Photolysis of mono- through deca-chlorinated biphenyls by ultraviolet irradiation in n-hexane and quantitative structure-property relationship analysis

The photolysis of 16 polychlorinated biphenyls （PCBs） （including mono- through deca-chlorinated） in n-hexane was investigated under ultraviolet irradiation using a 500-W high-pressure mercury lamp. Photolysis of PCBs follows pseudo-first-order reaction kinetics, with photolysis rate constants ranging between 0.0011 s^-1 for PCB-52 and 0.0574 s^-1 for PCB-118. The degradation rates of PCBs by high-pressure mercury lamp irradiation were remarkably independent with respect to the degree of chlorination. Furthermore, partial least squares （PLS） models were developed to provide insight into which aspect of the molecular structure influenced PCB photolysis rate constants. It was found that the photolysis rates of PCBs increased with an increase in the net charge on the carbon atom （qc）, （ELUMO-EHOMO）^2, and the Y-axis dipole moment （μy） values, or the decrease in the energy of the second highest occupied molecular orbital （EHOMO-1）, energy of the lowest unoccupied molecular orbital （ELUMO）, ELUMO ＋ EHOMO, ELUMO - EHOMO, most positive atomic charge （q^＋）, and the twist angle of the chlorine atom （TA） values.     

环境样品中多氯联苯的分析技术

作为一种持久性有机污染物,多氯联苯在地球上的分布十分广泛。然而由于多氯联苯在环境样品中残留浓度低、干扰物质多且组成复杂,必须对环境样品进行预处理。目前较为常用的含多氯联苯样品的前处理技术有：溶剂萃取技术、固相萃取技术、固相微萃取技术、超临界萃取技术、微波萃取技术和加速溶剂萃取技术等,分析经过技术处理以后的样品常用的方法有化学分析方法和生物分析方法,化学方法包括气相色谱法,气相色谱质谱分析法等;生物方法有生物传感器测定法、表面胞质团共振检测、以Ah受体为基础的生物分析法和酶联免疫检测法。中国在这方面的研究投入不够,应加大人力、财力和物力的支持,提高环境样品中多氯联苯的检测水平。     

Levels and distributions of polychlorinated biphenyls in sewage sludge of urban wastewater treatment plants

Concentrations of polychlorinated biphenyls (PCBs) have been measured in sewage sludge samples from 8 urban wastewater treatment plants in Beijing, China. The PCB congeners were analyzed by isotope dilution high resolution gas chromatography/high resolution mass spectrometry method. The concentration of PCBs ranged from 65.6 to 157 ng/g dry weight (dw), with a mean value of 101 ng/g dw. The dioxin-like PCB WHO-TEQs (World Health Organization-Toxic Equivalents) of the sludge were lower than 1 pg /g dw. Conse...     

苜蓿根瘤菌对多氯联苯降解转化特性研究

采用溶液摇瓶实验研究了苜蓿根瘤菌(Rhizobium meliloti)对三氯代联苯(2,4,4′-trichlorobiphenyl)单体以及18种多氯联苯(polychlorinated biphenyls,PCBs)混合物的降解转化能力.结果表明,接入苜蓿根瘤菌转化7d后,随着溶液中底物2,4,4′-TCB浓度的增加,该菌株对其的降解能力也逐渐提高,在1.0、5.0、10.0、25.0、50.0 mg.L-1浓度条件下该菌对2,4,4′-TCB的降解率分别为34.0%、48.3%、69.7%、96.0%、98.5%,并且通过气相质谱分析,发现溶液中出现了一些新的代谢产物.同时,苜蓿根瘤菌对不同浓度下18种PCBs同系物混合物的降解能力,随着底物浓度的升高呈现出从低到高,然后降低,并趋于平衡的趋势,其最高降解率可达54.7%,并存在高氯代PCBs向低氯代PCBs的转化过程.     

