉红螺中多氯联苯和多溴联苯醚的测定分析

应用GC/HRMS对渤海湾脉红螺中的PCBs(多氯联苯)和PBDEs(多溴联苯醚)2类持久性有机污染物进行了测定分析.结果表明:雄性脉红螺中PCB(3～10氯代)的质量分数(10.1 ng/g,以干质量计)和PBDEs(BDE28、BDE47、BDE99、BDE100、BDE153、BDE154、BDE209)的质量分数(1.74 ng//g)均高于雌性脉红螺(分别为8.09和1.38 ng/g);雄性脉红螺中PCBs的WHO-TEQ(毒性当量,8.41 pg/g,以脂肪质量计)高于雌性脉红螺(4.34 pg/g),其中PCB118和PCB126的贡献率分别为13%和77%.脉红螺的不同组织中,性腺和消化腺中w(PCBs)和w(PBDEs)最高,肌肉组织中最低;主要同类物为PCB118、PCB101、PCB28、PCB138、PCB180、PCB52、PCB153和5-PCB以及BDE209.渤海湾脉红螺的消化腺可以作为PCBs和PBDEs的生物指示物.     

广州地区典型多溴联苯醚迁移和归趋行为模拟

运用多介质逸度模型对典型PBDEs(BDE47、BDE99、BDE209)在广州地区大气、水体、土壤、沉积物中的浓度分布与多介质间的迁移、归趋进行了模拟研究并分析了3种化合物在研究区域环境多介质间的迁移通量,确定其在环境中的主要迁移过程;结合实际监测数据,对模型的可靠性进行验证;以BDE47和BDE209为例,对模型的输入参数进行灵敏度分析;并以BDE209为例,对模型进行不确定性分析.通过模拟浓度与实测浓度的对比,表明模型在该地区具有很好的适用性.结果表明,环境系统达到平衡时,BDE47、BDE99和BDE209在土壤和沉积物中的含量分别占其在环境系统总含量的17.73%和82.26%,14.65%和85.35%,4.81%和95.19%;PBDEs从环境系统中的消失途径主要为大气平流输出和土壤降解;logKow和大气平流输入是影响化合物在环境相中浓度分布的最主要因素;不确定性分析指出BDE209在土壤相中浓度的变异系数最大.     

低浓度重金属对蜡状芽孢杆菌复合菌降解BDE209性能的影响

针对电子废弃物引起的重金属及多溴联苯醚(PBDEs)复合污染问题,采用GC-MS, ICP、紫外扫描、红外光谱等分析方法,研究了蜡状芽孢杆菌(XPB、XPC)复合菌对十溴联苯醚(BDE209)的好氧脱溴降解性能及低浓度重金属对其降解特性的影响.结果表明,复合菌对BDE209有良好的脱溴性能,能将其降解为酚类有机物,反应1 d时其最高脱溴量可达1.18mg·L-1,脱溴率至少为14.16%.低浓度重金属的存在虽减缓BDE209的降解速率,但依然能保持良好的降解效果,脱溴率仍至少达13.92%.复合菌降解BDE209和吸附重金属的过程主要与羟基、酰胺基团和C--H键有关.单一降解BDE209过程中,复合菌大量释放K 和Na ,最高释放量分别为148.867和225.835μmol·g-1.复合菌在降解BDE209并吸附重金属的过程中,也存在K 和Na 的大量释放现象,且释放量高于单一的降解过程,最高释放量分别为156.482和261.217 μmol·g-1.菌体降解BDE209的同时,对Pb2 、Zn2 、Cu2 的吸附率最高值分别为89.47%、72.22%、39.83%.     

Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from Fuhe River and Baiyangdian Lake, North China

Nineteen surface sediment samples collected from Baiyangdian Lake and its inflowing river (Fuhe River) in North China were analyzed for polybrominated diphenyl ethers (PBDEs) and decabromodiphenylethane (DBDPE). The concentrations of PBDEs and DBDPE in sediments ranged from 5.5 to 300.7 ng/g dry weight (dw) and 1.1 to 68.2 ng/g dw, respectively. Their levels in sediments in Fuhe River were significantly higher than those in Baiyandian Lake. Compared to data from other regions, the PBDE levels in surface sediments from Baiyangdian Lake and Fuhe River were in the medium to lower range. Among the PBDE congeners, BDE209 was predominant, with contributions to the total PBDEs ranging from 79.4% to 97.3% in sediment samples. For the lowly brominated congeners (tri- to hepta-BDE), BDE47 and BDE99 were the most abundant, which contributed 52.1% and 44.1% to the sum of tri- to hepta-BDEs in the sediments from Baiyangdian Lake and Fuhe River, respectively. The compositional patterns of PBDEs in Baiyangdian Lake sediments indicated that technical deca-BDE mixture was the major pollutant sources with a minor contribution of penta-BDE mixture. The present study suggested that the importance of Fuhe River as a possibly potential sources of PBDEs contamination in Baiyangdian Lake.     

Advanced treatment of dyeing wastewater towards reuse by the combined Fenton oxidation and membrane bioreactor process

The performance of combined Fenton oxidation and membrane bioreactor (MBR) process for the advanced treatment of an effluent from an integrated dyeing wastewater treatment plant was evaluated. The experimental results revealed that under the optimum Fenton oxidation conditions (initial pH 5, H 2 O 2 dosage 17 mmol/L, and Fe 2+ 1.7 mmol/L) the average total organic carbon (TOC) and color removal ratios were 39.3% and 69.5% after 35 min of reaction, respectively. Results from Zahn-Wallens Test also represented that Fenton process was effective to enhance the biodegradability of the test wastewater. As for the further purification of MBR process, TOC removal capacity was examined at different hydraulic retention times (HRT) of 10, 18 and 25 hr. Under the optimum HRT of 18 hr, the average TOC concentration and color of the final MBR effluent were 16.8 mg/L and 2 dilution time, respectively. The sludge yield coefficient was 0.13 g MLSS/g TOC and TOC degradation rate was 0.078 kg TOC/(m 3 ·day). The final effluent of MBR can meet the reuse criteria of urban recycling water-water quality standard for miscellaneous water consumption GBT18920-2002.