五氯酚及其钠盐中氯代二恶英类分析

采用ＨＰＬＣ和ＧＣ／ＭＳ的方法，对国产ＰＣＰ及其钠盐中的ＰＣＤＤｓ，ＰＣＤＦｓ进行了分析。测定了所有２，３，７，８－取代同系物。此外，还根据各ＣＤＤｓ，ＣＤＦｓ的毒性当量因于ＴＥＦｓ，计算了其毒性当量Ｉ－ＴＥＱｓ，分别为１４２，９２ｎｇ．ｇ＾－１。在前述基础上，仨算了由于ＰＣＰ及其钠盐的应用，引起的ＰＣＤＤｓ，ＰＣＤＦｓ环境输入。约为２４０ｋｇ／ａ。     

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.     

Incidence of thyroid disease following exposure to polybrominated biphenyls and polychlorinated biphenyls, Michigan, 1974-2006

Thyroid hormones, which influence body metabolism and development, could be affected by persistent organic pollutants. We sought to examine the relationship between polybrominated biphenyls (PBBs) and polychlorinated biphenyls (PCBs) and thyroid disease. We employed incidence density sampling to perform a nested case control analysis of the Michigan Long-Term PBB Cohort. Cohort members (n = 3333) were exposed to PBBs through contaminated cattle feed in 1973-1974 and to PCBs through daily life. Those with detectable serum PBB and PCB concentrations at enrollment were categorized into tertiles of PBB and PCB exposure. Case-patients were cohort members answering “Yes” to “Has a healthcare provider ever told you that you had a thyroid problem?” during follow-up interviews; control-patients were cohort members answering “No”. We used odds ratios (OR) with 95% confidence intervals (CI) to compare odds of thyroid disease by PBB and PCB exposure and by various risk factors. Total cumulative thyroid disease incidence after 33 years was 13.9% among women and 2.6% among men. After adjusting for body mass index, we found no statistically significant differences in odds of any type of thyroid disease among women or men with elevated PBB or PCB exposure. Compared to control-patients, women with thyroid disease had increased odds of being overweight/obese (OR = 2.82, 95% CI: 1.94-4.11) and developing infertility (OR = 1.71, 95% CI: 1.08-2.69), diabetes (OR = 1.61, 95% CI: 1.04-2.51), or arthritis (OR = 1.71, 95% CI: 1.18-2.50) during follow-up. Additional research should explore potential associations between PBBs/PCBs and thyroid disease among children exposed in utero.     

PCDD/Fs-induced oxidative damage and antioxidant system responses in tobacco cell suspension cultures

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are ubiquitous contaminants and can be considerably accumulated by natural plants. In order to elucidate the biochemical and physiological responses of plant to PCDD/Fs, tobacco Bright Yellow-2 (BY-2) cells were selected as model plant and treated with time- and concentration-dependent PCDD/Fs. The toxic effect and oxidative stress caused by PCDD/Fs were evident, which could be indicted by the reduction in fresh mass, the increase in malondialdehyde (MDA) content, and the damage of tobacco cell ultrastructure. PCDD/Fs tolerance was correlated with changes in antioxidant system and hormones of tobacco cells. Superoxide dismutase (SOD) and peroxidase (POD) exhibited peak enzyme activities at the PCDD/Fs concentration of 1000 ng WHO₉₈-TEQ g⁻¹ fresh weight. Glutathione reductase (GR) enzyme activity increased monotonically at high level PCDD/Fs, but the activity of catalase (CAT) was only slightly affected at all treatment. Meanwhile, the exposure to PCDD/Fs resulted in the changes of hormones content. With the increase of exposure concentration of PCDD/Fs, the levels of indole-3-acetic acid (IAA) and abscisic acid (ABA) increased, whereas the concentration of jasmonates (JAs) decreased. The above results suggest that tobacco cells had the ability to cope with the oxidative stress induced by low concentration of PCDD/Fs through increasing the activities of antioxidant enzymes and alternating plant hormones levels. However, oxidative stress and toxicity would burst out when plant cells were exposed to the high levels of PCDD/Fs.     

