Dechlorination of 2,2＇,4,4＇,5,5＇-hexachlorobiphenyl by thermal reaction with activated carbon-supported copper or zinc

Activated carbon （AC）-supported copper or zinc made from ion exchange resin （IRCu-C and IRZn-C） have an increased metal load of 557.3 mg·g^-1 and 502.8 mg·g^-1 compared to those prepared by the traditional method involving impregnation with AC and copper （II） citrate or zinc citrate solution （LaCu-C and LaZn-C） of 12.9 mg·g^-1 and 46.0 mg·g^-1 respectively. When applied to decompose 2,2＇,4,4＇,5,5＇-hexachlorobiphenyl at 250 ℃, IRCu-C achieved higher activity of 99.0% decomposition efficiency than LaCu-C of 84.7%, IRZn-C of 90.5% and LaZn-C of 62.7%. When the reaction temperature rose to 350 ℃, all the four kinds of reactants can decompose PCB- 153 with efficiency above 90%. Further, X-ray photoelec- tron spectroscopy characterization of IRCu-C before and after the reaction indicated transformation of 19.1% of Cu atoms into Cu^2＋, illustrating that Cu is the active ingredient or electron donor promoting the decomposition of PCB- 153. The mechanism underlying this process differs from a traditional H donor. However, there is no significant change on the surface of IRZn-C before and after the reaction, suggesting that Zn acts as catalyst during the process of PCB-153 decomposition.     

北部湾潮间带波纹巴非蛤体内石油烃和多氯联苯的分布及风险评价

2011年春季在北部湾沿岸潮间带布设9个站位,采集双壳类动物波纹巴非蛤(Paphia undulata)并测定其软组织中的石油烃(TPH)和多氯联苯(PCBs)含量,研究两种污染物的分布特征、评价其生物质量并对巴非蛤体内残留PCBs可能造成的人体健康风险进行评价.结果表明,各站位TPH和∑PCBs含量范围分别为56.76—199.49μg.g-1和14.19—52.71 ng.g-1(干质量(dw)),就PCBs的组成而言,高氯代PCBs(PCB153、PCB180、PCB194)为优势同族体,所占比重较大.污染指数计算结果显示,除北海西场海域外,各站位的巴非蛤均受到TPH的重度污染,港口区尤为严重;而所有站位的巴非蛤均未受到PCBs污染.健康风险评价结果显示,所有站位的巴非蛤体内PCBs的非致癌风险处于可接受水平(RQ<1),但是,大多数站位的致癌风险指数(0.83×10-6—3.53×10-6)高于可接受的致癌风险低值(1×10-6),而存在一定的潜在致癌风险.     

金属及其氧化物催化降解多氯联苯的研究进展

催化降解因其高的反应速率和降解彻底性,在氯代有机物的削减中得到广泛应用.目前研究较多的催化剂为零价态和氧化态的碱金属和碱土金属、过渡金属及贵金属,包括单金属和双金属两种.这类催化剂表面活性位点多样,在氯代有机物的降解中显示出优异的活性.多氯联苯(Polychlorinated Biphenyls,简称PCBs)是一类有毒难降解的持久性有机污染物.本文阐述了不同价态的单金属和双金属催化剂催化降解PCBs的反应机理,并介绍了影响反应速率和产物选择性的因素.并对金属及其氧化物催化降解PCBs的应用现状做了评述,对该技术的发展进行展望.     

短链氯化石蜡及其环境污染现状与毒性效应研究

短链氯化石蜡是碳链长度为10至13个碳原子的正构烷烃经氯化衍生而成的复杂混合物.作为《关于持久性有机污染物的斯德哥尔摩公约》增列持久性有机污染物(persistent organic pollutants,POPs)中的一类化合物,2008年10月在瑞士日内瓦召开的联合国环境规划署POPs审查委员会的第     

污染地块土壤多氯联苯风险筛选值研究

污染地块土壤多氯联苯（PCBs）污染主要来自含PCBs电力设备封存点的泄漏及非故意产生源,建立土壤PCBs筛选标准是开展PCBs污染地块调查、评估和修复的基础.本研究通过文献分析统计了典型PCBs单体的占比,并基于人体健康风险评估模型推导了污染地块土壤PCBs风险筛选值.结果表明,不同商用PCBs混合物中共平面PCBs总量（∑Co-PCBs）占比为0.01%~16.10%,难以代表PCBs的总体风险水平.研究建立了PCBs总量、指示性PCBs总量（∑Id-PCBs）及∑Co-PCBs等3个指标共同作为土壤PCBs筛选值体系,敏感用地和非敏感用地情景下,PCBs总量、∑Id-PCBs、∑Co-PCBs分别为2.10、0.24、0.03 mg·kg^-1和6.20、0.71、0.09 mg·kg^-1.通过6个含PCBs电容器地下封存点485个污染土壤样品的分析,进一步证明了仅控制∑Co-PCBs将低估PCBs污染风险,采用本研究提出的3个指标进行筛选能够更有效地识别和评估PCBs污染地块的风险.     

