珠江三角洲流域土壤多溴联苯醚(PBDEs)的分布及环境行为

用索式抽提、复合硅胶/氧化铝层析柱分离纯化、GC-MS分析方法分析了珠江三角洲流域土壤中10种多溴联苯醚(BDE-28、-47、-66、-99、-100、-153、-154、-138、-183、-209)在土壤中的质量分数和组成分布.∑9PBDEs(不包括BDE209)的质量分数从0.133 ng·g-1干物质量到3.81 ng·g-1干物质量,平均质量分数为1.02 ng·g-1干物质量,BDE-209的质量分数从2.38ng·g-1干物质量到66.6 ng·g-1干物质量,平均质量分数为13.8 ng·g-1干物质量,与欧洲背景土壤中PBDEs的质量分数水平相当.同系物的组成分布说明珠江三角洲土壤中多溴联苯醚的污染来源主要是五溴、八溴及十溴产品的使用.土壤中∑9PBDEs和各同系物的含量与土壤总有机碳(TOC)的含量呈现显著的正相关.有机碳均一化后BDEs单体含量的对数与其log Kow正相关(除-47,r2=0.89),表明土壤有机质的吸附决定着PBDEs在环境中的分布和迁移.     

几种可利用多氯联苯和多溴联苯醚植物内生菌的分离及初步鉴定

采用PDA、NA以及高氏一号培养基,分别从毛白杨、绦柳、荻以及二穗短柄草植株内分离、纯化出37株内生菌,其中34株为细菌,3株为放线菌.以分离纯化得到菌株各自对应的营养培养基并添加不同浓度的污染物对获得的37株内生菌进行污染物的耐受筛选,发现24株分别对20 mg·L-1的aroclor1254和BDE209具有一定的耐受性.利用无机盐培养基并添加污染物作为微生物唯一碳源筛选,发现菌株CPY-4和菌株SGL-1可以在只提供4-BDE的无机盐培养基中存活,菌株CPY-4,SGL-1、菌株4、菌株13可以在提供BDE209和aroclor1254的无机盐培养基中存活.形态学观察和16Sr DNA序列同源性分析,初步确定菌株SGL-1为克雷伯氏菌属,菌株CPY-4为地衣芽胞杆菌,菌株4和菌株13为肠杆菌属.     

沉积物中多溴联苯醚的测定

采用索氏抽提、多层硅胶氧化铝复合柱净化和GC-NCI-MS检测对沉积物中的多溴联苯醚(PB-DEs)进行定量分析,以建立沉积物中多溴联苯醚的分析方法,指示物回收率为69．1％-118．3％,绝大多数目标化合物的回收率为65％-114％,沉积物样品的平均标准偏差为12．7％。     

典型电子废物集中处置场地及周边土壤中多溴联苯醚的污染特征

采用快速溶剂萃取-凝胶净化-气相色谱质谱法(GC-MS)测定了浙江省台州市某典型电子废物集中处置场地及周边土壤中多溴联苯醚(poly brominated diphenyl ethers,PBDEs)浓度,研究了8种PBDEs(BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183、BDE-209)的浓度水平、组成特征和垂直分布规律.结果表明,BDE-209污染与其他几种PBDEs污染之间具有很大的关联性;BDE-209是主要污染物,占8种PBDEs总含量的90%左右;处置场地内8种PBDEs的浓度高于其周边土壤,其平均质量含量分别为0.625和0.209 mg·kg-1;随着与场地集中区域中心距离的增加,PBDEs总含量呈逐渐下降趋势.     

