The Distribution and Impacts of Dioxins and Polychlorinated Biphenyls in the Taiwan Er-Jen River

Abstract

The distribution and impacts of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) and polychlorinated biphenyls (PCBs) in the Taiwan Er-Jen River were investigated by monitoring fish distribution and measuring PCDD/DFs and PCBs levels in sediment and fish samples. Most of the fish collected are pollution-resistant species such as Oreochromis spp, Liza macrolepsis, Channa spp and Megalops cyprinoides. the most polluted river sections are in the upstream where large amount of waste effluents from households, livestock rearing and nearby dumping sites were discharged into the river, and the lower reaches of the river where metal recovery activities including open burning of waste electrical wire/scrap occurred. Sediment samples collected near the burning site show 2,3,7,8-TCDD toxicity equivalents (TEQ) ranging from 0.014 to 14.2 ng g^?1 by PCDD/DFs and from 0.015 to 1.03 ng g^?1 by coplanar PCBs (Co-PCBs). the fish samples show TEQ ranging from 0.029 to 0.615 ng g^?1 by PCDD/DFs and from 0.012 to 0.12 ng g^?1 by Co-PCBs. Possible PCDD/DFs sources are discharged PCBs, open burning of waste wire/scrap, and pentachlorophenol. the consumption of these fish will cause an average intake of 54 pg kg^?1 d^?1 TEQ. the prevention of direct discharge of livestock and the dumping of waste effuents into River Er-Jen as well as the control of metal recovery activities appears to be the first step toward the restoration of River Er-Jen.     

类二噁英多氯联苯生殖毒性的研究进展

类二噁英多氯联苯(DlPCBs)作为典型的环境内分泌干扰物,会干扰接触个体或其后代的内分泌功能,破坏机体的神经系统、免疫系统,尤其对生殖系统的影响最为明显,比如对生殖器官的形态与功能、生殖内分泌、原始生殖细胞及其受精和早期胚胎发育等产生严重影响,最终导致各种生殖系统疾病的发生。DlPCBs的蓄积性及半挥发性使其在环境中分布广泛,半衰期长的特点使其将对动物及人类的生存和健康造成难以想象的影响。本文综述了DlPCBs的分类与构成、一般性质、生殖毒性以及其可能的致病机理,并对DlPCBs生殖毒性机理研究的重点方向进行了展望。     

西藏农田土和农作物中多氯联苯的分布、环境行为和健康风险评估

南亚排放的多氯联苯类污染物(PCBs)可随大气传输到西藏南部,并沉降到农田等区域。农田中的PCBs能够经食物链进入人体,从而可能对人体健康产生影响。但目前尚无西藏农田PCBs环境过程和农作物健康风险评估的研究。本研究通过同步采集西藏农田土壤和农作物,发现西藏农田土壤、青稞和油菜PCBs的浓度均值分别为5.1 pg·g-1dw、13.5 pg·g-1dw和10.9 pg·g-1dw,低于全球其他地区。青稞和油菜对PCBs的生物富集系数都大于1,说明PCBs在农作物中发生了生物富集现象。模型模拟结果显示,农田土壤中99.6%的PCBs都富集在土壤有机质中,只有0.38%的PCBs进入了植物根系。因此,青稞直接从大气中吸收PCBs是其对PCBs积累和富集的主要途径。基于饮食结构(青稞、牛肉、牛奶和酥油),西藏人群PCBs摄入均值为0.75 ng·kg-1bw·d-1,低于安全阈值约一个数量级。PCBs的食物摄入不会对西藏居民健康状况产生明显影响。     