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。     

Accumulation of hydroxylated polychlorinated biphenyls (OH-PCBs) and implications for PCBs metabolic capacities in three porpoise species

The present study investigated polychlorinated biphenyls (PCBs) and hydroxylated metabolites of PCBs (OH-PCBs) in blood from three porpoise species: finless porpoises (Neophocaena phocaenoides), harbor porpoises (Phocoena phocoena), and Dall’s porpoises (Phocoenoides dalli). The porpoises were found stranded or were bycaught along the Japanese coast. Concentrations of OH-PCB were the highest in Dall’s porpoises (58 pg g⁻¹ wet wt), second highest in finless porpoises (20 pg g⁻¹ wet wt), and lowest in harbor porpoises (8.3 pg g⁻¹ wet wt). The concentrations in Dall’s porpoises were significantly higher than the concentrations in finless porpoises and harbor porpoises (p < 0.05 and p < 0.01, respectively). There was a positive correlation between PCB and OH-PCB concentrations (r = 0.67, p < 0.001), suggesting the possible concentration-dependent induction of CYP enzymes. The three porpoise species may have exceptionally low metabolic capacities compared with other marine and terrestrial mammals, because low OH-PCB/PCB concentration ratios were found, which were 0.0016 for Dall’s porpoises, 0.0013 for harbor porpoises, and 0.00058 for finless porpoises. Distinct differences in the OH-PCB congener patterns were observed for the three species, even though they are taxonomically closely related.     

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.     

Seasonal variation of organochlorine contaminants in bonito (Sarda sarda L. 1758) and anchovy (Engraulis encrasicolus L. 1758) in Black Sea region, Turkey

The concentrations of indicator polychlorinated biphenyls (PCBs) and organochlorine insecticides were determined in bonito (Sardasarda L. 1758) and anchovy (Engraulisencrasicolus L. 1758) from the Black Sea, Turkey. Concentrations of total indicator PCBs ranged between <1-17.0 in bonito, and <1-17.5 ng/g fresh weight in anchovy, and total of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane and its metabolites’ (DDTs) concentrations ranged between 13.4-26.3, and 2.96-19.0 ng/g fresh weight in bonito and anchovy respectively. PCB 52, p,p′-DDE and endosulfan (α + β) were found dominant in both of the fish species. Except endosulfan, and some DDT metabolites, none of the studied organochlorine pesticides was detected in the fish samples. Concentrations of PCBs in anchovy were found higher than those in bonito, whereas DDT and endosulfan concentrations were found similar in both of the fish species. All of the fish samples had residue concentrations below the maximum residue limits (MRL) recommended by FAO/WHO Codex Alimentarius Commission.     

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).     

几种可利用多氯联苯和多溴联苯醚植物内生菌的分离及初步鉴定

采用PDA、NA以及高氏一号培养基,分别从毛白杨、绦柳、荻以及二穗短柄草植株内分离、纯化出37株内生菌,其中34株为细菌,3株为放线菌.以分离纯化得到菌株各自对应的营养培养基并添加不同浓度的污染物对获得的37株内生菌进行污染物的耐受筛选,发现24株分别对20 mg·L-1的aroclor1254和BDE209具有一定的耐受性.利用无机盐培养基并添加污染物作为微生物唯一碳源筛选,发现菌株CPY-4和菌株SGL-1可以在只提供4-BDE的无机盐培养基中存活,菌株CPY-4,SGL-1、菌株4、菌株13可以在提供BDE209和aroclor1254的无机盐培养基中存活.形态学观察和16Sr DNA序列同源性分析,初步确定菌株SGL-1为克雷伯氏菌属,菌株CPY-4为地衣芽胞杆菌,菌株4和菌株13为肠杆菌属.