多溴联苯醚的生物富集效应研究进展

研究污染物的生物富集效应对于预测污染物在生物体内的含量、建立环境标准以及评估污染物的生态风险具有重要的意义.论文结合近年来国内外有关多溴联苯醚(PBDEs)的生物富集及其沿食物链(网)生物放大效应的研究文献,对PBDEs的生物富集效应进行了综述.文献计算的生物富集因子(BAFs)、生物-沉积物/土壤生物富集因子(BSAFs)和生物放大因子(BMFs)表明,生物对大多数PBDEs具有生物富集作用,且生物对PBDEs的富集能力与其生物进化等级及其营养级有关.文献计算的营养级放大因子(TMFs)表明,大多数PBDE单体可以在食物网上产生生物放大效应,但只有较少单体具有统计上的显著性.生物的生理生化参数、化合物本身的特性以及环境条件等因素影响了PBDEs在生物体内及食物链(网)上的富集与放大.     

多溴联苯醚在不同粒径大气颗粒物上的分布及总有机碳的影响

利用Gc-Ms技术研究了大气不同粒径颗粒物上多溴联苯醚(PBDEs)的含量和分布,通过总有机碳(TOC)和PBDE单体含量的相关性探讨了它们在大气中的转移机制.研究结果表明,总颗粒物上∑15PBDEs含量为3745.5 pg·m-3,BDE47,99,209是三种主要单体.在<0.49μm粒径上∑15PBDEs含量最高(36.4%),<1.5μm的颗粒物上∑15PBDEs占61.9%.四溴和五溴的BDE47、66、100和99单体在不同粒径上的含量分布相似,约40%-50%分布在<0.49μm粒径的颗粒物上,约19%-23%分布在0.49-0.95μm粒径的颗粒物上;九溴的BDE208、207的分布和BDE47、99等明显不同,呈马鞍型分布;而十溴的BDE209主要分布在较粗颗粒上.结果表明大气中低溴PBDE对人体健康有重要影响,同时具有强的长距离迁移能力,BDE28、47、100和99与TOC间有良好的线性关系,可能表明这些低溴PBDE在大气中转移的主要机制是从气相分配进入颗粒相;而高溴的BDE207、208和209与TOC间相关性较差,可能表明高溴PBDE进人大气中的主要机制是依附在较大颗粒上直接进入大气.     

废弃塑料处置地典型植物多溴二苯醚污染特征

为了解土壤高污染的废弃塑料处置地植物体多溴二苯醚(PBDEs)累积水平,对废弃塑料处置地13种典型植物中21种多溴二苯醚的浓度水平、组成和污染特征进行了研究.结果表明,该区域植物中∑PBDEs含量为11.3—122 ng·g-1,平均为51.2 ng·g-1,与我国电子废物处置地植物体污染水平相似,远高于一般区域植物体PBDEs污染水平.不同植物体内PBDEs的含量差异较大,其中牵牛花中PBDEs的含量最高,牛筋草中PBDEs含量最低.废弃塑料处置地植物体中BDE 209的含量为10.8—116 ng·g-1,为最主要的PBDEs同系物单体,平均占∑PBDEs的96.9%以上.其余单体中,以BDE 47和BDE 208等含量相对较高,但占总PBDEs总含量均不到1%.废弃塑料处置地植物体较电子废物处置地和一般区域植物体表现出更明显的十溴二苯醚污染特征.     

电子垃圾拆解地翠鸟对多氯联苯的累积及风险评估

粗犷的电子垃圾拆解活动已造成当地野生生物多氯联苯(PCBs)严重污染,但PCBs在野生鸟类中的生物累积特征及潜在的毒害作用研究较少。本研究采集了广东省某电子垃圾拆解地翠鸟(Alcedo atthis)及其食物(各种小型鱼类)样品,研究翠鸟对PCBs的累积特征、生物放大效应及毒性风险。翠鸟肌肉中PCBs中值含量为220μg·g~(-1)脂重,比其他报道值高1~3个数量级。计算的生物放大因子(BMF)显示,大部分PCB单体的BMF值都大于1,表明翠鸟对PCBs具有生物放大效应。计算的共面PCBs毒性当量(TEQs)范围为39~23 600 pg·g~(-1)湿重,已经达到或超过了影响某些鸟类生殖或发育障碍的报道值。上述结果表明,电子垃圾拆卸活动已经造成了当地翠鸟PCBs严重污染,PCBs污染物对电子垃圾拆解地翠鸟及其他野生生物的毒性效应尚需进一步研究。     