多氯联苯对我国土壤微生物的生态毒理效应

作为持久性有机污染物(POPs),多氯联苯(PCBs)一旦进入土壤将长期存留并对土栖生物产生潜在危害。土壤微生物是土壤生态系统重要组成部分,研究外源PCBs对土壤微生物的生态毒理效应,筛选出指示PCBs污染的敏感指标并获取可靠的生态毒理数据十分重要。研究以江西红壤和天津潮土为供试土壤,在室内25℃连续培养28 d的条件下进行了生态毒理实验,选择了微生物量碳、呼吸强度、代谢熵、硝化作用、脱氢酶活性、脲酶活性和微生物群落功能多样性为微生物指标。结果显示:1)在28 d培养时间内,多氯联苯(PCBs)的毒性作用随培养时间的延长而增强,且在红壤中的毒性作用强于在潮土中,表明PCBs对土壤微生物的毒性作用存在时间效应并受土壤性质的影响。2)各微生物指标的敏感性不同,微生物量碳、脲酶活性和微生物功能多样性对PCBs污染反应不够敏感,而土壤呼吸强度、代谢熵、硝化作用和脱氢酶活性对PCBs污染反应敏感。3)14 d时,红壤中PCBs对脱氢酶活性、呼吸强度和代谢熵的EC10值分别为1.20、3.18和1.09 mg·kg-1,而在潮土中分别为6.31、4.73和50 mg·kg-1;28 d时,红壤中PCBs对硝化作用、脱氢酶活性、呼吸强度和代谢熵的EC10值分别为2.32、0.77、0.51和0.71mg·kg-1,而在潮土中分别为5.91、1.65、3.00和50 mg·kg-1。综合考虑经济和实际需要等因素,建议将呼吸强度、硝化作用和脱氢酶活性作为PCBs污染土壤生态毒理评价中的首选敏感指标,并建议培养时间设置为28 d。     

多氯联苯(Aroclor 1254)对非洲爪蟾变态发育的影响

为了研究多氯联苯(Aroclor 1254)对非洲爪蟾变态发育的影响,将非洲爪蟾受精卵暴露在一定浓度(0、400ng·L-1、2μg·L-1、10μg·L-1、20μg·L-1)的Aroclor 1254中,直至完全变态.结果表明,20μg·L-1Aroclor1254暴露可使变态所需时间显著延长(p<0.05),低于20μg·L-1的各组变态所需时间与对照组无显著差异.2μg·L-1以上的Aroclor1254暴露可使蝌蚪甲状腺发生明显的组织学改变,包括甲状腺组织滤泡扩张、胶体面积相对缩小,滤泡细胞增殖、高度增加,并且这种变化随暴露剂量的增加而愈发明显.提示多氯联苯可干扰非洲爪蟾的变态发育,引起甲状腺组织学改变.采用定量组织病理学技术检测甲状腺激素干扰物较为灵敏,方法简单易行,是一种切实可行的筛选和确证甲状腺干扰物的体内方法.     

多氯联苯对孔雀鱼卵黄蛋白原的诱导及检测

为探讨利用孔雀鱼(Poecilia reticulata)卵黄蛋白原(Vitellogenin,Vtg)作为生物标志物检测环境雌激素的可行性,采用浸浴法分别使用17β-雌二醇(E2)和多氯联苯(PCBs)对雄性孔雀鱼成鱼进行染毒,30d后测定其性腺系数(GSI)和肝指数(LSI),并将鱼体整体匀浆进行常规聚丙烯酰胺凝胶电泳(Native-PAGE)及磷、脂和糖蛋白特异染色分析.结果表明,PCBs对雄性孔雀鱼具有雌激素效应,和E2均可以诱导雄性孔雀鱼体内产生Vtg,但诱导组雄鱼GSI及LSI与对照组比较均无显著性差异(p>0.05).Native-PAGE及磷、脂、糖蛋白特异性分析表明,孔雀鱼Vtg是一种富含磷、脂、糖的蛋白,具有VtgⅠ、VtgⅡ和VtgⅢ等3种形式,其分子量分别为642kDa、541kDa和441kDa.雄性孔雀鱼Vtg可作为环境雌激素监测的有效生物标记物.     

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。     

被动加标在水生生态风险评价中的应用——以多氯联苯分配系数的测定为例

准确的水生生态风险评价需要可靠的毒性数据,而其获取要求在一定时间范围内,水体中污染物的浓度保持恒定。对疏水性有机污染物进行水体生物毒性测试时,通常采用有机溶剂加标,然而该方式可能因为污染物的挥发和降解、容器壁吸附、生物摄取等问题,水体中污染物浓度持续下降,导致污染物的浓度-效应关系难以明确。近期为了克服这些问题,被动加标用于替代溶剂加标,通过污染物在加标体系中平衡分配来维持精确和恒定的水体浓度,同时还可通过测定加标聚合物中污染物的浓度来监测水体浓度。首先介绍了被动加标方法及其材料选择,讨论了该方法在生态风险评价中的主要应用,包括分配系数的测定、体外细胞测试、体内生物积累及毒性测试,以及沉积物毒性评价等。然后,以测定代表污染物多氯联苯在聚二甲基硅氧烷与水间的分配系数为例,详细说明被动加标的操作流程。最后,讨论了被动加标方法的优缺点,并对其在水生生态风险中的应用前景进行了展望。     

