饲料级硫酸铜中二英类多氯联苯的污染特征及其来源研究

近年来,持久性有机污染物（POPs）对人体和环境带来的危害在世界范围内引起了广泛关注.饲料添加剂已成为畜禽动物养殖过程中必不可少的原料,为探明典型动物饲料添加剂饲料级硫酸铜（CuSO₄）中POPs的来源,本研究分析了饲料级CuSO₄、铜盐产品、蚀刻废液（包括酸性蚀刻废液、碱性蚀刻废液及微蚀废液）、蚀刻液（包括盐酸（HCl）和氧化剂）、硫酸（H₂SO₄）共计79个样品中二英类多氯联苯（DL-PCBs）的污染特征.结果发现,饲料级CuSO₄和铜盐产品中DL-PCBs均以PCB-77、PCB-169和PCB-126为主要检出单体,与其生产原料酸性蚀刻废液中具有完全一致的指纹分布特征,表明其来源的一致性;对于蚀刻液,DL-PCBs仅在工业HCl中有不同程度检出,然而指纹特征（单体组成以PCB-118、PCB-77和PCB-126为主）与其他样品中有所区别.通过主成分分析（PCA）进一步确认表明,工业HCl是蚀刻废液中DL-PCBs的一个重要来源,但亦可能存在其他未知来源.相关研究为去除和控制微量元素饲料添加剂尤其是铜盐产品中DL-PCBs提供了重要的科学依据.     

北京市密云县潮河周边土壤中类二恶英PCBs分析评价

为了探讨密云水库上游流域可能给水库带来的非点源污染,本研究测定了入库河流潮河下游周边土壤中12种类二恶英多氯联苯(DL-PCBs)的含量水平。结果表明,ΣDL-PCBs的总含量水平为0.0039~0.0365 ng·g-1,其中PCB-118,115,77为12种DL-PCBs的主要成分,PCB-81,114,157均低于检出限。草地、林地和果园中ΣDL-PCBs的含量高于玉米地,表明研究区的DL-PCBs主要受大气沉降和河流沉积物的影响,受当地人类活动影响不大。与其他研究相比,采样区域的PCBs含量总体处于偏低水平,毒性当量处于中等水平。而毒性当量因子(TEF)较高的PCB-126与PCB-169,可能会对人类和生物产生危害,应给予足够的重视。     

加速溶剂萃取—气相色谱法测定土壤中的类二噁英多氯联苯

采用加速溶剂萃取(ASE)—气相色谱法测定土壤中的12种类二噁英多氯联苯。在萃取温度100℃、萃取时间15min、萃取溶剂正己烷与丙酮的体积比1∶1、萃取试样量3g的最佳实验条件下,12种类二噁英多氯联苯的加标回收率为88.5%～109.8%,相对标准偏差为1.1%～6.7%。对小麦田实际土壤试样进行测定,共检出8种类二噁英多氯联苯,含量为50～671pg/g。     

Receptor modeling for analyzing PCDD/F and dioxin-like PCB sources in Hong Kong

A total of 96 ambient air samples were collected from January 2004 to December 2004 for the investigation of dioxins (polychlorinated dibenzo-para-dioxins and polychlorinated dibenzofurans [PCDD/Fs]) and dioxin-like profile for polychlorinated biphenyls (PCBs) in the atmosphere of Hong Kong. Two-day back-trajectories were obtained using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model from National Oceanic and Atmospheric Administration (NOAA) Air Resources Laboratory. Receptor models – potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) – were built based on the measured PCDD/Fs and dioxin-like PCBs total toxic equivalent (TEQ) concentrations. Both models were modified in this study so as to integrate the information obtained from three sampling sites in Hong Kong. The PSCF modeling resolved two main PCDD/F and dioxin-like PCB polluting paths from Mainland China. In line with previous studies, the northerly path around the Pearl River Delta might be one of the pollution sources of Hong Kong air. On the other hand, the receptor models also indicated another potential northeasterly source from Yangtze River Delta, which was seldom mentioned as the source region of Hong Kong air. Results from the CWT modeling suggested that the most toxic air mass affecting Hong Kong is probably attributable to the northeast path rather than the north path.     

Levels and congener profiles of PCDD/Fs and dioxin-like PCBs in Baltic wild salmon (Salmo salar)

Baltic salmons were caught from two Latvian rivers during the spawning seasons of 2010 and 2011 for the determination of seventeen 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (PCBs). A partially automated clean-up procedure was used for sample preparation, followed by capillary gas chromatography hyphenated to high-resolution mass spectrometry. The concentrations of PCDD/F&;PCB-TEQ ranged from 6.6 to 18.2?ng?kg^?1 fresh weight and this confirms the previous reports of relatively high concentrations of PCDD/Fs, and especially of dioxin-like PCBs in Baltic wild salmon, in most samples exceeding maximum recommended levels (MRLs) in toxicity equivalency quotients (PCDD/F-PCB-TEQ) of the World Health Organization (WHO 1998) according to EC COMMISSION REGULATION No 1881/2006. The results suggest that high consumption of Baltic wild salmon could entail the risk of exceeding the TDI for adults and teenagers. Extra care must be taken when Baltic wild salmon is included in childrens's diet to avoid exceedance of the recommended TDI of 4?pg?kg^?1 body weight for this group.     

