电子垃圾拆解区土壤中典型手性PCBs分布及对映体特征

龙塘镇位于广东省清远市,是国内最大的进口电子垃圾集中处理处置地之一.通过对龙塘镇土壤中7种手性PCBs对映体浓度和对映体百分数(enantiomer fractions,EF)值的测定,发现龙塘镇土壤样品除PCB45和PCB174外,其余5种手性PCBs在土壤中均有不同程度的检出.土壤中5种目标手性PCBs(PCB91、PCB95、PCB132、PCB136和PCB149)的总浓度为145.4—286.7 ng·g^-1,这与先前文献中测定清远市土壤中手性PCBs污染水平基本一致.5种同系物的含量排序为PCB95>PCB132>PCB136>PCB149>PCB91.在距离电子垃圾拆解区10km以外的区域也检测到手性PCBs,证实这些污染物已经迁移到周边地区.土壤中手性PCB91、PCB95、PCB132、PCB136和PCB149的EFs值分别为0.519±0.005、0.4443±0.006、0.427±0.003、0.379±0.016和0.494±0.008,其中PCB149具有双向选择性.在全部检出样品中26%的PCB91、78%的PCB95、100%的PCB132、86%的PCB136和53%的PCB149具有非外消旋特征,表明该地区土壤中手性对映体选择性降解的显著性.     

3,3',4,4',5-五氯联苯通过饲料在罗非鱼体内的转移富集净化规律及膳食暴露评估

鱼类是人体摄入二噁英样多氯联苯的重要途径,饲料又是鱼类摄入该类污染物的主要途径.本实验采用对鱼类毒性当量贡献最大的3,3',4,4',5-五氯联苯(PCB126),在饲料中添加接近欧盟饲料限量标准的化合物,考察了在50 d富集期和随后34 d净化期内PCB126在罗非鱼各组织中的转移富集净化规律,并做出膳食暴露评估.结果表明,PCB126易在鱼体内蓄积,富集期第1 d肝脏、肌肉、肾脏和血液中的PCB126水平上升了8倍多,随后肝脏和血液中污染物的富集呈现快速上升与平稳蓄积交替的现象,肌肉和肾脏中污染物水平峰值的出现晚于肝脏、血液.在净化期,除肉外其余组织中PCB126水平均出现显著下降,肉中PCB126净化缓慢.鱼肉的最高毒性当量为1.08 pg TEQ·kg-1鲜重(188.1 pg TEQ·kg~(-1)脂肪),本研究中我国居民的每日最高暴露量为2.82 pg TEQ·kg~(-1)体重,接近WHO推荐的每日耐受摄入量(TDI),其健康风险有待进一步评估.     

中国东海抹香鲸体内多氯联苯的组成特征及毒性当量

用气相色谱-质谱联用仪测定了一只中国东海海域抹香鲸(Physeter macrocephalus)皮脂24种多氯联苯(PCBs)同系物的含量,并分析了其组成特征以及国际毒性当量.结果表明,东海海域抹香鲸皮脂PCBs的湿重含量为1.12μg.g-1;PCBs同族体中以含6和5个氯原子的化合物为主,高氯代PCBs占总量的92.10%;PCBs同系物中以PCB153、PCB138、PCB101和PCB149居多,分别占到PCBs总量的21.28%、15.97%、10.29%和10.23%;抹香鲸皮脂的TEQs含量为1663.07 pg.g-1,其毒性主要来自PCB126,其次是PCB123和PCB118;初步推断中国东海海域的抹香鲸受PCBs污染程度较轻.     

微波辅助萃取法提取滇池沉积物中的多氯联苯

研究运用微波辅助萃取-固相萃取-气相色谱/质谱检测滇池沉积物中6种指示性多氯联苯（PCB28、PCB52、PCB101、PCB138、PCB153和PCB180）.重点优化了微波辅助萃取技术,在萃取温度为100℃和萃取时间为30 min（升温和恒温各15 min）条件下,以30 mL正己烷∶二氯甲烷（1∶1,V∶V）的...     