粤北星子河水生生物体内重金属污染特征及健康风险

本文分析了粤北星子河12种水生生物样品中Cd、Cr、Cu、Pb、Ni和Zn等6种金属元素的含量水平。利用综合污染指数法和目标危害系数法对水生生物中重金属的污染特征及其健康风险进行评价。结果表明:不同水生生物对重金属的富集程度存在明显差异,重金属的含量水平从低到高顺序依次为:CdNiPbCrCuZn;鱼类富集重金属明显低于贝类。在贝类样品中,Cr、Pb和Zn的含量均出现超标现象。鱼类重金属综合污染指数低于1,属于微污染;而田螺重金属综合污染指数大于1,属于轻度污染水平。不同鱼类中重金属的复合健康危害系数(TTHQ)均小于1,且每周评估摄入量(EDI)均远低于暂定每周允许摄入量(PTWI),居民通过鱼类摄入重金属的健康风险较低;田螺中重金属对人的复合健康危害系数大于1,长期食用田螺存在较高的健康风险,风险较高的重金属元素为Cr、Pb和Zn。     

胶州湾沉积物中多溴联苯醚的污染特征及风险评价

2015年8月,在胶州湾及邻近海域设置11个采样点,采集表层沉积物,采用索式抽提,利用气相-质谱联用测定了样品中14种多溴联苯醚(PBDEs)的含量,分析了PBDEs的分布与组成特征,探讨了含量与沉积物理化性质的关系,与世界上不同海域沉积物中PBDEs的含量进行了比较,并对其生态风险进行了评价.结果表明,胶州湾沉积物中14种PBDEs总含量的均值为7.48 ng·g~(-1),其中BDE209的均值为6.20 ng·g~(-1).胶州湾东岸海域PBDEs的含量要高于西岸海域,湾内海域的含量高于湾外.BDE209是主要的同系物,其次是BDE47、BDE71.除BDE209外的13种PBDEs的总含量和BDE209含量均与沉积物中的总有机碳含量呈显著正相关关系.与其他海域相比,胶州湾沉积物中PBDEs的含量低于污染严重的欧洲海域,高于中国部分海域.胶州湾海域的PBDEs主要是由陆源污染带来的十溴联苯醚的污染,同时存在商业五溴联苯醚产品的污染.四溴、五溴、十溴联苯醚具有潜在的低和中等生态风险.     

我国典型电子垃圾循环地区人体血清中多溴联苯醚浓度与特征的时间变化趋势

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一种传统的溴系阻燃剂,已逐渐被禁止使用.但是,由于其持久性、生物累积性和潜在的生物毒性,PBDEs相关的环境影响依然被关注.本文采集了2014年和2018年浙江省LQ地区普通人群和电子垃圾拆解工人的血清样本,对7种常见的多溴联苯醚同系物进行了检测.研究结果与本研究组2006年开展的LQ地区普通人群血清结果进行对比,以了解该地区人群PBDEs随时间的变化趋势.2014年和2018年普通人群血清中的∑PBDEs平均浓度分别为48.0 ng·g~(-1) lw(lipid weight)和44.2 ng·g~(-1) lw,虽然比当地电子垃圾拆解职业工人血清水平(269 ng·g~(-1) lw)低1个数量级,但远高于其他非电子垃圾拆解区域普通人群水平,说明电子垃圾拆解活动对LQ普通人群PBDEs负荷具有重要影响.从时间尺度上看,人群血清PBDEs水平,2014年和2018年两年均显著低于2006年(P0.05),这可能归因于PBDEs商业产品的限制和禁用,以及LQ当地政府近年来对该地区电子垃圾拆解活动的规范化管理.2014年和2018年PBDEs水平呈现出男性大于女性的特征(P0.05),这可能与男女饮食习惯和代谢能力的差异有关.本研究对LQ地区人群血清中的PBDEs负荷进行调研,可为电子垃圾拆解活动的管理提供数据基础.     