台州污染区蔬菜中多氯联苯污染特征分析

多氯联苯（polychlorinated Biphenyls,简称PCBs）已成为全球性的重要污染物之一。实验确立了浸泡-超声提取、硫酸硅胶-去活化硅胶-硝酸银硅胶复合层析柱净化、毛细管柱气相色谱法测定植物样品中痕量多氯联苯的方法。对浙江台州地区典型污染点玉露洋村、横街、莄李王村三地的植物样品（卷心菜、南瓜）进行测定,结果显示台州典型污染区内卷心菜中PCBs的浓度范围在5.98~112.36 ng/g,南瓜叶中PCBs平均值达130.70 ng/g,茎中达59.12 ng/g,三地在总体上污染严重。PCBs同系物间的污染水平存在显著差异,二氯联苯残留量大,四氯、五氯、六氯联苯分布较广、残留较高,高氯联苯有少量存在。     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of the cormorants (Phalacrocorax carbo) from Dongting Lake, China

Tissue distribution provides important information regarding the pharmacokinetic behavior of pollutants and is invaluable when analyzing the risk posed to avian species by the exposure to such kind of pollutants. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in muscle, liver, spleen, kidney, stomach, gall bladder, skin, heart, pancreas, intestine and lung tissue extracts of cormorants collected from Dongting Lake, China. Tissue distribution results showed preferential accumulation of PCDD/Fs in both liver and skin. The total concentration of PCDD/Fs ranged from 421 to 5696 pg/g lipid weight. Octachlorinated dibenzo-p-dioxin (OCDD) was the predominant congener in all tissues and contributed between 31% and 82% to all 17 PCDD/Fs in different tissues. The liver/muscle ratios progressively increased with the degree of chlorination of PCDDs, except for OCDD. The relative toxic potential of PCDDs and PCDFs in tissues were calculated using the World Health Organization (WHO) Toxic Equivalency Factors (TEFs) for birds. The concentrations of WHO-toxic equivalent in different tissues ranged between 14.8 and 2021 pg/g lipid weight. These results indicated PCDD/Fs may have been bio-accumulated in cormorant via food-web. Furthermore, when compared with studies reported in the literatures, the PCDD/Fs levels in the cormorant collected from Dongting Lake were still relatively high.     

Distribution of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in surface water and sediments from Baiyangdian Lake in North China

Persistent organochlorine compounds, including hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and polychlorinated biphenyls (PCBs) were analyzed in surface water and sediments from Baiyangdian Lake, North China. Total concentrations of HCHs, DDTs and PCBs in surface water were in the range of 3.13-10.60, 4.05-20.59 and 19.46-131.62 ng/L, respectively, and total concentrations of HCHs, DDTs and PCBs in sediments were 1.75-5.70, 0.91-6.48 and 5.96-29.61 ng/g dry weight, respectively. Among the groups of HCHs (sum of α-HCH, β-HCH, γ-HCH and δ-HCH) and DDTs (sum of DDT, DDD and DDE), the predominance of β-HCH, DDE and DDD in water and sediment samples was clearly observed. This observation suggested that β-HCH was resistant to biodegradation and the DDTs had been transformed to its metabolites, DDE and DDD. For PCBs, penta-, hexa- and hepta-chlorinated congeners were the most abundant compounds in the both phases. Furthermore, the partitioning of chlorinated compounds between sediment and water was investigated to understand their transport and fates in aquatic ecosystems. The results indicated that average logs of organic carbon-normalized sediment-water partition coefficients (logK_oc') for OCPs varied between 3.20 and 5.53, and for PCBs, logK_oc' values ranged from 3.19 to 5.57. The observed logK_oc' was lower than their equilibrium logK_oc predicted from linear model, which may be attributed to the solubility enhancement effect of colloidal matter in water phase and the disequilibrium between sediment and water.     

滨海城市大气中多氯联苯的污染特征

选取滨海城市厦门的城区、郊区、工业区和背景区为研究对象,于2008年10月至2009年9月对厦门市大气进行了为期四个季节的采样工作,用GC-MS对气相和颗粒相中的28种多氯联苯(PCBs)同系物进行测定。研究结果表明,厦门市PCBs具有明显的时空分布特征,PCBs的含量在66.94～689.59 pg/m3之间,平均值...     

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.     

加速溶剂萃取-气相色谱质谱法测定海洋沉积物中多氯联苯残留

样品采用加速溶剂萃取,萃取液依次经复合硅胶和石墨化炭黑柱净化后,采用GC-MS法测定样品中的多氯联苯残留。结果表明,方法检出限为(0.005～0.038)×10-9(湿重),样品加标回收率为68.5%～108.4%,RSD为2.1%～11.8%。本方法具有提取效率高,净化效果好,回收率高,准确灵敏等优点,可应用于海洋沉积物中多氯联苯等持久性有机污染物残留的监测。