3,3',4,4',5?五氯联苯(PCB126)在食用罗非鱼不同组织 中的蓄积、净化、迁移规律的动力学研究

为明确二■英及其类似物通过饲料在食用鱼体内的蓄积、净化、迁移规律,了解模型在预测可食部和饲料中污染水平及计算动力学参数方面的准确性,本研究测定了饲料暴露的二■英样多氯联苯(3,3′,4,4′,5-五氯联苯,PCB126)在养殖食用罗非鱼的肝脏、肌肉、肾脏、血液中的含量,利用非线性模型拟合了各组织的污染水平和清除速率常数等PCB126的蓄积、净化动力学参数.结果表明,该模型对肌肉中PCB126的污染水平有很好的预测效果(R~2=0.95),对各组织中污染物半衰期的预测也与实际接近.本研究用逸度表征污染物在各组织中的迁移趋势,结果表明肝脏可快速蓄积、清除PCB126,并在高浓度污染物刺激下生长以提高蓄积能力;肌肉中污染物的迁移不受暴露时长的影响,清除期污染物由其它组织迁移入肌肉,引起肌肉中污染物含量峰值的延后.     

Comparative Toxicity of PCBs and PBDEs Using Human Cancer Cell Lines and Zebrafish Embryos

研究了6种多氯联苯(PCBs)3,3′,4,4′-四氯联苯(PCB77)、2,3,3′,4,4′-五氯联苯(PCB105)、2,3′,4,4′,5-五氯联苯(PCB118)、3,3′,4,4′,5-五氯联苯(PCB126)、2,3,3',4,4',5-六氯联苯(PCB156)和商业型混合多氯联苯Aroclor1254,两种多溴联苯醚(PBDEs)2,2′,4,4′-四溴二苯醚(PBDE47)、十溴二苯醚(PBDE209)对人类癌细胞生长和斑马鱼脱膜与不脱膜胚胎发育的影响.8种化合物均使用0.01、0.1、1.0、10μmol·L-14个浓度进行1~6d的暴露实验.结果表明,PBDE209在最高浓度10μmol·L-1下对结肠癌细胞HCT116(暴露3d后)和RKO(暴露5d后)具有显著的生长抑制作用,所有化合物均对乳腺癌细胞没有显著影响.相比之下,化合物对受精后5~6h(5~6hpf)的斑马鱼胚胎的毒性效应显得比较明显,而各化合物对胚胎的致畸和致死效应又不相同,其毒性强弱依次为PCB126≈PCB156>PCB1254(Aroclor1254)>PBDE47>PCB77>PCB105≈PCB118≈PBDE209.其中PBDE209在未脱膜暴毒后均无致畸与致死现象,脱膜暴毒后最高浓度才表现出显著意义的致畸作用,而PBDE47在最高浓度下可产生高达80%的致畸率,这说明胚胎绒毛膜具有有效阻挡大分子物质如PBDE209进入的作用.PCBs的毒性效应与其空间结构密切相关.如PCB126和PCB105具有相同的分子式,前者在1μmol·L-1下就引起了显著的致死和致畸效应,而后者即使在10μmol·L-1下也没有显著的效应.实验结果也说明不同类型的实验对象所展示的毒性效应并不相同,化合物对体外培养的细胞和发育中的胚胎具有不同的影响.     

