手性农药的环境行为研究进展

手性农药由于其对映体选择性,在环境中具有特殊的归宿.研究其环境行为有助于准确评价生态系统和人体健康的风险性.文章综述了手性农药的研究进展,指出高效液相和气质联用法是不同环境介质中手性农约的主要分离分析方法;利用手性农药的对映体分数可研究农约在土壤-大气,水体-大气间的迁移过程;一些手性农药在土壤、水体和动物体内中发生的选择性降解与累积与微生物或特异性的酶有直接关系,可利用此性质修复被污染的土壤;归纳了在手性农约污染环境风险研究中应注意的问题;加强手性农约在环境中的选择性降解动力学、对映体转化及毒理学机制研究,并最终深人到代谢机理、蛋白和基因水平上,阐述产生手性对映体选择性的根源将是未来研究的方向.     

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.     

电子垃圾拆解区氯化石蜡和多氯联苯的分布特征——以广东清远龙塘镇为例

采用GC/MS法测定了广东清远龙塘镇电子垃圾拆解区电子垃圾、电子垃圾焚烧后残渣、当地池塘沉积物和对照区沉积物24种短链氯化石蜡(SCCPs)、24种中链氯化石蜡(MCCPs)和29种多氯联苯(PCBs)的浓度水平.结果显示,氯化石蜡(CPs)和PCBs大量存在于电子垃圾中.电子垃圾、残渣和池塘沉积物SCCPs和MCCPs浓度范围(干重)分别为1.6—46.8μg·g-1和7.3—215μg·g-1,PCBs的浓度范围(干重)为0.15—370.6μg·g-1,明显高于对照区,对周边造成了极大环境风险.SCCPs、MCCPs和PCBs均呈现低碳低氯同系物的相对含量在电子垃圾、电子垃圾焚烧残渣、拆解区池塘沉积物、对照区沉积物中依次递增的现象,表明CPs和PCBs在由电子垃圾向沉积物迁移过程中可能存在脱碳脱氯的降解过程.     

手性有机磷农药在土壤中对映体选择性降解特征

马拉硫磷和丙溴磷是2种常用的有机磷杀虫剂,均有一个手性中心存在2个对映体.采用室内避光培养的方法,在对映体水平上研究了马拉硫磷和丙溴磷在2种土壤中的降解情况.结果表明,2种农药在土壤中的降解均较快,马拉硫磷和丙溴磷的降解半衰期分别为:黄土中3.5 h和21.5 h,红土中4.3 h和29.4 h.进一步的手性测定表明2种农药的降解均存在一定的对映体差异,丙溴磷对映体的选择性明显高于马拉硫磷,在2种土壤中马拉硫磷的左旋对映体降解快于右旋对映体,丙溴磷的右旋体降解快于左旋体.研究有助于深入认识2种有机磷农药在环境中的归趋,并对其生态风险性进行更合理的评估.     

手性农药对映体选择性环境行为的研究进展

目前使用的农药中有25%是手性的,手性农药的生物活性存在对映体差异性,其活性往往只存在于一个或少数几个对映体中,而手性农药的对映体在环境中的消解和归趋往往也有明显的不同,即一个手性化合物的不同对映体具有不同的毒性.只有在对映体水平上研究手性农药的环境行为,考察手性农药的归趋和生态效应,才能更准确的评估其生态风险性以及对人类健康的影响,对手性农药的合理使用也有较好的指导作用.文章综述了近年来国际上有机氯、芳氧基羧酸和酰胺、有机磷和菊酯等手性农药对映体选择性环境行为的研究进展.提出今后的研究方向是拓展手性农药的研究种类、研究深度和广度,对映体选择性的毒理学研究,手性稳定性和手性转化,选择性的机制与相关微生物和酶学研究等.     

