无锡市大气中类二噁英多氯联苯污染水平

为了了解无锡市大气中类二噁英多氯联苯(Dioxin-like PCBs,DL-PCBs)水平,利用大流量空气采样器在无锡市分别采集了6个气相和6个颗粒相大气样品,气相色谱-质谱(GC-NCI-MS)测定样品中12种类二噁英多氯联苯。结果显示,大气样品中∑_(12)DL-PCBs的总浓度(气相+颗粒相)为1157～2 747 fg/m³,平均浓度为1759 fg/m3,平均浓度为1759 fg/m³。其中,气相的浓度为11 124～2 721 fg/m3。其中,气相的浓度为11 124～2 721 fg/m³,平均值为1 701fg/m3,平均值为1 701fg/m³;颗粒相的浓度为26～143 fg/m3;颗粒相的浓度为26～143 fg/m³,平均值为58fg/m3,平均值为58fg/m³。气相中∑_(12)DL-PCB含量占总量的97%,而颗粒相仅占3%。DL-PCBs的总毒性当量(气相+颗粒相)为2.16～4.47fg TEQ/m3。气相中∑_(12)DL-PCB含量占总量的97%,而颗粒相仅占3%。DL-PCBs的总毒性当量(气相+颗粒相)为2.16～4.47fg TEQ/m³,平均值为3.53fg TEQ/m3,平均值为3.53fg TEQ/m³。DL-PCBs单体中PCB-118的浓度最高,平均占总浓度的54%,其次是PCB-105和PCB-77,PCB+81在所有样品中均未检出。在所有DL-PCBs中,毒性当量浓度的主要贡献者为PCB-126,其平均贡献率为95%,其次为PCB-169,平均贡献率为3%。     

广州市类二噁英-多氯联苯大气沉降通量和组成

研究了广州市4个采样点2005年11月到2006年3月期间的类二噁英-多氯联苯(DL-PCBs)的沉降通量和组成.研究表明,广州市DL-PCBs的平均沉降通量为223pg·m-·2d-1,对应的毒性当量为1.5pg·m-·2d-1.城区DL-PCBs的沉降通量是郊区的1.6倍.各采样点DL-PCBs同系物分布相同,主要的同系物为PCB118、PCB105、PCB77,其平均含量分别为30%、18%和17%.湿季的DL-PCBs的沉降通量高于干季,表明降水对沉降通量影响明显.通过初步的源分析,发现某些含PCBs产品和固体废物焚烧可能是大气中DL-PCBs主要的来源.     

基于大气被动式采样的人体头发中类二(口恶)英多氯联苯暴露的途径

本研究通过分析采集自云南省开远市的13个树皮混合样品和13个相应的头发混合样品中DL-PCBs的水平、同族体分布及相关性,研究了当地人群对DL-PCBs的主要暴露途径.结果表明,云南开远树皮和头发样品中DL-PCBs的含量分别为4.0~88.9 pg·g^-1和4.1~19.3 pg·g^-1,其在当地环境和人体中的污染程度均较轻.树皮和头发样品中主要的DL-PCB同族体均是PCB-118,分别占总含量的48%和61%.树皮样品中DL-PCBs的各同族体具有相同的源,其主要的来源可能是大气的长距离输移.云南开远市居民头发中的PCBs可能来源于内部暴露和外部暴露的综合作用,其中外部暴露对低氯代PCBs的贡献要高于高氯代PCBs.     

四川凉山藏彝青少年头发中多氯联苯污染水平的研究

本研究采用索式提取-气相色谱-质谱(GC-MS)分析了39份来自四川省凉山州藏族、彝族青少年(11~19岁)头发样品中的12种类二英多氯联苯(DL-PCBs)的浓度水平及其同族体组成,并分析了其浓度与民族、食肉和饮奶习惯及性别的相关性.结果表明,头发样品中PCBs的检出率为100%,DL-PCBs的总含量为(102.2±14.3)pg·g-1,含量范围9.6~991.6pg·g-1,表明该地区受到DL-PCBs的污染程度较轻.PCB-77、PCB-105、PCB-118为主要单体,占ΣDL-PCBs的84.7%.凉山州彝族青少年头发样品中的PCBs浓度显著高于藏族,且其浓度与每周食肉、饮奶频次具有相关性(P0.05),表明通过饮食摄取的PCBs可能是造成浓度差异的原因之一.该地区藏、彝青少年女性发样中PCBs浓度显著高于男性(P0.05).     