多氯联苯(PCBs)胁迫下鲫鱼肝脏EROD酶活性与血清性激素含量的相关性研究

以鲫鱼(Carassius auratus)为试验鱼类,研究其暴露于不同浓度的PCBs(多氯联苯)后鱼肝组织中EROD酶活性和血清性激素含量的动态变化,探讨了2者间的相关性。结果表明,鲫鱼在PCBs中暴露后,其肝脏组织中EROD酶被诱导,酶活性随PCBs浓度增大而增强,呈明显的剂量-效应关系;EROD酶活性随暴露时间延长而上升,10 d后达平衡;鲫鱼血清中睾酮含量随PCBs浓度增大和暴露时间延长呈下降趋势,但雌二醇含量则显著上升,表明PCBs对鱼类具有环境雌激素效应;在一定浓度范围内,EROD酶活性与血清睾酮含量呈负相关,与血清雌二醇含量呈正相关。因此可用鱼肝EROD酶和血清性激素含量的协同变化作为污染生物标志物来评价PCBs的早期污染生态效应。     

太湖流域水源地多氯联苯分布特征与污染水平

为系统了解太湖流域主要水源地多氯联苯(PCBs)的污染现状,于2012年3月和6月分别采集水相、悬浮颗粒物和沉积物样品,并利用气相色谱-质谱联用仪(GC-MS)对PCBs的浓度进行了分析。结果表明,3月水相、悬浮颗粒物和沉积物中均未检测出PCBs类物质。6月水相中PCBs质量浓度在ND~1.04 ng·L~(-1)之间,平均值为0.57 ng·L~(-1),悬浮颗粒物和沉积物中PCBs质量浓度分别在0.96~2.72 ng·g-1和0.47~1.29 ng·g-1之间。Aroclor 1016和Aroclor 1260在3种介质中均有检出,且Aroclor1016浓度均为最高。与国内外研究相比较,太湖流域主要水源地PCBs污染水平较低。水相中PCBs浓度水平低于我国地表水环境质量标准;悬浮颗粒物和沉积物中PCBs浓度水平均低于加拿大保护水生环境沉积物化学品风险评价标准的LEL值,说明各样点PCBs对底栖动物无毒性影响。     

现代黄河三角洲土壤特性对多氯联苯分布的影响规律

对现代黄河三角洲22个表层土壤样品中类二嗯英类多氯联苯（PCBs）进行双毛细管柱GC．ECD结合MS测试,并使用相关数学统计学分析方法一相关性研究方法研究了现代黄河三角洲地区土壤特性对PCBs分布的影响,结果表明：土壤有机质量分数与其类二嗯英类PCBs的总质量浓度呈弱的正相关关系。土壤粒径组成中粘粒质量分数与其类二嗯英类PCBs的总质量浓度呈相关性关系,且达到极显著的水平;粉砂粒的质量分数与类二嗯英类PCBs的总质量浓度无相关关系;砂粒质量分数与类二嗯英类PCBs的质量浓度呈负相关关系,达到显著相关的水平。土壤溶解盐质量分数及pH值与类二嗯英类PCBs的总量没有明显的相关性。可见,土壤中有机质、土壤颗粒组成中粘粒和砂粒质量分数是影响现代黄河三角洲地区土壤中PCBs分布的主要因素。     

青岛近海生物体内多环芳烃、多氯联苯和有机氯农药的含量和分布特征(Concentrations and Distribution Characteristic of PAHs, PCBs and OCPs in the Marine Organisms of Qingdao Coastal Area)

为初步了解青岛近海生物体内多环芳烃、多氯联苯和有机氯农药的含量和组成特征,于2007年10～11月采集了青岛近海13个站位的鱼、虾和软体类动物,分析了其肌肉中的多环芳烃、多氯联苯和有机氯农药的含量和组成.结果表明,多环芳烃、多氯联苯和有机氯农药更易在鱼类体内富集,其含量远大于软体类和虾类.高氯代联苯和高环芳烃在同系物中的比例在鱼类体内最小,这可能是由鱼类和虾类、软体类不同的生活习性造成的.有机氯农药中,滴滴涕的含量显著高于六六六.     