深圳市大气中多氯联苯污染水平

为了解深圳市大气中多氯联苯(PCBs),包括类二噁英类多氯联苯(Dioxin-Like PCB,DL-PCB)和指示性多氯联苯(indicator PCBs)的污染水平和分布特征,利用大流量空气采样器分别采集6个采样点的空气样品,每个采样点采集两个平行样品.通过高分辨气相色谱-高分辨双聚焦磁式质谱仪(HRGC/HRMS)对大气样品中12种二噁英类多氯联苯和6种指示性的PCBs单体进行了定性和定量分析.结果显示,∑PCBs的浓度为25.70—66.65pg.m-3,平均值为44.97 pg.m-3.DL-PCBs总毒性当量为2.50—19.55 fg(TEQ).m-3,平均值为10.8 fg(TEQ).m-3.深圳市成人每天呼吸进入体内的DL-PCBs平均为1.81 fg WHO-TEQ.kg-1BW.d-1;在指示性PCBs单体中,PCB28是浓度最高的单体,贡献率分别为71.6%—87.8%,其次是PCB52,占总浓度的11.8%—19.2%.DL-PCBs单体中PCB118的浓度最高,占总浓度的27.1%—50.7%,其次是PCB77和PCB105.PCB126是毒性当量浓度的主要贡献者,其平均贡献率为94.6%,其次为PCB169,其平均贡献率为2.17%.指示性多氯联苯浓度和DL-PCBs浓度显示了良好的一致性和相关性.深圳市大气样品中PCBs的浓度水平明显低于韩国京畿道以及我国台州的水平,大气中的多氯联苯TEQ浓度水平与横滨、曼彻斯特的浓度水平接近,略低于1998年日本城市均值和我国的北京市.     

茚虫威对映体在土壤中的选择性降解

研究了茚虫威在4种不同类型的农田土壤中的降解动态和选择性降解行为.结果表明,添加水平在0.1—5.0 mg.kg-1的条件下,茚虫威对映体在土壤中添加回收率在(78.56±3.16)%—(108.16±5.32)%之间,最低检测限为0.01 mg.kg-1,定量限为0.05 mg.kg-1.茚虫威在土壤中的消解符合一级动力学规律,消解过程受土壤pH值、有机质含量等因素的影响.茚虫威对映体在1#—4#土壤中的降解速率存在明显的差异性,E1的半衰期分别为15.33 d、19.09 d、10.61 d、11.40 d,E2的半衰期分别为15.44 d、15.61 d、8.58 d、11.13 d,降解快慢顺序为:3#>4#>1#>2#,表明茚虫威在偏碱性的土壤中的降解速率要快于在酸性土壤中,且对映体的半衰期差异在有机质含量较高的土壤中表现得更加明显;对映体分数EF值(enantiomer fraction)表明茚虫威对映体在4种供试土壤中除了1#土壤外均存在明显的立体选择性降解.     

电子垃圾拆解区土壤中多氯联苯的垂直分布

以典型电子垃圾拆解区作为研究区域,采集土芯样品,研究不同深度土壤中多氯联苯(PCBs)的污染状况.研究表明,从事电子垃圾拆解时间较短的采样点A土芯以及从事拆解时间较长的采样点B土芯不同深度土壤中PCBs总含量分别为0.54—45.43 ng·g-1干重和2.16—543.96 ng·g-1干重,两个采样点均受到了不同程度的PCBs污染,B土芯较A土芯污染严重.A和B土芯中PCBs含量由上到下呈下降趋势,表层(0—5cm)最高,5—10 cm层分别减少96.4%和92.6%.A土芯不同深度土壤中PCBs组成有所差异;B土芯各层土壤中PCBs组成较接近,含量较高的PCBs同系物均为5-CBs和6-CBs.相关性分析表明,土芯中1-CBs至9-CBs有相同的污染来源,即电子垃圾拆解,1-CBs至9-CBs随土壤深度向下迁移的能力接近.     