OsZEP2基因沉默对2,2',5-三氯联苯胁迫下水稻抗氧化反应的影响

载脂蛋白基因OsZEP2沉默突变株(mutation type, MT)和野生型(wide type, WT)的水稻愈伤组织被暴露于10、50、100μg·mL~(-1)的2,2′,5-三氯联苯(PCB18)的培养基3 d后,通过比较两种水稻愈伤组织的生长、PCB18积累和抗氧化反应的变化情况,来探究水稻在多氯联苯胁迫下OsZEP2基因对水稻解毒响应机制的影响.实验发现,PCB18可以抑制WT和MT的生长,但PCB18的中浓度胁迫对两种愈伤组织生长的促进作用十分明显,即有"hormesis"效应.PCB18对MT生长的抑制高于WT,低浓度CB18(10μg·mL~(-1))胁迫抑制MT生长(4.5%),中浓度PCB18(50μg·mL~(-1))促进MT生长(8.3%),高浓度PCB18(100μg·mL~(-1))抑制MT生长(9.9%).OsZEP2基因沉默后促进了PCB18在愈伤组织的积累,并导致培养基中的PCB18去除效率提高.OsZEP2基因沉默降低类胡萝卜素含量,导致MT本身的氧化胁迫增强;并且在不同浓度PCB18胁迫下,MT的类胡萝卜素含量稳定,MT的抗氧化反应活性低与WT.在PCB18胁迫下,MT体内的SOD和CAT酶的活性都明显低于WT,这可能是导致膜脂过氧化程度显著升高的重要原因之一.另外,两种嫩弱的愈伤组织中的POD酶抗氧化活性较弱,但OsZEP2沉默可以促进POD酶活性升高.因此,OsZEP2基因沉默导致植物体内的PCB18积累增多,抗氧化反应减弱,不利于植物对PCB18毒性的抵抗.     

离子色谱在大气环境中的离线和在线应用

回顾了离子色谱在大气环境中的离线和在线应用.离子色谱离线检测应用技术主要分析物种为无机水溶性组分、有机酸和糖类.在线离子色谱可获得高频数据,为研究相关污染形成机理和制定政策提供科学依据.     

循环经济与PCB行业废弃物循环利用

从不同角度阐述了循环经济的内涵，认为循环经济是一种“三赢”经济，是工业可持续发展的必然选择。并针对我国印制电路板(PCB)行业快速发展过程中产生大量有回收利用价值的PCB废弃物的现状，将循环经济发展模式运用于PCB行业废弃物的回收处理，探讨了PCB废弃物处理模式从“单向非闭合型”向“循环闭合型”转变的途径，进而实现PCB行业的可持续发展。     

基于功能化纳米材料的环境中重金属快速检测研究进展

重金属污染对生态环境和人类健康均具有极大危害,建立灵敏、快捷、高效的重金属检测技术具有非常重要的现实意义.现有检测技术对大型仪器设备具有较强的依赖性,并且在检测条件、时间以及成本上的要求较高,难以满足当前重金属快速监测和预警工作的需要.纳米材料的飞速发展为解决环境重金属污染物检测所面临的问题提供了良好的理论基础和技术支持.功能化纳米材料与传统检测方法的结合,衍生出具有高灵敏、高通量的快速检测方法.本文主要综述了近年来常用的几种功能识别分子和功能化纳米材料在环境中重金属快速检测应用的研究进展,指出了重金属快速检测技术在实际应用中可能面临的问题,并对未来的发展前景进行了展望.     

Detection of polychlorinated biphenyls employing chemical dechlorination followed by biphenyl whole cell sensing system

Polychlorinated biphenyls (PCBs) are a mixture of 209 individual chlorinated compounds commonly known as PCB congeners. These compounds are hydrophobic and are persistent in the environment. Their use was banned in the US a few decades ago because of harmful health effects. Therefore, detection of PCBs in environmental samples is increasingly important. To that end, we have developed a two-step simple and sensitive method for the detection of total PCBs. Specifically, our method involves dechlorination of PCBs to biphenyl followed by detection of biphenyl using a whole cell sensing system as the detection system. The whole cell sensing system consists of cells of the strain Pseudomonas pseudoalcaligenes KF707 harboring plasmid pSD7000. Plasmid pSD7000 contains the gene of lacZ, a reporter protein under the control of the bph operon. The detection is achieved through the emission of light afforded by the expression of reporter protein triggered by the presence of biphenyl. Due to the fact that this operon is activated only by few PCB congeners, a chemical dechlorination method was employed to convert all PCBs to biphenyl, and thus all the PCBs present in a given sample are able to be detected. The results showed that PCB congeners were rapidly (30?min) and efficiently (>98.5%) dechlorinated to biphenyl using a Mg/K₂PdCl₆ catalyst, and the biphenyl could be subsequently quantified using the whole cell sensing system. This hybrid analytical method that combines classical dechlorination with novel biosensing methods may find applications in the on-site monitoring of PCBs contamination levels.     