电子废弃物拆解地水体多溴联苯醚分布特征

为了解和比较广东贵屿电子废弃物拆解地和珠三角城市地区水体中多溴联苯醚的种类、含量及分布特征,于2011年9月在广东贵屿周边地区和广州采集了20个地下水、7个地表水和4个珠江水,用反相C18萃取小柱提取净化后,利用气相色谱-质谱法测定了样品中的8种多溴联苯醚（PBDEs）。研究结果表明：贵屿地区地下水中PBDEs浓度总体上较高,总质量浓度范围为2.54~71.74 ng·L-1,平均为22.97 ng·L-1,各类PBDEs的检出率为25%~95%。三溴联苯醚（BDE28）、四溴联苯醚（BDE47）、五溴联苯醚（BDE99和BDE100之和）、六溴联苯醚（BDE153和BDE154之和）、七溴联苯醚（BDE183）和十溴联苯醚（BDE209）的质量浓度分布分别为nd~0.64、nd~18.43、nd~25.26、nd~13.92、nd~9.06和nd~15.60 ng·L-1。从物种上来看,分别源于四溴、五溴和十溴联苯醚产品的BDE47、BDE99和BDE209是贵屿地区地下水样中的优势同系物。通过比率P=（BDE47＋BDE99）/BDE209研究发现：低溴代联苯醚比高溴代联苯醚更易被地表径流迁移转换进入到地下水中。贵屿地区地表水中PBDEs的质量浓度范围为3.41~63.83 ng·L-1,平均总质量浓度为19.38 ng·L-1,稍低于当地地下水中PBDEs的平均总质量浓度,PBDEs的组成以高溴代的BDE209为特征,与世界其他水体研究结果相比,可以发现贵屿地区的地表水中PBDEs的平均总质量浓度明显偏高,说明该地区的地表水受到较严重的PBDEs污染,必须引起足够的重视。珠江水中PBDEs的总质量浓度范围为3.48~20.84 ng·L-1,平均为10.39 ng·L-1,表明近年来珠江水体中PBDEs污染有逐渐恶化的趋势。     

多溴联苯醚代谢产物的合成

通过偶合、氧化、溴化、甲基化等基本有机反应,合成制备了40种羟基(或甲氧基)-多溴联苯醚标样,并通过色谱-质谱(GC-MS)和氢谱核磁共振(1H-NMR)对产物的结构进行了测试与表征.结果表明,合成制备的产物与设计的目标产物结构完全一致,且纯度达到99%以上.     

塑料企业周边水体中多溴联苯醚的污染特征

多溴联苯醚(PBDEs)是一种新型的持久性有机污染物(POPs)。采用固相萃取-气相色谱法测定了某塑料企业周边及当地自然水体中的PBDEs浓度,主要针对BDE~(-1)7、28、47、66、85、99、100、138、153、154、183、203及BDE-209共13个PBDE同系物的浓度水平、组成分布和污染特征进行分析。结果显示,使用企业周边水体中除BDE-203在水体中未检出外,其余12种PBDE同系物均有不同程度的检出。Σ13PBDEs质量范围处于未检出~363 ng·L~(-1),各同系物的平均质量浓度为未检出~42.6ng·L~(-1)。其中BDE-209为最大检出质量丰度同系物,但其检出率仅为25.0%,检出率较高的同系物是BDE~(-1)7、BDE-28和BDE~(-1)00,检出率分别为75.0%、75.0%、58.3%,低溴代联苯醚的检出率显著高于高溴代联苯醚。当地自然水体中13种PBDEs均有不同程度的检出,检出浓度在0.161~1.83 ng·L~(-1)。企业周边水体中PBDEs的污染水平显著高于自然水体,是自然水体浓度的5~100倍。因此,企业周边区域水体中PBDEs的污染情况应引起相关部门关注。     

室内环境中多溴联苯醚的污染特征和暴露风险研究进展

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一类常见的溴代阻燃剂,具有生育毒性、生殖毒性以及致癌性等慢性毒性.作为典型的溴代阻燃剂,多溴联苯醚常被加入到各种产品中以提高产品的安全性,但在各种商业产品的使用过程中,多溴联苯醚会不可避免地逸出至室内环境中,存在于空气或者灰尘中被人体摄入.研究表明,人类一生有80%—90%的时间处于室内环境中,因此,通过了解目前室内环境中多溴联苯醚的污染现状,进而评估通过室内环境暴露多溴联苯醚对人体的潜在危害极为重要.本文总结了室内环境中多溴联苯醚的浓度水平、组成特征以及人体暴露风险,并对未来的研究提出建议.     

降尘中多溴联苯醚及有机氯农药的分析方法

利用硅胶吸附色谱和凝胶渗透色谱结合净化的方法,实现了对降尘中有机氯农药和多溴联苯醚的同时分离净化,有效地避免了降尘中干扰物质对有机氯农药和多溴联苯醚检测时产生的干扰.在优化的条件下,浮尘样本中有机氯农药和多溴联苯醚的添加回收率分别在65.8%—115%和58.6%—112%之间,检测限分别在0.002—0.011 n·...     

