Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.     

浅谈串联四极杆质谱（GC—QqQ-MS／MS）在土壤样品有机污染物分析中的应用

建立了ASE-GPC—GC-QqQ—MS／MS测定土壤中17种有机氯农药和19种多氯联苯以及MAE-SPE—GC-QqQ—MS／MS测定土壤中16种多环芳烃和18种邻苯二甲酸酯的方法。多环芳烃和邻苯二甲酸酯定量限在0．02～2．81μg／kg之间,有机氯农药和多氯联苯定量限在0．01～0．51μg/kg之间。样品加标浓度在5μg/kg时多环芳烃和邻苯二甲酸酯的平均回收率在66．6％～122．1％之间,相对标准偏差均小于20％;有机氯农药和多氯联苯平均回收率在79．6％～93．2％之间,相对标准偏差均小于15％。     

Monitoring gas- and particulate-phase short-chain polychlorinated paraffins in the urban air of Dalian by a self-developed passive sampler

The concentration of short-chain polychlorinated paraffins(SCCPs) in the urban air of Dalian,China was monitored from September 2016 to August 2017 with a self-developed passive sampler(PAS1) and an active high-volume sampler, simultaneously. PAS1 successfully collected the entire target SCCPs in the ambient air. Air SCCPs sampled by PAS1 were found be in the linear uptake stage during 181 days of sampling. Passive and active samples showed comparable congener profiles, and the dominant contributors of SCCPs in the two kinds of samples were similar. A significant linear correlation was observed between the total concentration of SCCPs sampled by PAS1 and active sampler in the four seasons. The passive sampling rates of the PAS1 for the gas and particulate phases of SCCPs were measured. The quantitative structure–property relationship of the sampling rate of PAS1(Rair) for gas-phase SCCPs was studied. From the molecular point of view, Rairwas mainly affected by the molecular weight and sub-cooled liquid vapor pressure of SCCPs. In general, SCCPs in the urban air of Dalian mainly existed in gas phase,lower molecular weight SCCPs primarily occurred in the gas phase, whereas higher molecular weight SCCPs were predominately adsorbed or absorbed on airborne particles. The air concentration of SCCPs in the four seasons were different, the correlation of the concentration of SCCPs in the air with the meteorology parameters was conducted. The exposure risk by intake air SCCPs of the residents around the sampling sites was evaluated according to the European risk assessment standards.     

中国近海海洋环境多氯联苯(PCBs)污染现状及影响因素

对中国近海海洋环境(水体、表层沉积物和生物体)中多氯联苯(PCBs)的空间分布、污染程度、来源及影响因素进行了总结,得出如下结果:①我国近海海域水体中,PCBs的含量水平呈现由北向南逐渐增加的趋势,以东部沿海工农业发达地区为最高,我国大部分近海海域水体中PCBs都超过美国EPA制定的30 ng·L-1的标准,污染比较严重;②我国近海海域表层沉积物中PCBs只有小部分超过ISQG(interim sediment quality guideline)和ERL(effects range-low)值,引起生物负效应的几率比较小,污染程度较轻;③生物体内富集的PCBs以4、5和6等高氯代联苯为主,其含量都低于《食品中污染物限量标准》2 000ng·g-1,不会对人类健康造成影响.④我国近海海洋环境中PCBs主要来源于周围大型工厂排放的废水以及电子垃圾拆解造成的PCBs泄漏,影响PCBs含量水平的主要因素有距离陆地的远近程度、水流交换情况、水量大小、季节的变化、沉积物颗粒大小、有机碳含量等等.     

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。