手性药物的水环境行为、毒性效应及生态风险

药物污染已经成为一个重要的环境问题,目前生产和使用的药物中大部分为手性药物,进入地表水环境后,2个对映异构体在生物降解和生态毒性等方面可能存在显著的差异。本文以8种手性药物为研究对象,系统综述了手性药物在水环境中的暴露特征和降解转化规律,分析其对不同生物靶点的毒性效应和机理,探讨了其对水生态系统的潜在风险。结果表明,8种手性药物在国内外地表水中的检出浓度达到μg·L^-1水平。手性药物在地表水环境中的对映体构成受药物种类、环境条件和时间的影响;布洛芬、普萘洛尔等差异显著的手性药物可以作为污染源示踪的特征污染物;不同污水处理工艺的对映体选择性也有较大差异,导致污水处理厂出水中手性药物对映体分数(enantiomer fraction, EF)值不同。由于手性药物在生物体内发生手性代谢和手性转化,导致体外毒性实验与体内毒性效果差异很大,手性药物在不同水生生物类群体内的受体或生物利用率有所差异,从而表现出不同的立体选择性。基于外消旋体的生态风险评估研究表明,目前布洛芬、卡马西平和萘普生等手性药物对水生生物具有潜在的风险,而不同对映体对水生生物的毒性存在一定差异。因此,有必...     

华南电子垃圾回收区农田土壤重金属污染及其化学形态分布

广东清远龙塘镇作为电子垃圾回收地区,已从事电子垃圾处置超过30年,可能给当地的农田土壤带来了严重的风险。为评价龙塘农田土壤中重金属污染程度,采集28个农田土壤样品,用于研究As、Cd、Co、Cr、Cu、Hg、Ni、Pb、Sn、Zn10种重金属含量及其不同存在形态。结果表明,与中国食用农产品产地环境质量标准比较,大多数当地农田土壤已在不同程度上受到重金属污染,85.7%的土壤样品中有一种或多种重金属的含量超过了相应的评价标准值。化学形态分析结果表明,除Hg外,人为来源的其她重金属更多地进入了可迁移形态部分(弱酸可溶态+可还原态+可氧化态),从而具有更高的毒害性和生物有效性,该电子垃圾处置区农田土壤已基本不适于食用农产品种植。大多数重金属在0.05或0.01水平上具有显著的相关性,这表明龙塘镇土壤重金属污染主要来源于不受控制的电子垃圾回收活动。对中国或其他国家具有类似的粗放式电子垃圾回收处置地区来说,有关龙塘镇农田土壤中重金属污染水平及其潜在的生物毒害性研究具有代表性意义。     

Polychlorinated biphenyls and their hydroxylated metabolites in the serum of e-waste dismantling workers from eastern China

A number of studies have reported on the exposure of e-waste dismantling workers to significantly high concentrations of halogenated organic pollutants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers. Such exposure can have adverse health effects. However, little information on the metabolites of these contaminants exists. In this study, we investigated PCBs levels and their hydroxylated metabolites (OH-PCB) in the serum of e-waste workers in Taizhou in eastern China. Our results indicate elevated PCB and OH-PCB levels in the serum of the workers, with medians of 443.7 and 133.9 ng/g lw, respectively. Tri- to hexachlorinated PCB congeners were the dominant homologue groups in all of the samples. 4-OH-CB107 was the predominant homologue among the hydroxylated metabolites, accounting for 88.9% of the total OH-PCB concentrations. While dietary sources (e.g., fish) appear to be an important route for PCB accumulation in non-occupational exposure groups, exposure via ingestion of house dust and inhalation of pollutants derived from the recycling of PCB-containing e-wastes may primarily contribute to the high body burden observed in the occupational groups. Since we found concentrations of metabolites higher than those of their parent compounds, further studies need to pay more attention to their bioaccumulation and toxicity.     

典型灌区稻田多氯联苯残留特征及生态风险评估

以南方典型小灌区的两块稻田为试验小区,采用GC-ECD对其田间水体和土壤中EPA优控14种多氯联苯（PCBs）进行了检测和定量分析。结果表明,14种PCBs同系物有不同程度检出,优势残留物主要以3氯和5氯取代PCBs为主,水和土壤占PCBs总量的88.24%、90.13%。水中∑PCBs质量浓度为24.09～310.34ng·L^-1,其中地表水均值为245.84ng·L^-1,地下水均值为96.46ng·L^-1;土壤中∑PCBs质量分数为10.01～54.63ng·g^-1,均值为33.92ng·g^-1。稻田地表水中的PCBs质量浓度远高于地下水,垂向迁移明显但速度较慢;稻田地表及地下水中PCBs质量浓度有随时间衰减的趋势,可能与水稻的生育周期有关;淹灌处理稻田PCBs质量分数高于节水灌溉。研究区毒性当量TEQ在2.65×10^-2～7.54×10^-2pg·g^-1之间,生态风险处于中等水平。地表及地下水均遭到污染,再加上PCBs具有生态累积效应,危害不容忽视。     