Determination of 3,4-dichlorinated biphenyl in soil samples by real-time immuno-PCR assay

A real-time fluorescent quantitative immuno-polymerase chain reaction (RT-IPCR) assay was developed for the detection of non-dioxin-like polychlorinated biphenyl (PCB) congener in soil samples. Based on the construction of 3,4-dichlorinated biphenyl (IUPAC PCB12) hapten and its immunogen, the specific polyclonal antibodies (pAbs) to PCB12 was obtained and used to develop a direct competitive RT-IPCR assay. Using the optimized assay, a standard curve for PCB12 was prepared. The linear range for the determination of PCB12 was from 10.0 to 1.0 × 10⁶ fg/mL with a correlation coefficient of 0.98 and a detection limit of 1.53 fg/mL. The RT-IPCR assays were tested for their cross-reactivity profiles using four selected congeners and four Aroclor products. The results for the soil samples correlated with the concentrations of PCBs obtained by gas chromatography/mass spectrometry. This highly specific, sensitive, and robust assay can be applied to on-site tests of PCBs and serve as a model for other pollutant immunoassays.     

Spatial distribution of polychlorinated biphenyls in soil around a municipal solid waste incinerator

The impact of a typical municipal solid waste incinerator (MSWI) on polychlorinated biphenyl (PCB) concentrations in the surrounding soil was studied. Six stack gas samples were taken from the MSWI and 21 soil samples were collected from sampling sites between 300 and 1700 m from the MSWI stack. The total (∑PCB) concentrations of dioxin-like (dl) PCBs and indicator PCBs in the stack gas samples were between 3.41 and 34.3 ng/m3, and the corresponding toxic equivalents (TEQs) ranged from 4.45 to 66.9 pg WHO-TEQ/m3, with a mean of 28.6 pg WHO-TEQ/m3. A total of 2.43 g WHO-TEQ of PCBs per year was calculated to be released into the environment from MSWIs in China. The ∑PCB concentrations in the soil samples ranged from 28.0 to 264.4 pg/g, with mean and median values of 127.6 and 127.7 pg/g, respectively, while the TEQ values were between 0.020 and 0.18 pg WHO-TEQ/g, with mean and median values of 0.074 and 0.062 pg WHO-TEQ/g, respectively. Comparing this study with other studies performed around the world suggest that PCB emission from incinerators has a critical influence on PCB concentrations in the surrounding soil. An exponential function equation is proposed, which indicates a clear decline in ∑PCB concentrations with increasing distance from the stack. A contour map created using an ordinary kriging interpolation technique showed that a limited area (1250 m radius) from the stack was clearly influenced by PCB emission from the MSWI.     

长江中游干流及22条支流表层水中多氯联苯的分布特征及其潜在风险

采用GC/MS/MS技术对长江中游重庆至宜昌段22条支流和干流的47个表层水样进行分析.实验发现支流表层水样中PCB8、28、52和118是优势污染物,而干流表层水样中PCB8和28是优势污染物.ΣPCBs在支流和干流表层水样中的几何均值分别为20.71 ng.L-1和13.25 ng.L-1,ΣPCBs最高检出浓度61.79 ng.L-1出现在支流壤渡河,最低浓度3.77 ng.L-1出现在支流草塘河;85%的支流表层水样中ΣPCBs的浓度高于美国环境保护署制定的连续暴露基准浓度14 ng.L-1,但所有支流和干流水样中ΣPCBs的检出浓度都远低于国家饮用水标准限值500 ng.L-1;实验结果与国内外相关文献报道值相比较,也显示该研究区域表层水中PCBs浓度处于较低水平,癌症风险评价结果表明饮用支流和干流的水因摄入PCBs而带来的风险分别为2.07×10-7和1.33×10-7,说明研究区水样中因PCBs污染引起的癌症风险较低.     