上海市受纳污水河流中多溴联苯醚的生态风险评价

以上海市某污水处理厂出水及其受纳河流为研究对象,测定了19种多溴联苯醚(PBDEs)同系物的浓度和分布特征,估算了污水处理厂PBDEs的年度排放负荷,并初步评价了受纳污水河流PBDEs的生态风险水平.结果表明,污水、河流水体及沉积物中PBDEs的总浓度分别为5050 pg.L-1、1310 pg.L-1和3.8 ng.g-1干重,其中BDE-209为主要成分.在排污口下游,PBDEs并没有随距离的增加而明显降低.该污水厂每年通过污水排放的五溴、八溴和十溴联苯醚分别为2.2、5.1和56.2 g.生态风险评价表明,目前该污水厂污水受纳河流中PBDEs导致的生态风险较低.     

Photocatalytic degradation of polybrominated diphenyl ethers in pure water system

Due to the low water solubility of polybrominated diphenyl ethers, organic solvent is usually added into the oxidation system to enhance the removal efficiency. In this study the photocatalytic degradation of decabromodiphenyl ether (BDE209), a type of polybrominated diphenyl ether used throughout the world, in pure water without the addition of organic solvent was investigated. In the pure water system, BDE209 was not dissolved but dispersed as nano-scale particles with a mean diameter of 166 nm. Most of BDE209 (>98%) were removed within 4 h and the final debromination ratio was greater than 80%. Although the addition of organic solvent (tetrahydrofuran, THF) could lead to a relatively high BDE209 degradation rate, the final debromination ratio (<50%) was much lower than that in pure water system. Major oxidation intermediates of tetrahydrofuran, including tetrahydro-2-furanol and γ-butyrolactone, were detected indicating the engagement of THF in the BDE209 degradation process. The photocatalytic degradation of BDE209 in the pure water system followed first-order kinetics. The BDE209 degradation rate constant increased from 0.0011 to 0.0023 min⁻¹ as the pH increased from 3 to 9.     

Removing polybrominated diphenyl ethers in pure water using Fe/Pd bimetallic nanoparticles

Polybrominated diphenyl ethers (PBDEs) have been widely used as fire-retardants. Due to their high production volume, widespread usage, and environmental persistence, PBDEs have become ubiquitous contaminants in various environments.Nanoscale zero-valent iron (ZVI) is an effective reductant for many halogenated organic compounds. To enhance the degradation efficiency, ZVI/Palladium bimetallic nanoparticles (nZVI/Pd) were synthesized in this study to degrade decabromodiphenyl ether (BDE209) in water. Approximately 90% of BDE209 was rapidly removed by nZVI/Pd within 80 min, whereas about 25% of BDE209 was removed by nZVI. Degradation of BDE209 by nZVI/Pd fits pseudo-first-order kinetics. An increase in pH led to sharply decrease the rate of BDE209 degradation. The degradation rate constant in the treatment with initial pH at 9.0 was more than 6.8 × higher than that under pH 5.0. The degradation intermediates of BDE209 by nZVI/Pd were identified and the degradation pathways were hypothesized. Results from this study suggest that nZVI/Pd may be an effective tool for treating polybrominated diphenyl ethers (PBDEs) in water.     

五氟苯甲酰氯衍生色谱法分析水体中痕量羟基多溴联苯醚

以五氟苯甲酰氯(PFBCl)作为衍生化试剂,气相色谱-电子捕获检测器(Gas chromatography-electron capture detector,GC-ECD)为检测手段,建立了水体中痕量羟基多溴联苯醚(Hydroxylated polybrominated diphenyl ethers,简称OH-PBDEs)的酰基化衍生-GC/ECD检测方法.通过实验讨论了衍生化缓冲溶液、衍生化时间以及衍生后萃取溶液异辛烷的用量对检测结果的影响,确定了最佳的衍生化条件.在最佳的衍生化条件下,4-OH-BDE 42、4’-OH-BDE 49、6-OH-BDE 47、2’-OH-BDE 68和6’-OH-BDE 99的衍生化产物均获得了良好的分离度和色谱响应值.本方法的仪器检出限为0.02—0.14 pg,方法检出限为0.61—4.67 pg.L-1,标准曲线线性相关系数的范围为0.9973—0.9996,相对标准偏差均小于10%.3种采自大连市不同地区环境水样的加标回收率检测结果表明,所建立的分析方法适于水体中痕量OH-PBDEs的检测.     