电子垃圾拆解对台州氯代/溴代二噁英浓度和组成的影响

电子垃圾拆解会导致有毒有害污染物向大气的排放,造成环境污染的产生。为了解电子垃圾拆解及废旧金属再生活动对拆解地及邻近地区空气质量的影响,对台州峰江金属再生园区附近及对照区路桥市区大气中(气态和颗粒态)氯代二噁英(PCDD/Fs)、溴代二噁英(PBDD/Fs)的含量、同系物组成及气/固分配规律进行了研究,通过相关性分析探讨了PCDD/Fs和PBDD/Fs的可能来源。结果显示,金属再生园区冬季采样期间17种2,3,7,8-PCDD/Fs和8种2,3,7,8-PBDD/Fs的平均浓度分别为212.2 pg·m-3和17.6 pg·m-3,夏季采样期间的平均浓度分别为84.5 pg·m-3和5.4 pg·m-3,均显著高于对照点。夏季采样期间对照点处于再生园区的下风向,其二噁英浓度高于冬季,说明其受到了金属再生园区的明显影响。基于相关性分析的结果,塑料焚烧是金属再生活动中氯代和溴代二噁英的主要来源。初步的暴露风险评价表明,金属再生园区附近居民每日摄入的二噁英含量远远超过世界卫生组织规定的人体每日耐受量(1~4 pg W-TEQ·kg-1·d-1)。上述研究结果为规范电子垃圾拆解活动提供了基础数据。     

生物滴滤塔耦合光催化氧化技术处理电子垃圾拆解车间排放废气的中试研究

采用生物滴滤塔（BTF）与光催化一体化（PCO）联用工艺应用于电子垃圾拆解现场废气处理的中试研究,研究结果表明：电子垃圾拆解现场排放的废气中含有高浓度的总悬浮颗粒物（TSP）和挥发性有机污染物（VOCs）。其中TSP的质量浓度为3792.5~7387.9μg·m-3,远高于中国环境空气质量控制标准（GB3095—2012）的二级标准（300μg·m-3）;VOCs主要由芳香烃类VOCs、含氮含氧类VOCs、卤代烃类VOCs和脂肪烃类VOCs组成,总VOCs的质量浓度为（5 499.1±854.7）~（26 834.0±447.0）μg·m-3,其中芳香烃类VOCs含量最高,其质量浓度为（2369.9±359.8）~（24419.6±229.5）μg·m-3,其次是含氮含氧类VOCs和卤代烃类VOCs,分别为（1018.2±142.1）~（2144.2±167.5）和（1170.6±146.5）~（1 936.6±353.3）μg·m-3,脂肪烃类VOCs的质量浓度最低,只有（44.6±0.8）~（174.4±0.5）μg·m-3。相较单一BTF和PCO工艺,BTF-PCO联用工艺可以更为有效地去除电子垃圾拆解现场排放废气中的TSP和VOCs。研究结果表明,经过BTF-PCO处理后,出口TSP的质量浓度降低到747.4~1750.9μg·m-3,其去除率在76.3%以上,而对于VOCs来说,出口浓度下降更为明显,芳香烃类VOCs、含氮含氧类VOCs、卤代烃类VOCs和脂肪烃类VOCs的去除率分别大于或者等于97.0%、92.4%、83.4%和100%。     

Detailed analysis of PCBs and PCDD/Fs impurities in a dielectric oil sample （ASKAREL Nr 1740） from an imported transformer in China

Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil （ASKAREL Nr 1740） in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry （HRGC/HRMS）. The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners （i.e., # 153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181） account for more than 50% of the total PCB concentrations. Total concentration ofPCDDs, PCDFs and dioxin-like PCBs （DL-PCBs） was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF 〉 HxCDFs 〉 HpCDFs 〉 PeCDFs 〉 TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners （i.e., #118, #156, #157） accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.     

