饲料级硫酸铜中二英类多氯联苯的污染特征及其来源研究

近年来,持久性有机污染物（POPs）对人体和环境带来的危害在世界范围内引起了广泛关注.饲料添加剂已成为畜禽动物养殖过程中必不可少的原料,为探明典型动物饲料添加剂饲料级硫酸铜（CuSO₄）中POPs的来源,本研究分析了饲料级CuSO₄、铜盐产品、蚀刻废液（包括酸性蚀刻废液、碱性蚀刻废液及微蚀废液）、蚀刻液（包括盐酸（HCl）和氧化剂）、硫酸（H₂SO₄）共计79个样品中二英类多氯联苯（DL-PCBs）的污染特征.结果发现,饲料级CuSO₄和铜盐产品中DL-PCBs均以PCB-77、PCB-169和PCB-126为主要检出单体,与其生产原料酸性蚀刻废液中具有完全一致的指纹分布特征,表明其来源的一致性;对于蚀刻液,DL-PCBs仅在工业HCl中有不同程度检出,然而指纹特征（单体组成以PCB-118、PCB-77和PCB-126为主）与其他样品中有所区别.通过主成分分析（PCA）进一步确认表明,工业HCl是蚀刻废液中DL-PCBs的一个重要来源,但亦可能存在其他未知来源.相关研究为去除和控制微量元素饲料添加剂尤其是铜盐产品中DL-PCBs提供了重要的科学依据.     

PCDFs的Ah受体结合能力的定量结构效应关系

应用单苯环氯取代方法取G₁～G₁₀10个分子结构描述符,通过正向逐步线性回归方法构建对于Ah受体结合能力的定量结构-性质相关(QSAR)模型.与有关文献相比,此模型能更好地预测多氯代二苯并呋喃(PCDFs)竞争结合Ah受体logEC₅₀值,各自变量间不存在共线性.模型可以较好地反映PCDFs分子Ah受体结合能力与其分子氯取代位点之间的关系.     

珠江三角洲沉积物中毒害有机物的污染现状及评价

参照美国EPA8000系列方法及质量保证和质量控制(QA/QC),对珠江三角洲河流和河口表层沉积物中的有机氯农药、多氯联苯(PCBs)和多环芳烃(PAHs)进行了定量分析。与世界各地表层沉积物中毒害有机污染物的浓度进行对比,分析了珠江三角洲地区沉积物的污染现状;与国外生态风险评价标准对比表明,广州河段和澳门河口的沉积物为高生态风险区。      

利用紫外光降解多氯联苯(PCBs)的研究进展

本文综述了PCBs在各种溶剂中的紫外光化学反应特性和降解途径 :PCB的光化学反应以氢取代氯的脱氯反应为主 ,除此之外 ,在水或醇等极性溶液中 ,还存在羟基化反应 ;PCB的光化学反应活性与其氯原子的数量和取代位置有关。文章最后还简述了光降解在治理受PCB污染土壤方面的应用     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r ² > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.     

Relative velocities of DNAPL and aqueous phase plume migration

Numerical simulation is used to examine the relative velocities of DNAPL and aqueous phase plumes in sandy aquifers where lateral spreading of DNAPL has occurred at the base of the aquifer. The scenario being modeled is one where a permeable aquifer is underlain by a sloping aquitard, which results in lateral migration of the DNAPL down the slope, in addition to lateral migration of an aqueous phase plume subject to a specified hydraulic gradient. A sensitivity analysis is presented to the impacts of both DNAPL properties and geologic properties. The most important chemical properties governing the relative velocities of the DNAPL and the shallow aqueous phase plume are the DNAPL viscosity and the aqueous component soil-water partition coefficient (Kd). The dip of the underlying aquitard was found to be relatively unimportant, at least for the range of values studied. The scenario under consideration can be important in conceptual model development and remedial design, as in certain cases DNAPL could be migrating in areas without the evidence of a well-developed aqueous phase plume. The implication of this work is that the absence of a shallow aqueous phase plume directly downgradient of a DNAPL source zone does not rule out the possibility of deep occurrences of DNAPL beyond the shallow monitoring well network. A further finding of this study is that the occurrence of a highly sorbing compound in groundwater at virtually any concentration may indicate the immediate upgradient presence of residual or pooled DNAPL.     