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。     

鸟类对卤系阻燃剂的累积及生物放大研究进展

卤系阻燃剂(Halogenated flame retardants,HFRs)是人工合成的,能阻止聚合物材料引燃或抑制火焰传播的含卤(主要是溴和氯)化合物,由于其具环境持久性、可生物富集性和潜在的生物毒性,近年来,HFRs所引起的环境问题已成为全球环境科学研究的热点。鸟类作为自然生态系统的重要组成部分,常被用作指示性生物来研究区域环境的污染现状。研究HFRs在鸟类体内的积累特性及其在鸟类食物链上产生的生物放大效应,对评价HFRs的环境行为和生态风险具有重要的意义。本文结合近年来国内外有关多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)、六溴环十二烷(Hexabromocyclododecane,HBCDs)、十溴二苯乙烷(Decabromodiphenyl ethane,DBDPE)、1,2双(三溴苯氧基)乙烷(1,2-bis(2,4,6-tribromophenoxy)ethane,BTBPE)和双(六氯环戊二烯)环辛烷(Dechlorane Plus,DPs)等HFRs在鸟类体内的积累特性及在食物链上的生物放大效应进行了综述。已有的研究报道显示:在鸟类的脑、肌肉、肝脏、肾脏和鸟蛋等组织中都检测到了HFRs残留;而相关生物放大因子(Biomagnification factors,BMFs)的计算结果显示,几乎全部的PBDEs、α-HBCD和BTBPE都可以在鸟类食物链上产生生物放大效应,特别是BTBPE这种新型的替代型阻燃剂在鸟类食物链上产生的生物放大效应和已被禁用的五溴PBDEs相当,暗示这种新型溴系阻燃剂可能具有较大的生态风险。今后应对HFRs在陆生和水生鸟类中的生物放大效益及影响因素方面进行深入系统的研究,为认识HFRs的环境归趋,全面评价这些污染物的生态风险提供科学依据。     

持久性有机污染物在食物链中积累与放大研究进展

研究持久性有机污染物(Persistent organic pollutants,POPs)在食物链中的积累与放大是进行环境风险评估和有效污染控制的生态学基础.本文综述了POPs的基本特征,POPs在食物链中的生物积累与放大的机制、影响因素以及POPs在食物链中积累与放大的模型等的研究进展.国外学者对POPs在水生食物链的积累与放大方面研究较多,并提出了较为完善的预测模型,而有关POPs在陆生食物链中的生物积累与放大的研究报道较少.大部分学者并未对完整食物链进行过系统而完整的研究.与国外相比,国内学者对POPs在水生陆生食物链中的生物积累、生物放大和预测模型探讨较少.目前POPs对环境和人体健康危害越来越严重,开展对POPs在食物链中积累、放大及相关预测模型更深入更完整的研究,已成为当前生态学和环境科学研究的重点课题和前沿领域.     

Polybrominated diphenyl ethers in plastic products,indoor dust,sediment and fish from informal e-waste recycling sites in Vietnam: a comprehensive assessment of contamination,accumulation pattern,emissions, and human exposure

Residue concentrations of polybrominated diphenyl ethers (PBDEs) in different kinds of samples including consumer products, indoor dust, sediment and fish collected from two e-waste recycling sites, and some industrial, urban and suburban areas in Vietnam were determined to provide a comprehensive assessment of the contamination levels, accumulation pattern, emission potential and human exposure through dust ingestion and fish consumption. There was a large variation of PBDE levels in plastic parts of obsolete electronic equipment (from 1730 to 97,300 ng/g), which is a common result observed in consumer plastic products reported elsewhere. PBDE levels in indoor dust samples collected from e-waste recycling sites ranged from 250 to 8740 ng/g, which were markedly higher than those in industrial areas and household offices. Emission rate of PBDEs from plastic parts of disposed electronic equipment to dust was estimated to be in a range from 3.4 × 10^?7 to 1.2 × 10^?5 (year^?1) for total PBDEs and from 2.9 × 10^?7 to 7.2 × 10^?6 (year^?1) for BDE-209. Some fish species collected from ponds in e-waste recycling villages contained elevated levels of PBDEs, especially BDE-209, which were markedly higher than those in fish previously reported. Overall, levels and patterns of PBDE accumulation in different kinds of samples suggest significant emission from e-waste sites and that these areas are potential sources of PBDE contamination. Intakes of PBDEs via fish consumption were generally higher than those estimated through dust ingestion. Intake of BDE-99 and BDE-209 through dust ingestion contributes a large proportion due to higher concentrations in dust and fish. Body weight normalized daily intake through dust ingestion estimated for the e-waste recycling sites (0.10–3.46 ng/day/kg body wt.) were in a high range as compared to those reported in other countries. Our results highlight the potential releases of PBDEs from informal recycling activities and the high degree of human exposure and suggest the need for continuous investigations on environmental pollution and toxic impacts of e-waste-related hazardous chemicals.     