A mathematical model of PCB bioaccumulation in plankton

In batch experiments exposing individual plankton constituents to Aroclor 1254 PCB, the rate at which the organism approaches partitioning equilibrium appears to be partly size-dependent while the extent of PCB accumulation is species-specific. The sorptive desorptive kinetics of PCB in these experiments can be described mathematically by a first-order expression. Employing this expression in a model plankton food web permits examination of the role of feeding and sorptive processes in determining PCB body burden under various environmental conditions. When ingestion rates exceed desorption and excretion rates, a consuming organism accumulates PCB above levels predicted by equilibrium partitioning relationships. Feeding-induced oscillations in PCB body burden could thus obscure the reduction of soluble PCB concentration which determine a “baseline” PCB body burden. Unless referenced to a specific set of biological and environmental conditions, the importance of direct partitioning from water vs. food uptake appears to be a moot topic.     

Nematodentest

For the assessment of contaminated and remediated soils and substrates, and the estimation of chronic toxicity of soil contaminations, an ecotoxicological test was developed using the terrestrial nematodePanagrellus redivivus. The population dynamics expressed by the reproduction factor (VF) allows an estimation of soil quality within seven days. Due to the rapid generation time ofPanagrellus (< 5 d), the short test duration is considered to be sufficient. The suitability of this test duration is considered to be sufficient. The suitability of this test was evaluated by investigating soils which had been contaminated using applications of specific pollutants (lindane and PCB 52).     

Congener-specific analysis of polychlorinated biphenyl in human blood from Japanese

Polychlorinated biphenyl (PCB) congeners were analyzed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) of whole blood samples taken from 24 healthy adult Japanese volunteers (12 males and 12 females; age range 25–46 years). On average, 95 PCB congeners were detected in whole blood samples. The mean of total PCB concentration in whole blood was 771.9 pg g^–1 whole blood (139.6 ng per g-lipid). Congener-specific analysis identified the predominant PCB congeners as #153 (22.2), #180 (11.6), #138 (8.4), #182/187 (6.6), #118 (5.6), #163/164 (5.0), #99 (3.9), #74 (3.6), #146 (3.3), #170 (3.0) and #156 (2.2), representing 75.6 of all PCBs detected in the human blood samples. Among the predominant PCB congeners, #153, #180, #138, #187 #118, #99 and #74 had chlorine as the substituent at the 2-, 4- and 5- positions of the phenyl-ring. In human blood in Japanese individuals, it is assumed that these congeners would be characteristic of the entire population, based on the relation between PCB ingestion and metabolism. Measuring 209 PCB congeners has the advantage of providing detailed information regarding the congener distribution within the blood samples, which can be compared to congener patterns in other matrices. Congener-specific analysis of 209 PCB congeners is especially useful in evaluating human exposure to PCBs.     

Foodweb modeling for polychlorinated biphenyls (PCBs) in the Twelvemile Creek Arm of Lake Hartwell,South Carolina,USA