北部湾潮间带沉积物中重金属和多氯联苯的分布特征及生态风险评价

选择北部湾9个典型采样点,研究了潮间带沉积物中重金属和多氯联苯(PCBs)的分布特征和生态风险.分析结果表明,Hg、As、Cu、Pb、Zn、Cd、Cr等重金属和总PCBs的平均含量分别为0.100、10.00、19.89、45.97、208.65、0.098、17.86 mg.kg-1和1.48!g.kg-1.重金属和PCBs表现出不同的空间变化规律.相关性分析表明,北部湾潮间带的重金属主要来自人为污染;沉积物的粒度参数和有机质含量等性质特征是影响PCBs分布和迁移的重要因素;重金属和PCBs总量之间不存在明显的相关性.生态风险评价结果表明,PCBs和Cd是北部湾潮间带最主要的生态风险因子,Zn和PCBs是优势污染物;研究区域总体处于中等生态风险等级,表明沿岸港口和临海工业等人为活动已经对北部湾滨海地区造成了一定的环境压力.     

近海沉积物DlPCBs对斑马鱼胚胎EROD和cyp1a mRNA的影响

为探究湛江近海域海洋沉积物中类二噁英多氯联苯(dioxin-like polychlorinated biphenyls,Dl PCBs)的生物学毒性效应,选取湛江近海域2个地点(近工业区TS和近生活区JSW)采集沉积物样品,制备近海域沉积物Dl PCBs提取物,将斑马鱼胚胎暴露于不同浓度的Dl PCBs提取物,测定斑马鱼胚胎7-乙氧基异吩恶唑脱乙基酶(ethoxyresorufin-O-deethylase,EROD)活性和cyp1a m RNA相对表达量。结果发现,JSW采样点Dl PCBs提取物染毒组EROD酶活性变化与TS采样点Dl PCBs提取物一致,在各染毒浓度下,斑马鱼仔鱼EROD酶活性为对照组的1.1~1.8倍。TS和JSW采样点不同浓度Dl PCBs提取物暴露斑马鱼胚胎96 h后,使斑马鱼仔鱼cyp1a m RNA相对表达量是对照组的3.36~19.45倍。说明一定浓度的近海沉积物Dl PCBs能诱导斑马鱼仔鱼EROD酶活性和cyp1a m RNA表达量升高,且呈现浓度-效应关系。     

Methane Production in River and Lake Sediments in Taiwan

To investigate the relationship between methane production in the sediments and pollution of the river and lake, biochemical oxygen demand (BOD) and chemical oxygen demand (COD) of the water sample, organic matter content and methane production of the sediment were measured. Experimental results indicated that BOD, COD and organic matter contents were low in Bei-tan Lake, the I-lan River and reservoirs; and methane production of these sediments ranged from 0.24 to 1.06 mg L- 1. However, BOD, COD and organic matter contents were high in the Hsin-dan River, Keelung River, drainage river of Taoyuan County, park pond and fishery pond. Methane production of these sediments was between 11.75 and 54.54 mg L-1. Sediments of drain river and fishery pond had high methane production, at 25.41 to 54.54 mg methane L. Methane production of sediments had a good correlation with BOD, COD and organic matter contents. Methane production was proportional to the increment in incubation temperature from 12 to 40C.     

Biotransformations of Chlorophenols in River Sediments

The accumulation of chlorophenols, including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), from river sediments from southern Taiwan were studied. Through simple or more exhaustive extractions, the results showed that 99% of the samples containing 2,4,6-TCP and PCP could be removed by simple extraction. the concentrations were found to range from non-detectable to 16.60 ngg¹ for 2,4,6-TCP and to 25.02 ngg¹ for PCP. Partition coefficients (K_p) were 0.71, 0.74 mlg¹ for 2,4,6-TCP, 1.35 and 1.41 mlg¹ for PCP. Biodegradation by DCP-adapted or unadapted anaerobes in sediment was carried out. During 21 days' incubation, the complete degradation time for 2,4,6-TCP in DCP-adapted anaerobic, unadapted anaerobic, and unadapted aerobic conditions were found to be 9, 10, 12 days for N3 sediment, and 8, 10, 11 days for N6 sediment, respectively; for PCP it was 19 days, without degradation, 14 days for N3 sediment, and 13, 17, 10 days for N6 sediment, respectively. the biodegradable products were identified as 2,3,4,5-tetrachlorophenol (2,3,4,5-TeCP), 3,4,5-TCP, 3,5-DCP, 3-MCP, phenol, methylphenol, and benzoate for PCP, and 2,4-DCP, 4-MCP, phenol, methylphenol, and benzoate for 2,4,6-TCP.     