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.     

电子废弃物拆解地水体多溴联苯醚分布特征

为了解和比较广东贵屿电子废弃物拆解地和珠三角城市地区水体中多溴联苯醚的种类、含量及分布特征,于2011年9月在广东贵屿周边地区和广州采集了20个地下水、7个地表水和4个珠江水,用反相C18萃取小柱提取净化后,利用气相色谱-质谱法测定了样品中的8种多溴联苯醚（PBDEs）。研究结果表明：贵屿地区地下水中PBDEs浓度总体上较高,总质量浓度范围为2.54~71.74 ng·L-1,平均为22.97 ng·L-1,各类PBDEs的检出率为25%~95%。三溴联苯醚（BDE28）、四溴联苯醚（BDE47）、五溴联苯醚（BDE99和BDE100之和）、六溴联苯醚（BDE153和BDE154之和）、七溴联苯醚（BDE183）和十溴联苯醚（BDE209）的质量浓度分布分别为nd~0.64、nd~18.43、nd~25.26、nd~13.92、nd~9.06和nd~15.60 ng·L-1。从物种上来看,分别源于四溴、五溴和十溴联苯醚产品的BDE47、BDE99和BDE209是贵屿地区地下水样中的优势同系物。通过比率P=（BDE47＋BDE99）/BDE209研究发现：低溴代联苯醚比高溴代联苯醚更易被地表径流迁移转换进入到地下水中。贵屿地区地表水中PBDEs的质量浓度范围为3.41~63.83 ng·L-1,平均总质量浓度为19.38 ng·L-1,稍低于当地地下水中PBDEs的平均总质量浓度,PBDEs的组成以高溴代的BDE209为特征,与世界其他水体研究结果相比,可以发现贵屿地区的地表水中PBDEs的平均总质量浓度明显偏高,说明该地区的地表水受到较严重的PBDEs污染,必须引起足够的重视。珠江水中PBDEs的总质量浓度范围为3.48~20.84 ng·L-1,平均为10.39 ng·L-1,表明近年来珠江水体中PBDEs污染有逐渐恶化的趋势。     

Legacies and health risks of heavy metals,polybrominated diphenyl ethers,and polychlorinated dibenzo-dioxins/furans at e-waste recycling sites in South China

● Heavy metals and organic toxins may persist in legacy sites for a long time. ● Contaminants pose potential harms to the nearby community (HI > 1). ● PCDD/Fs had the risk of endocrine disruption and reproductive risk. ● Further intervention is needed to reduce pollution and related risks. Informal electronic-waste (e-waste) recycling sites pose substantial health risks to surrounding environments and populations, yet they are not properly regulated. In this study, the soil levels of copper, lead, cadmium, eight polybrominated diphenyl ethers (PBDEs), and 18 polychlorinated dibenzo-dioxins/furans (PCDD/Fs) were measured at two e-waste recycling sites in South China between 2014 and 2019. Both sites have been abandoned for natural restoration. Our results indicate that the mean Cd and PCDD/F levels at Site A in 2019 were higher than those recommended by current safety guidelines. Meanwhile, the highest exposure among children was 1.36 × 10⁻² mg/(kg·d) for Cu, followed by 5.05 × 10⁻³ mg/(kg·d) for Pb, 9.71 ng/(kg·d) for PBDEs, and 6.82 ng TEQ/(kg·d) for PCDD/Fs. Children were at elevated risk for health problem posed by Pb and Cu exposure at both sites (hazard quotient > 1) and by PCDD/Fs at Site A. Further risk assessment was conducted on the target organs and endpoints of heavy metals and PCDD/Fs. The hazard index (HI) for the target organ mixed-risk of heavy metals was high (HI = 1.27), as was that of PCDD/Fs (HI = 1.66), which can disrupt endocrine function and pose a risk of reproductive toxicity in children. Owing to incomplete cleaning, contaminants persist in soils over long periods and may harm nearby environments and communities. Our study demonstrates that heavy metal, PBDE, and PCDD/F contamination have not yet been remediated, and intervention is needed to reduce pollution and associated risks in areas affected by e-waste.     