PCBs from the Sangamo-Weston Superfund Site near Clemson, South Carolina, USA, were released into the Twelvemile Creek Arm of Lake Hartwell until the early 1990s. Monitoring data have shown that while PCB concentration in sediments declined since 1995, PCB concentrations in fish have remained elevated, e.g., largemouth bass (Micropterus salmoides) concentrations have ranged from 5 to 10 ppm. The EPA aquatic ecosystem model AQUATOX was applied to this system to better characterize foodweb dynamics that lead to biomagnification of PCBs. The model was calibrated with observed fish biomass data. Simulated PCB loading over a 12-year period provided a reasonable fit to observed PCB data in fish. The model demonstrated that contaminated labile detritus loaded to the system was incorporated into the foodweb rather than deposited, thereby maintaining the PCB concentrations in fish while concentrations in the sediment declined. A dominant PCB pathway was from detritus to daphnia to shad to largemouth bass. Fish PCB concentrations showed moderate sensitivity to toxicant parameters; model runs incorporating uncertainty in these parameters predicted recovery (<2 ppm PCB) for all species in the range of years from 2008 to 2013. The high sensitivity of the model to parameters related to growth strongly affected PCB concentrations in fish and should be considered in future AQUATOX applications.     

Polychlorinated biphenyls: Accumulation from contaminated sediments and water by the polychaete Nereis diversicolor

Comparisons were made of the accumulation of a polychlorinated biphenyl (PCB) mixture from sediments and from water by the benthic worm Nereis diversicolor. Uptake from sediments was dose-dependent, attaining equilibrium concentration factors of approximately 3 to 4 after 2 months. Subsequent PCB elimination rates were concentration-dependent, with higher initial loss rates evident in the worms containing higher levels of PCBs. Accumulation of PCBs from water was much more rapid; concentration factors reached approximately 800 after only 2 weeks. Estimates were made of the relative importance of sediments and water as a source of PCBs to worms exposed to these contaminants in the natural environment. Calculations based on experimentally derived PCB concentration factors and ambient PCB levels in sediments and water suggest that compared to water, sediments contribute the bulk of these compounds to the worms. The possible mechanisms involved in the uptake of sediment-associated PCBs are discussed.     

Accumulation of polychlorinated biphenyls in the cockle Cerastoderma edule and the tellin Macoma balthica

Two species of marine bivalve, Cerastoderma edule (Linnaeus) and Macoma balthica (Linnaeus), were exposed to particles contaminated with three commercial polychlorinated biphenyl (PCB) mixtures, Aroclors^® 1242, 1254 and 1260. The accumulation of PCB in bivalve tissue was monitored for periods of up to 40 days. In addition to measuring total PCB concentrations, which reached 60 ppm of Aroclor 1242 in M. balthica, the fate of individual PCB homologues of different chlorine content, ranging from 2 to 8 chlorine atoms per biphenyl molecule, was also determined. Selective accumulation of PCBs with 5 chlorine atoms per biphenyl molecule occurred, whilst isomers of very low and very high molecular weights were accumulated at much slower rates.     

V-shaped substrate for surface and volume enhanced Raman spectroscopic analysis of microplastics

● V-shaped substrate was obtained for SERS analysis of microplastics (diameter ≈ 1 μm). ● Enhancement factor of V-shaped substrate can reach 20 in microplastics detection. ● V-shaped nanopore array can bring additional volume enhancement. ● V-shaped substrate was more economic in application compared to Klarite substrate. Research on the microplastics (MPs) is developing towards smaller size, but corresponding methods for the rapid and accurate detection of microplastics, especially nanoplastics still present challenge. In this work, a novel surface and volume enhanced Raman spectroscopy substrate was developed for the rapid detection of microplastic particles below 5 μm. The gold nanoparticles (NPs) were deposited onto the surface and into the V-shaped nanopores of anodized aluminum oxide (AAO) through magnetron sputtering or ion sputtering, and then AuNPs@V-shaped AAO SERS substrate was obtained and studied for microplastic detection. SERS performance of AuNPs@V-shaped AAO SERS substrate was evaluated through the detection of polystyrene and polymethyl methacrylate microspheres. Results indicated that individual polystyrene sphere with a diameter of 1 μm can be well detected on AuNPs@V-shaped AAO SERS substrate, and the maximum enhancement factor (EF) can reach 20. In addition, microplastics in ambient atmospheric samples were collected and tested to verify the effectiveness of the AuNPs@V-shaped AAO SERS substrate in the real environment. This study provides a rapid, economic and simple method for detecting and identifying microplastics with small size.