短链脂肪酸对太湖底泥多氯联苯微生物厌氧脱氯的影响

选取二氯联苯PCB5和PCB12、四氯联苯PCB64和PCB71、类二噁英五氯联苯PCB105和PCB114、六氯联苯PCB149和PCB153、七氯联苯PCB170,考察了添加7.5mmol/L乙酸和7.5mmol/L混合酸（乙酸：丙酸：丁酸=1：1：1）条件下,9种典型商业多氯联苯单体在太湖底泥厌氧微环境中24周内的脱氯降解情况.结果表明：乙酸和混合酸的添加均在一定程度上强化了多氯联苯的降解,多氯联苯总浓度降低速率由（0.276±0.023） mg/（kg·week）分别加快至（0.383±0.033）和（0.410±0.036） mg/（kg·week）;提高了部分脱氯路径的相对反应速率,特别是单侧氯取代的对位脱氯,但未改变脱氯微生物对多氯联苯降解底物的选择性及主要脱氯路径;进一步降低了体系类二噁英多氯联苯总毒性当量（TEQ）,24周降幅均在95%以上;乙酸和混合酸所起到的促进效果并无显著性差异.     

济南市道路尘中类二噁英类多氯联苯残留情况

通过采集济南市区主要路段道路尘样品,用气相色谱-电子俘获检测器(GC-ECD)方法分析了济南市区主要路段道路尘中毒性较高的12种类二噁英类多氯联苯(DL-PCBs)的残留情况,并对样品中DL-PCBs的含量、污染水平及同系物的组成进行了详细研究。结果发现,DL-PCBs在各采样点均有检出,残留总浓度在0.20～22.84ng/g(干重)范围内,平均值为0.0051ng/kg,同系物PCB81的检出率最高为90%,而同系物PCB189未被检出。计算的毒性当量(TEQ)值显示,对毒性当量贡献最大的是同系物PCB126,其TEQ值高达117.100pg/g(干重)。由平均残留百分含量较大的同系物结构分析可知,济南市区主要路段道路尘中非邻位氯取代的剧毒类二噁英类PCBs含量相对较大。     

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...     

废弃电容器封存点及旧工业场地多氯联苯的污染特征

研究了四川资阳机车厂废弃电力电容器封存点与旧工业场地土壤与降尘中28种多氯联苯（PCBs）的污染水平与组成特征.电容器封存山洞未封闭洞口处土壤中PCBs含量最高,28种PCBs的总含量（ΣPCBs）达227 502 ng.g-1,铸铁车间窗台降尘中也有高残留的PCBs,ΣPCBs在10μg.g-1以上,封存点和铸铁车间样品中PCBs单体含量之间均存在显著的正相关关系（P〈0.01）.高污染样品中PCBs的同族体分布均以四氯代PCBs为最高,其次为三氯代PCBs和五氯代PCBs.与封存点土壤相比,铸铁车间样品中高氯代PCBs的贡献更大.12种类二英PCBs的毒性当量（TEQ）介于75.43～24 027 pg.g-1之间,远大于电子垃圾拆解区土壤,但普遍都以PCB126的毒性当量贡献占绝对优势.     

典型钢铁厂周边土壤中多氯联苯分布特征研究

钢铁厂中各工业热过程车间都会产生污染物并对周边环境造成危害,本文以迁安市钢铁厂周边土壤为研究对象,对该市内及钢铁厂周边土壤样品进行采集,采用同位素稀释高分辨气相色谱-高分辨质谱方法(HRGC/HRMS)测定了多氯联苯(PCBs)的含量,研究了PCBs的同类物分布特征.结果发现,市内及钢铁厂周边土壤样品中dl-PCBs的总含量为4.77~462.04 pg·g~(-1),WHO-TEQ(Toxic Equivalent Quantity)即毒性当量值为0.03~1.34 pg·g~(-1).由此可以看出,该市及钢铁厂周边环境土壤受到了PCBs等有毒污染物的影响.大部分土壤样品的同类物分布特征相似;PCB~(-1)18对土壤dl-PCBs含量贡献率最大,贡献率为34%.PCB~(-1)01对土壤指示性PCBs含量贡献率最大,贡献率为42.5%.同时,通过对样品中同类物分布可以看出,低氯代的同类物(Tr CBs~Hx CBs)的含量要远高于高氯代同类物(Hp CBs~De CBs).     