Microbial Communities in Composite Biofilms Participating in the Degradation of PCB

A moorland soil site polluted with PCB showed a high diversity ofmetabolically active bacteria. Beside frequent types of 16S rRNAsequences similar to those of the species ofSphingomonasand the Acidobacterium phylum an unusual high number ofsequences from the genus Burkholderia were found. Burkholderia was also the main genus in isolates enriched onbiphenyl or various chlorobenzoates. In microcosm experimentssterilized surfaces exposed to PCB polluted soil always showed thepresence of clay aggregates formed by bacteria attached to thesubstratum. The bacteria use the PCB loaded clay colloids astransport medium for the water insoluble substrate to get accessto the carbon source. This is a novel mechanism of how bacteria dealwith hydrophobic substrates.     

电子垃圾拆解区污染池塘中鱼类多氯联苯及其代谢产物的组织分配及暴露风险

对一受电子垃圾污染池塘内两种鱼类(鲮鱼和乌鳢)体内各组织中多氯联苯(PCBs)及其甲磺基代谢产物(Me SO2-PCBs)进行了分析.鲮鱼和乌鳢体内各组织中总PCBs(ΣPCBs)的平均含量分别为560~10 462 ng·g-1和580~50 492ng·g-1(湿重),两种鱼体内肝脏中的PCBs含量均高于其他组织.PCBs在鱼体组织内的分布与不同组织的脂肪含量有关.鲮鱼和乌鳢体内各组织中ΣMe SO2-PCBs的平均含量分别为0.44~53 ng·g-1和1.86~132 ng·g-1,这一浓度水平比之前国外报道的最高浓度高1个数量级.除PCB149外,鲮鱼体内手性PCB单体的EF值与沉积物相比存在下降趋势;而在乌鳢体内则正相反,在鲮鱼体内已下降的EF值在乌鳢体内则出现回升,有些单体的EF值甚至高于沉积物.这一结果可能表明PCBs在两种鱼体内的手性选择性代谢特征正好相反.鱼体内高含量的ΣPCBs和ΣMe SO2-PCBs对当地居民具有较高的暴露风险,因此,限制这些鱼类在市场的流通对于降低当地居民健康风险具有重要意义.     

环境因子对脱氯功能念珠藻Nostoc PD-2降解多氯联苯过程中基因表达的影响

以分离筛选自多氯联苯污染水稻田中的脱氯功能蓝藻Nostoc PD-2为材料,两种典型的三氯代多氯联苯PCB28和PCB30为目标污染物,在不同的氮源、碳源和培养温度条件下,研究了脱氯功能藻种Nostoc PD-2中双加氧酶基因和细胞色素b6f复合体铁硫蛋白基因的表达情况及两种基因对脱氯作用的影响.结果显示,以硝酸钠作为氮源时,与氮气氮源组相比,PCB28和PCB30降解组中的两种基因均显著上调表达,双加氧酶基因的上调倍数分别为1.9和5.7倍,铁硫蛋白基因的上调倍数分别为1.1和1.7倍;添加碳酸钠时,与对照相比,双加氧酶基因最高上调了2.2倍,铁硫蛋白基因最高上调了3.4倍;提高温度对双加氧酶基因和铁硫蛋白基因的表达均有促进作用.相较于铁硫蛋白,双加氧酶基因相对表达量与PCB28和PCB30的脱氯百分比之间的相关系数分别为0.872和0.832,表明双加氧酶基因活性与功能藻种PD-2脱氯降解PCBs的相关性更高.本研究结果表明,不同环境因子可引起脱氯功能藻种Nostoc PD-2降解PCBs过程中双加氧酶基因和铁硫蛋白基因的差异表达,添加碳源对降解效果的促进作用最明显,脱氯功能藻种在工程应用中采用优化的环境条件有利于提高降解效率.