Distribution of polychlorinated biphenyls and polybrominated diphenyl ethers in soils of a previous E-waste processing center

Surface soil samples were taken from a previous electronic waste (E-waste) recycling centerin Taizhou area, Zhejiang province, China. Concentrations, profiles, and possible sources of 19 polychlorinated biphenyls and 7 poly-brominated diphenyl ethers were analyzed to assess their current state in the soil after phase out of massive dismantling of E-wastes. The concentrations of the 7 polybrominated diphenyl ethers ranged from 11 to 128 µg kg^?1 with an average of 41 ± 10 µg kg^?1 (dw), with 2,2′,4,4′-tetrabromdiphenyl ether being the most abundant. These values were substantially lower than the levels in 2006. The concentrations of the 19 polychlorinated biphenyls ranged from 36 to 760 µg kg^?1, with an average of 181 ± 68 µgkg^?1 (dw) which was also lower than the levels in 1995 or 2006. However, the concentrations of some tetra-, penta- and hexa-chlorobiphenyls were comparable or even higher than before. Furthermore, the average concentration of 7 indicator polychlorinated biphenyls was 108 ± 41 µg kg^?1(dw) which exceeded the New Dutch List target value of 20 µgkg^?1. Principal component analysis indicated that polychlorinated biphenyls were mainly distributed into three groups in accordance with the number of chlorine atoms and anthropogenic source. Therefore, the impact of the historical dismantling of E-wastes is still significant.     

多溴联苯醚、六溴环十二烷和四溴双酚A在环境中污染现状的研究进展

作为最主要的三大传统溴系阻燃剂(BFRs),多溴联苯醚(PBDEs)、六溴环十二烷(HBCD)、四溴双酚A(TBBPA)具有半挥发性、环境持久性和远距离传输性,目前在全球各种环境介质、生物体内广泛存在.毒理学研究表明,PBDEs、HBCD、TBBPA均具有明显的生物毒性和致癌性,对生态环境和人体健康存在潜在危害.本文简...     

多氯联苯复合污染土壤的微生物群落结构多样性变化

土壤微生物群落结构多样性是指示土壤生态系统稳定性及其功能的重要传感器。采用磷脂脂肪酸(Phospholipid fatty acids,PLFAs)方法,对长江三角洲地区某POPs高风险区PCBs长期复合污染土壤的微生物群落结构多样性进行了初步研究。结果表明,PCBs重度污染土壤中格兰氏阴性菌(16:1w9、cy17:0等)和厌氧微生物(18:1w7)的PLFAs组分含量较多,而格兰氏阳性菌(如i15:0、i17:0等)、放线菌(16:0(10Me))及真菌(18:2ω6,9)和好氧性微生物的PLFAs含量较低,表明PCBs污染土壤中微生物群落结构与组成发生了明显变化。这一结果为PCBs降解微生物资源的定向筛选提供了科学依据。     

Trophic transfer of polybrominated diphenyl ethers and polychlorinated biphenyls in a tidal freshwater marsh

The John Heinz National Wildlife Refuge (NWR) at Tinicum Marsh contains one of the last remaining tidal freshwater marsh communities along the Pennsylvania side of the Delaware River Estuary. The marsh receives a significant load of nutrients and sediment-associated contaminants and is hypothesised to act as an effective trap for these chemicals. The goal of this study was to quantify the levels of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) at various trophic levels at two sites within Tinicum Marsh and assess the factors important in determining their bioaccumulation and trophic transfer. For both PCBs and PBDEs, lipid variation for all species was a large factor in determining contaminant body burden. Also, concentrations in biota increased with increasing trophic level as determined by nitrogen isotope analysis (δ¹⁵N values) at the downstream site within Tinicum Marsh. This trend was less apparent at the upstream site and may be due to differences in feeding behaviours among species between the two sites and/or differences in carbon and nitrogen sources and recycling. These data are valuable in assisting bioaccumulation/trophic transfer studies and serve as benchmarks to which future PCB and PBDE concentrations will be compared.     

Remediation of soil heavily polluted with polychlorinated biphenyls using a low-temperature plasma technique

Polychlorinated biphenyls （PCBs） were removed by low-temperature plasma technique （dielectric barrier discharge） from heavily polluted soil and their intermediate products were analyzed. The removal rate ranged from 40.1 to 84.6% by different treatments, and they were also influenced significantly （P 〈 0.01） by soil particle-size, electric power, gas flow rate and reaction time. The optimal reaction conditions of PCB removal from the soil were obtained experimentally when soil particle-size, electrical power, flow rate and reaction time were 5-10mm, 21w, 120mL. rain and 90rain, respectively. However, decreasing electrical power, flow rate and reaction time to 18 w, 60 mL. min- and 60 min respectively were also acceptable in view of the cost of remediation. This technique was characterized by the additional advantage of thorough oxidation of PCBs in the soil, with no formation of intermediate products after reaction. The technique therefore shows some promise for application in the remediation of soils contaminated with persistent organic pollutants in brown field sites in urban areas.