洞庭湖不同营养级鱼组织中PCBs的分布特征

采用稳定同位素分析技术和气相色谱-高分辨质谱联用技术,测定了洞庭湖6种鱼组织的稳定氮同位素丰度值（δ¹⁵N值）和多氯联苯（PCBs）的含量,研究了鱼组织中PCBs分布特征及其与营养级的相关性.结果表明,∑PCBs₁₁₅的浓度范围为0.04~9.77ng/g湿重,在鲤鱼性腺组织中最高.毒性当量为：0.0003~2.39pg/g湿重,在鳡鱼脂肪组织中最高.洞庭湖鱼中PCBs的含量处于较低水平.PCB28,52,95,99,101,105,110,118,138,153,155和209在所有组织中检出.Co-PCBs,Ind-PCBs和PCB209具有组织分布特异性.不同计量方式下,鱼组织中PCBs与δ¹⁵N值具有相关性的同类物不同.     

Pollution level and distribution of PCDD/PCDF congeners between vapor phase and particulate phase in winter air of Dalian,China

In December 2009, ambient air was sampled with active high-volume air samplers at two sites: on the roof of the No. l building of Dalian Jiaotong University and on the roof of the building of Dalian Meteorological Observatory. The concentrations and the congeners between vapor phase and particulate phase of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the air were measured. Sample analysis results showed that the concentrations of PCDD/Fs in particulate phase was higher than that in gaseous phase. The ratio of PCDD to PCDF in gaseous phase and particulate phase was lower than 0.4 in all samples. The total I-TEQ value in gaseous phase and particulate phase was 5.5 and 453.8 fg/m³ at Dalian Jiaotong University, 16.6 and 462.1 fg/m³ at Dalian Meteorological Observatory, respectively. The I-TEQ value of Dalian atmosphere was 5.5-462.1 fg/m³ which was lower than international standard, the atmospheric quality in Dalian is better.     

Levels of polychlorinated biphenyls in 1,4-dichlorobenzene mothballs

Although polychlorinated biphenyls(PCBs) are globally recognized pollutant, an understanding of their resources as by-products in chemical industry is poorly investigated. This paper presents data from a study that was conducted in order to determine the extent of PCBs in 1,4-dichlorobenzene(p-DCB) mothballs. Total PCBs and dioxin-like PCBs were detected in five mothball samples. Total PCB concentrations ranged from 328 ng/g to 1798 ng/g, while the levels of WHO-TEQ were between 0.16 pg/g and 13 pg/g. Mean concentrations of total PCBs and WHO-TEQ in the samples were 724 ng/g and 3.2 pg/g, respectively. The highest level of PCB congeners was that of trichlorinated biphenyls(537 ng/g), which maybe due to the relatively low chlorination in the process of p-DCB production. A mechanism of the formation of PCBs from polychlorinated benzene in the presence of chlorine is also suggested. The results suggested that re-estimation on the risk of p-DCB products, especially the products for daily use such as mothballs, is expected.     

Seasonal trend of ambient PCDD/Fs in Tianjin City, northern China using active sampling strategy