环境监测中POPs分析的关键问题与对策

系统介绍了采用EPA8081A与8082方法进行环境样品中持久性有机污染物(POPs)分析的关键问题与对策。包括POPs的气相色谱分析与验证双柱系统,DDT与异狄氏剂在进样系统中的分解及其处理方法,应用目测识别法、手型法与透明复印胶片法等经验方法快速定性多氯联苯(PCBs)、氯丹与毒杀芬等多峰化合物,影响外标法准确定量PCBs、氯丹与毒杀芬等多峰POPs的关键因素,以及质量控制要求。提出应根据中国POPs的环境污染特点,建立相应的POPs标样库与标准图谱库,为中国的POPs污染调查与环境监测提供技术支持。     

搅拌子吸附-热脱附-气相色谱-质谱法分析北京大气中33种多氯联苯

用包覆聚二甲基硅氧烷(PDMS)吸附层的搅拌子作被动大气采样器,建立了搅拌子吸附-热脱附-气相色谱-质谱法(SBSE-TD-GC-MS)分析大气中多氯联苯(PCBs)的方法。优化后的热脱附温度为280℃,热脱附时间为6 min,聚焦冷阱的温度为-40℃,33种PCB单体的热脱附残留比例低于7%。验证了方法的线性、精密度和重复性。标准曲线5个点线性关系良好,33种PCB单体的相关系数r>0.998。方法精密度验证的相对标准偏差(RSD)为0.79%~20.2%(n=8),日内重复性实验的RSD为0.43%~29.8%(n=10),日间重复性实验的RSD为3.20%~29.6%(n=20),方法检出限(LOD)为0.01~2.51 pg,回收率为98%±18%。将建立的方法用于北京大气中PCBs的分析。检出8种PCB单体,质量为2.94~129 pg。在32 d的采样周期内PCB-52、PCB-123、PCB-155一直处于线性吸附阶段,而PCB-1和PCB-3经过了线性吸附阶段、曲线吸附阶段和平衡阶段。研究结果表明,SBSE-TD-GC-MS可以用于大气中PCBs的样品采集和快速分析。     

Formation rates of polychlorinated dibenzofurans and dibenzo-p-dioxins from polycyclic aromatic hydrocarbons, activated carbon and phenol

The formation rates of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from polycyclic aromatic hydrocarbons (PAHs), activated carbon, and phenol were compared. The heat treatment at 300°C of all tested PAH on silica in the presence of CUCl₂ Preferred PCDDs over PCDDs. Perylene reproducibly gave a higher yield of PCDDs than activated carbon gave under the same conditions. The formation rate of PCDDs from perylene could be higher than the values in this study because the residence time of perylene in the reactor is shorter than that of activated carbon. PCDDs were mainly formed from phenol.     

SEMIPERMEABLE MEMBRANE DEVICES USED TO ESTIMATE BIOCONCENTRATION OF POLYCHLORINATED BIPHENYLS1

ABSTRACT: Aquatic organisms passively accumulate hydrophobic organic compounds, such as polychlorinated biphenyls, even when ambient water concentrations of the contaminant are below analytical detection limits. However, contaminant concentrations in tissue samples are subject to an inherently high level of variability due to differences in species, life stage, and gender bioconcentration potentials. Semipermeable membrane devices (SPMDs) were used to sample Aroclor 1254, a mixture of readily bioconcentrated polychlorinated biphenyls (PCBs), in a contaminated wetland near Flat Top, WV. The devices consisted of triolein, a lipid found in fish, enclosed in a polyethylene membrane. SPMDs were deployed in the water column and in direct contact with wetland sediments along a previously identified concentration gradient of PCBs. The devices were retrieved after a 25-day exposure period. Analytes were recovered by dialyzing the devices in nanograde hexane. Hexane dialysates were condensed and analyzed by gas chromatography. All deployed devices sequestered quantifiable amounts of Aroclor 1254. Water-column SPMDs accumulated PCBs far in excess of ambient water concentrations. The devices contacting sediments accumulated PCBs at all sites, though accumulated concentrations did not exceed concentrations in sediment. Patterns of PCB concentration in the devices corresponded to the identified gradient at the site. Results from the water-column SPMDs were used to estimate the concentration of the dissolved, bioavailable fraction of PCBs present in the water column. These concentrations ranged from 0.01 to 0.09 μg/L of bioavailable Aroclor 1254.     

长江口滨岸潮滩动物体中PCBs和OCPs的分布

利用GC-ECD对长江口滨岸潮滩中动物进行研究,分析了PCBs和OCPs(DDTs和HCHs)的含量分布.结果表明PCBs含量水平为43.7～1260.4ng/g,均值为342.5ng/g;DDTs为1.5～159.4ng/g,均值为33.7ng/g;HCHs为0.9～77.0ng/g,均值为13.0ng/g.从空间上看,同种动物对不同污染物的累积和同种污染物在不同动物体内的累积均无明显的规律,但同属种样品则有雄性个体污染物含量高于雌性个体、小个体高于大个体的规律.对动物体内POPs污染进行了初步评价,结果显示:该区动物均不同程度地受到污染,污染已达中等水平.