手性多氯联苯在电子垃圾拆解地鱼类体内的分布及累积规律

电子垃圾拆解活动已造成当地鱼类多氯联苯（Polychlorinated Biphenyls,简称PCBs）污染,但手性PCBs在鱼类体内的分布特征和选择性富集则较少有报道.本研究采集了广东省清远市龙塘镇某电子垃圾拆解区附近水塘的鱼类样品,研究鱼肉样品中手性PCBs污染水平、分布规律和对映体选择性.结果表明,在电子垃圾拆解区鱼肉样品中均检测到7种手性PCBs,总PCBs（ΣPCBs）含量为386.7~602.8 ng·g^-1（湿重）,证实当地鱼类已受到手性PCBs的污染.PCB45、PCB91、PCB95、PCB132、PCB136和PCB174在鱼类样品的对映体分数（EF值）与沉积物具有显著差异,表明这些手性PCBs在鱼类体内可能具有对映体选择性富集和代谢作用.不同种类的鱼肉样品中EF值不同,说明它们对PCBs的富集能力不同.鲮鱼、鲫鱼和乌鳢对PCBs的生物/沉积物富集因子（BSAF）分别为0.31~1.71、0.30~1.86和0.50~2.64.根据乌鳢/鲮鱼和乌鳢/鲫鱼食物关系计算的生物放大因子（BMF）范围分别为1.35~4.51和2.17~5.10,表明乌鳢对手性PCBs具有生物放大作用.     

Theoretical study on the formation mechanism of polychlorinated dibenzothiophenes/thianthrenes from 2-chlorothiophenol molecules

Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes(PCDT/TAs),sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans(PCDD/Fs), has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol(2-CTP) as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene(1-MCTA), 1,6-dichlorothianthrene(1,6-DCTA), 4,6-dichlorodibenzothiophene(4,6-DCDT)and 1,6-dichlorodibenzothiophene(1,6-DCDT). The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.     

Prediction of the PCDD/F and dl-PCB 2005-WHO-TEQ content based on the contribution of six congeners: Toward a new screening approach for fish samples?

Current European Union regulation regarding polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in food and feed is based on Toxic Equivalent Quotient (TEQ) concept. For confirmatory purpose, the isotope-dilution method associated to a measurement by gas chromatography coupled with high resolution mass spectrometry is usually the method of choice for precisely measuring the 29 target congeners in three separated fractions. Time and cost related to these analyses are very significant. Various kinds of screening concepts can be considered. In the present study, we elaborated and validated a prediction model for the 2005 World Health Organization TEQ in fish, based on the measurement of 4 PCDD/F and 2 non-ortho dl-PCB congeners, potentially analyzable in a single extracted fraction by gas chromatography coupled with mass spectrometry. Large independent datasets have been used for model elaboration (n = 108) and validation (n = 363, n = 357 and n = 6).     

Polybrominated diphenyl ethers, polychlorinated naphthalenes and polycyclic musks in human fat from Italy: Comparison to polychlorinated biphenyls and organochlorine pesticides

Prior to this study, reports of occurrence of polycyclic musks and polychlorinated naphthalenes (PCNs) in human tissues from Italy were not available. In this study, concentrations of PCNs and polycyclic musks were determined in human adipose tissue from Italy collected during 2005-2006; for comparison, legacy organohalogen pollutants such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined. ΣPCN concentrations ranged from 0.5 to 14 ng/g lipid wt (lw). Polycyclic musks such as HHCB and AHTN were found in 92% and 83% of the human samples, respectively. Concentrations of PBDEs in Italian adipose tissue ranged between 3.2 and 35.6 ng/g lw.     

Organochlorine pesticides and polychlorinated biphenyls in riverine runoff of the Pearl River Delta, China: assessment of mass loading, input source and environmental fate

A large-scale sampling program was conducted to simultaneously collect water samples at the eight major riverine runoff outlets of the Pearl River Delta (PRD), South China to assess the importance of riverine runoff in transporting anthropogenic pollutants from terrestrial sources to the coastal ocean. The concentrations of ∑₂₁OCPs (sum of 21 OCP components) and ∑₂₀PCBs (sum of 20 PCB congeners) were 2.57-41.2 and 0.12-1.47 ng/L, respectively. Compositional distributions of DDTs suggested the possibility of new input sources in the study area, but contributions from dicofol seemed considerably low. The annual inputs of ∑₂₁OCPs and ∑₂₀PCBs were 3090 and 215 kg, with those of total HCHs and DDTs being 1110 and 1020 kg, respectively. A mass balance consideration indicated that riverine runoff is the major mode carrying OCPs from the PRD to the coastal ocean, and the majority of OCPs is further dissipated to open seas.     

