岩溶地下水水体中有机氯农药和多氯联苯的残留特征及健康风险评价

采用气相色谱-微池电子捕获检测器（GC-μECD）测定南山老龙洞岩溶地下水水体中有机氯农药（OCPs）和多氯联苯（PCBs）残留量,并探究了OCPs和PCBs的浓度、分布和来源等残留特征.结果表明,OCPs总浓度范围为34.8~623.2 ng·L^-1,均值为215.6 ng·L^-1,其中,HCHs、DDTs和其它类OCPs总浓度范围分别为8.2~23.6、4.5~363.7和22.2~235.9 ng·L^-1,均值分别为15.9、104.5和95.3 ng·L^-1;PCBs总浓度范围为6.0~40.7 ng·L^-1,均值为16.8 ng·L^-1.总体而言,OCPs和PCBs污染处于中上水平;多重比较结果显示部分OCPs和PCBs平均浓度具有统计学意义上的显著差异.研究区各采样点水体中污染水平差异较大,但OCPs和PCBs的季节分布相对均匀.源解析表明,HCHs源于周围环境中林丹的输入;DDTs源于近期工业DDT的非法使用;其它类OCPs源于大气沉降和农业活动输入;PCBs来源既有历史残留,又有企业排污活动;Pearson相关分析表明部分有机卤素污染物具有同源性,或有类似的来源和分解机制.结合健康风险评价模型,研究区饮用水不会对人体健康产生明显危害,但儿童对污染物的敏感性高于成人.     

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.     

东营市孤岛地区土壤中类二噁英类PCBs的污染特征

2011年4月采集了东营市孤岛地区20个表层土壤样品,采用索氏提取-弗罗里土柱净化-气相色谱-电子捕获检测器检测的方法对采集的样品进行测定,揭示了该地区表层土壤中类二英类PCBs(dioxin-like polychlorinated biphenyls,DL-PCBs)的污染特征.结果表明,DL-PCBs的含量范围为1.4～7.4μg·kg-1,平均含量为(3.5±1.7)μg·kg-1;DL-PCBs的毒性当量为1.2～31.8 ng·kg-1,平均值为5.4 ng·kg-1,超过了加拿大土壤环境质量标准(4.0 ng·kg-1).各采样点间DL-PCBs的同系物组成相似,均以四氯联苯和五氯联苯为主,两者之和超过DL-PCBs总量的80%;从孤岛城镇到郊区,DL-PCBs的含量逐渐降低,这与许多化工厂分布在城镇周围有关.相关性分析显示,土壤中DL-PCBs的含量与土壤有机碳含量与黏粒含量显著正相关(R2分别为0.732和0.687,P<0.01),而与土壤砂粒含量负相关(R2=-0.438,P<0.05).     

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.     

中国部分沿海海域水体中溶解态有机氯农药和多氯联苯的残留分布特征

分析调查了中国部分海域海水中溶解态有机氯农药(OCPs,25种)和多氯联苯(PCBs,6种)的残留分布特征。结果表明,所有采样点都不同程度地受到了OCPs和PCBs的污染,其中福建省福州平潭和莆田湄洲岛的OCPs污染较为严重,浓度分别达到1752.59和796.19 ng/L;而辽宁省的大连老虎滩OCPs污染较轻,浓度为53.63 ng/L。各采样点海域海水中HCHs污染程度一般高于DDTs,HCHs主要以早期残留为主;根据DDT/DDTs的比值推测,在福州平潭、莆田湄洲岛和珠海淇澳岛水体显示有新的DDT输入。在各海域水体中溶解态PCBs的浓度为33.55~474.92 ng/L,均超过了美国环保局规定的海水浓度限值。因此目前我国沿海海域水体中持久性有机污染物有机氯农药和多氯联苯污染仍不能忽视。     

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.