典型电子垃圾拆解区大气中多溴联苯醚（PBDEs）的季节变化特征

电子垃圾污染问题已经引起了人们的广泛关注。研究了一典型电子垃圾拆解区及其上下风向大气中PBDEs的季节变化特征。结果表明,夏季电子垃圾拆解区大气中∑17BDEs总浓度为9930pg·m-3,冬季∑20BDEs的总浓度高达41476pg·m-3;和夏季相比,冬季五溴-联苯醚的百分比降低了16.7%,而十溴-联苯醚升高了10.2%,但是,其组成仍然是五溴-联苯醚为主,十溴-联苯醚次之,八溴-联苯醚最少。上下风向地区大气中PBDEs浓度及其组成成分由于受到电子垃圾拆解、本地生产方式和季节变化的影响也表现出相应的变化形式。     

PCBs,PCDDs and PCDFs in soil samples from uncontrolled burning of waste electrical material for metal reclamation

PCDDs, PCDFs and PCBs have been analysed in soil samples where waste electrical equipment has been burned directly on the ground in three locations of Burgos (Spain). High levels of PCDDs, PCDFs and PCBs were detected in the centre of combustion sites. The results show PCB levels between 0.824 and 1.240 μg/g, and PCDDs and PCDFs levels between 8.73–36.37 ng/g and 12.79–50.95 ng/g. The I‐TEF values between 2.96–9.15 for dioxins and furans indicate that these soils are heavily polluted and may represent a risk for human and animal health.     

PCB disposition and different biological effects in rats following direct soil exposure vs. PCBs off-gassed from the soil

A comparison of PCB congener profiles and limited biological effects was made between direct exposure to PCB-contaminated soil and vapor phase PCBs from that soil to determine congener patterns useful for identifying exposure sources in humans and wildlife. Weanling female Sprague–Dawley rats were exposed to either control or PCB-contaminated soil (from a landfill in Southern Illinois) for 1 and 2 weeks. The exposures were via direct contact with the soil or via airborne exposure with the rats isolated from the soil by a wire screen. Total PCB of 25% contaminated soil used in the study was 13?500?ppm. No PCBs were detectable in control rats. In direct-exposed rats, total PCB residues in fat pad, ear skin, serum, liver, and inguinal lymph nodes after the 1-week exposure were 6256, 185, 3.2, 149, and 41?ppm, respectively, but decreased to 465, 72, 1.7, 106, and 32.4?ppm after the 2-week exposure. In airborne-exposed rats, total PCB residues were 7.8, 1.6, 0.03, 0.2, and 0.6 in the same manner and slightly increased in fat pad and ear skin to 11.6 and 2.14, respectively. Decreases in both the concentrations and percentages of “episodic” PCBs (those congeners rapidly metabolized) in the fat pad were apparent following the 2-week exposure compared to the 1-week exposure by both routes. Both EROD and BROD activities were significantly increased in the direct-exposed rats, whereas only BROD activity increased in airborne-exposed rats. Serum T ₄ levels were depleted in the direct-exposed rats regardless of time of exposure but were increased insignificantly after 1-week and significantly after 2 weeks in the airborne-exposed rats. No significant changes in serum insulin levels were apparent in any of the treated groups. The results suggested that exposure of animals to PCBs via different routes could result in different PCB profiles, which could cause different biological effects.     

PBDEs and PCDD/Fs in surface soil taken from the Taizhou e-waste recycling area,China

The emerging issue of electronic wastes (e-waste) and the associated environmental problems has gained considerable attention from the scientific community in recent decades. In the present study, the levels of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the surface soil obtained from the Taizhou e-waste recycling area of China were investigated. Also the correlation among these chemicals and previously published data of heavy metals, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls was analysed. We determined that the pollution levels of eight PBDEs congeners were serious, ranging from 27.9 to 3128.4 μg/kg. The concentration of PCDD/Fs was in the range of 218.3–3122.2 pg/g with a mean value of 659.5 pg/g. The PBDEs were not well-correlated with organic pollutants (PAHs and PCBs) in soil, whereas PCDD/Fs exhibited a significant positive correlation with the PCBs. The higher levels of persistent organic pollutants may pose potential adverse effects to soil quality and human beings and needs to be properly managed and remediated.