The spatial concentrations, seasonal trends, profiles and congener pairs of ambient polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were investigated within a seasonally active sampling scheme during Jun 2008 and Jan 2009 in Tianjin City, northern China. The PCDD/F concentrations ranged 14.2-172 fg I-TEQ/m³ (average 69.3 fg I-TEQ/m³) in summer and (89.8-1.01) × 10³ fg I-TEQ/m³ (average 509 fg I-TEQ/m³) in winter, respectively, except for the E-waste dismantling site where much higher values were observed (1.04 × 10³ fg I-TEQ/m³ in summer and 7.123 × 10³ fg I-TEQ/m³ in winter). The results indicated a significantly seasonal trend with higher TEQ values in winter as compared with summer, which could be related to increased emission sources and seasonal variations of the atmospheric boundary layer height. 2,3,4,7,8-PeCDF was the dominant contributor to the total PCDD/F toxic equivalents, and 2,3,7,8-TCDD was detected at almost all the sampling sites in winter. Most of the similarly substituted PCDD/F congener pairs exhibited high correlations, suggesting that they might have similar environmental fate or sources. But different seasonal and spatial distributions of PCDD/F concentrations indicated that the emission sources might be intermittent.     

重庆市大气二(口恶)英污染水平及季节变化

一年内分季节对重庆市不同功能区大气中二英(PCDD/Fs)污染情况进行了监测研究.结果表明,重庆市大气中PCDD/Fs浓度范围和平均值(以TEQ计)分别为0.017~0.21 pg·m-3和(0.094±0.054)pg·m-3.PCDD/Fs污染水平区域分布和季节变化明显,分别为:商住区>郊区>对照点,冬季>春季>秋季>夏季.其中,冬季时大气中的二英浓度约为夏季时的2.2~4.6倍.主成分分析结果显示,PCDD/Fs同系物分布特征季节变化明显:冬、春季时主要表现为颗粒相中的分布特征,夏、秋季节则主要表现为气相中的.相关性分析表明,PCDD/Fs异构体质量浓度与SO2、NO2、PM10和TSP等常规参数含量大都呈显著正相关,与O3则呈负相关,但未达显著性水平.这表明,重庆大气PCDD/Fs的空间分布和季节变化与SO2、NO2、PM10和TSP等环境空气质量常规指标的分布情况基本一致,重庆大气PCDD/Fs污染与常规污染物的排放源密切相关.     

松花江流域河流沉积物中多氯联苯的分布、来源及风险评价

为查明松花江流域沉积物中多氯联苯(PCBs)分布、来源及污染现状,利用GC-ECD和GC-MS测定松花江流域沉积物中PCBs含量,并运用美国国家环保署法(EPA)、加拿大沉积物环境质量标准(SQG)和潜在生态危害指数法(Er)对沉积物中PCBs生态风险进行评价.结果表明,河流沉积物中均有2～10氯代的PCBs同系物被检出;松花江流域沉积物中PCBs含量介于0.83～125.53 ng.g-1,其中嫩江为0.83～4.44 ng.g-1,第二松花江为12.44～125.53 ng.g-1,松花江干流为1.74～6.25ng.g-1;沉积物中PCBs含量最高的是第二松花江,主要来源于沿江分布的与油漆、绝缘材料等工业品有关的污染源,其它河流沉积物中以二氯联苯为主的PCBs主要来源于大气沉降.3种方法(EPA、SQG、Er)的风险评价显示第二松花江沉积物中的PCBs已达到中等到较强程度的污染,其它河流沉积物中的PCBs暂无生态风险.     

电子垃圾拆解地周边土壤中二(口恶)英和二(口恶)英类多氯联苯的浓度水平

采集了电子垃圾拆解地周边125个点位的151个土壤样品,分析了土壤中4~8氯代二噁英和二噁英类多氯联苯的浓度.表层土壤样品中总二噁英的浓度范围为280~7 010 pg·g-1,平均浓度为1 380 pg·g-1.中层和深层土壤样品中总二噁英的平均浓度分别为表土的63%和38%.表土样品中二噁英毒性当量浓度(以I-TEQ计)范围为1.4~94.8 pg·g-1.根据德国关于毒性当量浓度的指导方针,125个土壤样品中只有19个(15%)可以被认为对人体健康无害,其余85%的土壤需要调查二噁英的来源.如果考虑多氯联苯对毒性当量的贡献,则有98%的土壤需要调查二噁英的来源.主因子分析被用来调查这一地区二噁英的排放源.通过对土壤中二噁英的同系物分布进行分析,发现拆解活动是这一地区热过程二噁英的主要排放源,也是这一地区土壤中二噁英的主要来源.