喜马拉雅山区葇籽草和棘豆样品中PCBs、PBDEs和PCDD/Fs的分析

应用同位素稀释-高分辨气相色谱/高分辨质谱(HRGC/HRMS)法分析了喜马拉雅山区海拔5000 m以上的葇籽草和棘豆样品中多氯联苯(PCBs)、多溴联苯醚(PBDEs)和二噁英(PCDD/Fs)的含量.这两种植物样品中污染物含量与世界其它偏远地区的水平基本保持一致.其中PCBs的总含量在1.94—3.62 ng.g-1干重(dw)范围内,平均值为2.60 ng.g-1dw;PCB-28和PCB-52的浓度明显较高,约占7种指示性PCBs总量的90%以上.14种PBDEs的总浓度在83.3—142 pg.g-1dw之间,平均值为116 pg.g-1dw;除BDE-85、-138、-154,以及高溴代的BDE-190和BDE-209未检出外,其它9种单体均有不同程度的检出,且以低溴代的BDE-28为主,含量占45%以上.样品中PCDD/Fs基本上未检出.由于样品采集点位于喜马拉雅山人迹罕至的珠穆朗玛峰北坡地区,周围并无工业污染源,因此植物样品中PCBs及PBDEs可能是污染物发生大气长距离传输和生物富集的结果.     

Role of the fish Astyanax aeneus (Characidae) as a keystone nutrient recycler in low-nutrient neotropical streams

Nutrient recycling by animals is a potentially important biogeochemical process in both terrestrial and aquatic ecosystems. Stoichiometric traits of individual species may result in some taxa playing disproportionately important roles in the recycling of nutrients relative to their biomass, acting as keystone nutrient recyclers. We examined factors controlling the relative contribution of 12 Neotropical fish species to nutrient recycling in four streams spanning a range of phosphorus (P) levels. In high-P conditions (135 microg/L soluble reactive phosphorus, SRP), most species fed on P-enriched diets and P excretion rates were high across species. In low-P conditions (3 microg/L SRP), aquatic food resources were depleted in P, and species with higher body P content showed low rates of P recycling. However, fishes that were subsidized by terrestrial inputs were decoupled from aquatic P availability and therefore excreted P at disproportionately high rates. One of these species, Astyanax aeneus (Characidae), represented 12% of the total population and 18% of the total biomass of the fish assemblage in our focal low-P study stream but had P excretion rates > 10-fold higher than other abundant fishes. As a result, we estimated that P excretion by A. aeneus accounted for 90% of the P recycled by this fish assemblage and also supplied approximately 90% of the stream P demand in this P-limited ecosystem. Nitrogen excretion rates showed little variation among species, and the contribution of a given species to ecosystem N recycling was largely dependent upon the total biomass of that species. Because of the high variability in P excretion rates among fish species, ecosystem-level P recycling could be particularly sensitive to changes in fish community structure in P-limited systems.     

DDTs对水生哺乳动物的组织残留基准初步研究

作为一种曾经广泛使用的氯化烃杀虫剂,DDT及其主要代谢产物DDE和DDD(合称为DDTs)是一类典型的具有持久性和生物累积性的有毒污染物。亲脂性和持久性使得DDTs可以通过食物链进行生物放大,从而对处于高营养级的水生哺乳动物造成严重的毒害作用。在综述DDTs对哺乳动物的毒性研究基础上,采用物种敏感度分布(species sensitivity distribution,SSD)和毒性百分数排序法(toxicity percentile rank method,TPRM)推导DDTs保护水生哺乳动物的组织残留基准(Tissue Residue Guideline,TRG)。使用SSD和TPRM得到的TRG分别为23.9和22.7 ng·g-1食物(湿重)。相应的,DDTs保护水生哺乳动物的水质基准分别为188.2和178.7 pg·L-1。依据研究得到的DDTs的组织残留基准及其在鱼类体内的含量评估对水生哺乳动物的风险。研究结果可用于评估DDTs对水生哺乳动物的生态风险,并为DDTs的风险管理提供理论依据。     

珠江入海口水体中多溴联苯醚及其来源分析

2005年3月至2006年2月,选取珠江8个入海口,进行每月1次为期1周年的水样采集。检测了96个水样的多溴联苯醚（PBDEs,包括BDE 28、47、66、85、99、100、138、153、154、183、196、197、203、206、207、208和209）的残留状况。水体中PBDEs的质量浓度为0.344～68.0 ng·L-1。PBDEs的组成分析结果表明：珠江水体PBDEs的来源以土壤和沉积物源为主,而目前珠三角陆地环境中PBDEs仍不断蓄积,其通过珠江地表径流迁移转换的PBDEs将逐年增多,给珠三角水生态环境带来的压力逐日增加,所造成的生态环境及公众健康影响将是深远的。