BAT and BEP as instruments for reducing emissions of unintentionally produced POPs and development of guidelines under the stockholm convention

The 6th Intergovernmental Negotiating Committee (INC 6), under the Stockholm Convention on POPs, gave an expert group the mandate to develop guidelines for the application and implementation of best available techniques (BAT) and best environmental practices (BEP) for the prevention and reduction of unintentionally produced and emitted POPs, including polychlorinated dibenzodioxins/-furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB). Measures to reduce or eliminate the release of these POPs to the environment can be found in Article 5 of the Convention. BAT and BEP are already being applied as emission reduction instruments in a number of industrialised countries and are elements of other major international treaties, e.g. the UN ECE Protocol on POPs and the Marine Convention's OSPAR and HELCOM, and of the EU Directive for Integrated Pollution Prevention and Control (IPPC Directive). Existing concepts are presented and compared with the requirements of the Stockholm Convention. Consequences, perspectives and questions for the future intersessional work of the above-mentioned Expert Group are discussed.     

近海沉积物DlPCBs对斑马鱼胚胎EROD和cyp1a mRNA的影响

为探究湛江近海域海洋沉积物中类二噁英多氯联苯(dioxin-like polychlorinated biphenyls,Dl PCBs)的生物学毒性效应,选取湛江近海域2个地点(近工业区TS和近生活区JSW)采集沉积物样品,制备近海域沉积物Dl PCBs提取物,将斑马鱼胚胎暴露于不同浓度的Dl PCBs提取物,测定斑马鱼胚胎7-乙氧基异吩恶唑脱乙基酶(ethoxyresorufin-O-deethylase,EROD)活性和cyp1a m RNA相对表达量。结果发现,JSW采样点Dl PCBs提取物染毒组EROD酶活性变化与TS采样点Dl PCBs提取物一致,在各染毒浓度下,斑马鱼仔鱼EROD酶活性为对照组的1.1~1.8倍。TS和JSW采样点不同浓度Dl PCBs提取物暴露斑马鱼胚胎96 h后,使斑马鱼仔鱼cyp1a m RNA相对表达量是对照组的3.36~19.45倍。说明一定浓度的近海沉积物Dl PCBs能诱导斑马鱼仔鱼EROD酶活性和cyp1a m RNA表达量升高,且呈现浓度-效应关系。     

Polychlorinated biphenyl (PCB) residues in European roe deer (Capreolus capreolus) and red deer (Cervus elaphus) from north-western Poland

The purpose of this study was to evaluate polychlorinated biphenyls (PCBs) contamination levels in roe and red deer from north-western Poland and to assess environmental pollution in this area. A quantitative analysis was conducted using a capillary gas chromatography/mass spectrometry method. The mean concentrations of ΣPCBs (sum of PCBs: 28, 52, 101, 138, 153, 180) in liver samples were 30.24±12.35 ng·g^?1 of lipid weight (l.w.) in roe deer and 60.13±14.23 ng·g^?1 l.w. in red deer, compared with 24.21±10.02 and 45.22±9.77 ng·g^?1 in the lungs of roe and red deer, respectively. PCBs 138, 153 and 180 were the dominant congeners in the liver samples of the analysed animals, whereas PCB 138 and 153 in the lungs. TEQs levels calculated for only dioxin-like PCBs were low: 0.32 and 0.29 pg WHO-PCB-TEQ·g^?1 fat in liver of red deer and roe deer, respectively. The mean PCB concentrations obtained in our study for organs of roe deer and red deer were several times lower than those reported elsewhere. These findings show that the investigated roe and red deer originated from an area with low levels of PCB contamination.     

现代黄河三角洲土壤特性对多氯联苯分布的影响规律

对现代黄河三角洲22个表层土壤样品中类二嗯英类多氯联苯（PCBs）进行双毛细管柱GC．ECD结合MS测试,并使用相关数学统计学分析方法一相关性研究方法研究了现代黄河三角洲地区土壤特性对PCBs分布的影响,结果表明：土壤有机质量分数与其类二嗯英类PCBs的总质量浓度呈弱的正相关关系。土壤粒径组成中粘粒质量分数与其类二嗯英类PCBs的总质量浓度呈相关性关系,且达到极显著的水平;粉砂粒的质量分数与类二嗯英类PCBs的总质量浓度无相关关系;砂粒质量分数与类二嗯英类PCBs的质量浓度呈负相关关系,达到显著相关的水平。土壤溶解盐质量分数及pH值与类二嗯英类PCBs的总量没有明显的相关性。可见,土壤中有机质、土壤颗粒组成中粘粒和砂粒质量分数是影响现代黄河三角洲地区土壤中PCBs分布的主要因素。     

黄河表层沉积物中类二(口恶)英多氯联苯水平分布

从青藏高原到黄河入海口,采集了黄河流域不同地区15个采样点的表层沉积物,使用GC-MS测定了表层沉积物中类二(口恶)英多氯联苯(DL-PCBs)的浓度水平,黄河流域15个采样点ΣDL-PCBs浓度范围(以dw计,下同)为2.3~14.8 pg·g-1,毒性当量在0.0014~0.0231 pg·g-1之间,平均值为0.0073 pg·g-1,与国内外其他河流的研究相比,黄河沉积物中DL-PCBs水平和毒性当量处于较低水平.黄河沉积物中DL-PCBs同族体主要以四氯代和五氯代为主,其中黄河流经的乡村与经济欠发达地区沉积物中DL-PCBs同族体组分较为相似,而流经工业发达、人口众多地区的沉积物中DL-PCBs同族体分布相似.研究表明石化企业及水利水电设施影响沉积物中DL-PCBs同族体的组成分布,并且黄河表层沉积物中ΣDL-PCBs的浓度与当地人均GDP显著相关,黄河流经经济发达地区的沉积物中的DL-PCBs水平高于偏远地区.