Biotransformations of Chlorophenols in River Sediments

Abstract

The accumulation of chlorophenols, including 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), from river sediments from southern Taiwan were studied. Through simple or more exhaustive extractions, the results showed that 99% of the samples containing 2,4,6-TCP and PCP could be removed by simple extraction. the concentrations were found to range from non-detectable to 16.60 ngg¹ for 2,4,6-TCP and to 25.02 ngg¹ for PCP. Partition coefficients (K_p) were 0.71, 0.74 mlg¹ for 2,4,6-TCP, 1.35 and 1.41 mlg¹ for PCP. Biodegradation by DCP-adapted or unadapted anaerobes in sediment was carried out. During 21 days' incubation, the complete degradation time for 2,4,6-TCP in DCP-adapted anaerobic, unadapted anaerobic, and unadapted aerobic conditions were found to be 9, 10, 12 days for N3 sediment, and 8, 10, 11 days for N6 sediment, respectively; for PCP it was 19 days, without degradation, 14 days for N3 sediment, and 13, 17, 10 days for N6 sediment, respectively. the biodegradable products were identified as 2,3,4,5-tetrachlorophenol (2,3,4,5-TeCP), 3,4,5-TCP, 3,5-DCP, 3-MCP, phenol, methylphenol, and benzoate for PCP, and 2,4-DCP, 4-MCP, phenol, methylphenol, and benzoate for 2,4,6-TCP.     

北京市密云县潮河周边土壤中类二恶英PCBs分析评价

为了探讨密云水库上游流域可能给水库带来的非点源污染,本研究测定了入库河流潮河下游周边土壤中12种类二恶英多氯联苯(DL-PCBs)的含量水平。结果表明,ΣDL-PCBs的总含量水平为0.0039~0.0365 ng·g-1,其中PCB-118,115,77为12种DL-PCBs的主要成分,PCB-81,114,157均低于检出限。草地、林地和果园中ΣDL-PCBs的含量高于玉米地,表明研究区的DL-PCBs主要受大气沉降和河流沉积物的影响,受当地人类活动影响不大。与其他研究相比,采样区域的PCBs含量总体处于偏低水平,毒性当量处于中等水平。而毒性当量因子(TEF)较高的PCB-126与PCB-169,可能会对人类和生物产生危害,应给予足够的重视。     

Distribution of Trace Metals in the Surface Sediments of Two Pristine Subalpine Lakes in Taiwan

Sediment cores were collected from two remote subalpine lakes: the rather shallow (1.5 m) Little Ghost Lake at 2040 m elevation and the deeper, Great Ghost Lake (40 m) at 2150 m elevation. Different early diagenesis of metals were observed. the seasonally anoxic hypolimnion drives the annual iron redox cycle and causes the remobilization of metals in the mobile fractions of sediments in the Great Ghost Lake. These result in the redistribution of metals in the mobile fractions of sediment and poor correlation between metal concentrations. in the Little Ghost Lake, the shallow water column is always oxic with less change of metals in the mobile fractions of sediments. As a result, most metals have strong positive correlations with each other.

The distributions of metal/Al ratios, total metal contents and acid-leached metal concentrations in the near-surface sediments of these two lakes suggest that the anthropogenic inputs from the atmospheric fallouts in recent decades are one of the major factors affecting the distributions of metals such as cadmium, lead and, to a lessor extent, zinc. the Pb-206/Pb-207 ratios confirm the anthropogenic lead input in these surface sediments.     

Distribution of Trace Metals in the Surface Sediments of Two Pristine Subalpine Lakes in Taiwan

Sediment cores were collected from two remote subalpine lakes: the rather shallow (1.5 m) Little Ghost Lake at 2040 m elevation and the deeper, Great Ghost Lake (40 m) at 2150 m elevation. Different early diagenesis of metals were observed. the seasonally anoxic hypolimnion drives the annual iron redox cycle and causes the remobilization of metals in the mobile fractions of sediments in the Great Ghost Lake. These result in the redistribution of metals in the mobile fractions of sediment and poor correlation between metal concentrations. in the Little Ghost Lake, the shallow water column is always oxic with less change of metals in the mobile fractions of sediments. As a result, most metals have strong positive correlations with each other.

The distributions of metal/Al ratios, total metal contents and acid-leached metal concentrations in the near-surface sediments of these two lakes suggest that the anthropogenic inputs from the atmospheric fallouts in recent decades are one of the major factors affecting the distributions of metals such as cadmium, lead and, to a lessor extent, zinc. the Pb-206/Pb-207 ratios confirm the anthropogenic lead input in these surface sediments.