Decomposition of 2,2',4,4',5,5'-hexachlorobiphenyl with iron supported on an activated carbon from an ion-exchange resin

An activated carbon (AC) containing a high concentration (374 mg g⁻¹) of Fe was prepared by carbonization of an ion-exchange resin. To examine its chemical reactivity as a catalyst to decompose 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB-153), the decomposition parameters of temperature and time were varied under air or N₂. Decomposition at 350 °C was achieved within 15 min under air and 30 min under N₂, and the efficiency of PCB-153 decomposition was 99.7% and 98.0%, respectively. An analysis of inorganic chloride ions revealed that PCB-153 was mineralized effectively during the decomposition. The Brunauer-Emmett-Teller (BET) surface area and pore volume of the AC were measured to assess the adsorption capacity before and after the decomposition. The differences between decomposition under air and N₂ reflected the differences in the BET surface and pore volume measurements. A decomposition pathway was postulated, and the reactive characteristics of chlorine atoms loaded on the benzene rings followed the order of para > meta > ortho, which agrees with the calculated results from a density functional theory study.     

Assays of PCB congeners and organochlorine insecticides with the transgenic Arabidopsis and tobacco plants carrying recombinant guinea pig AhR and GUS reporter genes

Certain congeners of polychlorinated biphenyls (PCBs) and organochlorine insecticides are ligands of aryl hydrocarbon receptors (AhRs) in animals. A recombinant guinea pig (g) AhR, XgDV, was constructed by fusing the ligand-binding domain of gAhR, the DNA-binding domain of LexA, and the transactivating domain of VP16. Then, the expression unit of β-glucuronidase (GUS) reporter gene regulated by XgDV was introduced into Arabidopsis and tobacco plants. When the transgenic Arabidopsis XgDV plants were cultured on Murashige–Skoog (MS) medium containing PCB congeners, the GUS activity in the plants increased toxic equivalent (TEQ)-dependently. The GUS activity in the transgenic Arabidopsis XgDV plants cultured on MS medium containing the organochlorine insecticide dieldrin was also induced. On the other hand, in the case of DDT, the GUS activity induced by 3-methylcholanthere in the plants decreased. The transgenic Arabidopsis XgDV plants detected 1000 ng g^?1 PCB126 in 1 g of soils. Thus the XgDV plants seemed to be useful for convenient assays of PCB congeners and organochlorine insecticides, without any extraction and purification steps.     

气相色谱法同时测定水中28种多氯联苯单体

采用液液萃取-浓硫酸磺化净化-气相色谱电子捕获检测器同时测定水中28种多氯联苯单体,必要时利用质谱选择离子监测模式定性,考察了萃取溶剂种类和体积及盐析效应对测定的影响,比较了硫酸磺化和弗罗里硅土柱对萃取液的净化效果。方法在1.00μg/L~47.6μg/L范围内线性良好,当取样体积为200 mL时,方法检出限为0.001μg/L~0.002μg/L,基体加标回收率为95.8%~103%,相对标准偏差≤18.7%。     

西葫芦对土壤持久性有机氯化物污染的指示性研究

西葫芦(Cucurbita pepo L.)对土壤中持久性有机氯化物的超强吸收能力已被证实,意味其具有指示区域土壤持久性有机氯化物污染状况的潜能。本研究采用农田小区试验,考察了西葫芦不同组织器官(根、过渡茎、茎、叶和果实)在6个生长期对有机氯化物的累积吸收行为;采用同位素稀释高分辨气相色谱-高分辨质谱法,分析了种植土壤及西葫芦各组织器官中的21种有机氯农药(OCPs)和18种多氯联苯(PCBs)。结果表明,西葫芦可将根吸收的OCPs和PCBs传递到过渡茎和茎。不同生长期采集的西葫芦根、过渡茎和茎中的OCPs和PCBs浓度基本稳定,无明显生物稀释效应,且此3个组织器官中OCPs和PCBs的分布模式与土壤中的分布模式基本一致。因此,可以用西葫芦根和茎中持久性有机氯化物的浓度指示土壤中持久性有机氯化物的污染水平,根和茎的采样时间可以不受西葫芦生长期的限制。     

QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P_L) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P_L predicted by models used varied between ?3.94 to ?2.66 for Mono-; ?4.85 to ?2.97 for Di-; ?5.18 to ?3.17 for Tri-; ?6.02 to ?3.77 for Tetra-; ?6.64 to ?4.64 for Penta-; ?7.36 to ?4.76 for Hexa-; ?7.54 to ?5.79 for Hepta-; ?7.75 to ?6.64 for Octa-; ?7.89 to ?7.44 for Nona-Ct-Abs; and ?8.09 and ?8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P_L ?4 to ?2) and low (log P_L < ?4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.