Characterization and composition of heavy metals and persistent organic pollutants in water and estuarine sediments from Gao-ping River, Taiwan

The objective of this study was to determine the concentrations and possible sources of heavy metals and persistent organic pollutants (POPs) in water and estuarine sediments from Gao-ping River in order to evaluate the environmental quality of aquatic system in southern Taiwan. High concentrations of heavy metals including Cr, Zn, Ni, Cu and As, ranging from 10.7 to 180 mg/kg-dry weight (dw), were detected in sediments from Gao-ping River. When normalized to the principal component analysis (PCA), swinery and electroplating wastewaters were found to be the most important pollution sources for heavy metals. Of various organochlorine pesticide (OCP) residues detected, aldrin and total-hexachlorocyclohexane (HCH) were frequently found in sediments. The total concentrations of OCPs were in the range 0.47-47.4 ng/g-dw. Also, the total-HCH, total-cyclodiene, and total-dichlorodiphenyltrichloroethane (DDT) were in the range 0.37-36.3, 0.21-19.0, and 0.44-1.88 ng/g-dw, respectively. The polychlorinated biphenyl (PCB) concentrations in sediments from Gao-ping River ranged between 0.37 and 5.89 ng/g-dw. The PCB concentrations are positively correlated to the organic contents of the sediment particles. alpha-HCH was found to be the dominant compound of HCH in the sediments, showing that long-range transport may be the possible source for the contamination of HCH in sediments from Gao-ping River. In summary, trace amounts of POPs in estuarine sediments from Gao-ping River were detected, showing that there still exist a wide variety of POP residues in the river sediments in Taiwan. These POP residues may be mainly from long-range transport and weathered agricultural soils, while heavy metal contamination is primarily from the swinery and industrial wastewaters.     

Contaminants still high in top-level carnivores in the Southern California Bight: levels of DDT and PCBs in resident and transient pinnipeds

Highly industrialized areas, such as the Southern California Bight, often have high levels of contaminants in marine sediments, which can cause chronic exposure to organisms long after their use has ceased. tDDT and tPCB were analyzed in the blubber of 145 stranded pinnipeds that died at local marine mammal centers between 1994 and 2006. Resident species (California sea lion and Pacific harbor seal) had significantly higher concentrations of tDDT and tPCB than the transient species (northern elephant seal). Adult female California sea lions had significantly lower concentrations of tDDT and tPCB than pups, yearlings, and adult males. Concentrations of both tDDT and tPCB in California sea lions significantly declined over time, but did not change in northern elephant seals. Current concentrations of tDDT and tPCB in California sea lions and harbor seals are among the highest values reported worldwide for marine mammals and exceed those reported to cause adverse health effects.     

东湖水体中多氯联苯的研究

于1994年6月,采用高分子多孔聚合树脂对武汉东湖水进行富集采样,样品经净化后利用毛细管柱色谱进行多氯联苯（PCBs）总量及同类物（congeners）的分离测定。结果表明,东湖水样中PCBs总含量为2．7ng／L,检出的20多个PCBs同类物其含量分别在0．002－1．12ng／L范围内。其同类物中低氯取代的PCBs相对含量明显高于工业用商品PCBs中的相应含量。     

中华白海豚(Sousa chinensis)组织中多氯联苯的研究

以珠江口海域的两头中华白海豚为研究对象,采用气相色谱法分析了海豚组织中多氯联苯（PCBs）的含量分布特征和毒性水平。结果表明,PCBs在海豚10种不同组织中的含量范围为25．1—85567．3ng／g,PCBs含量最高的组织为额隆和皮肤,其次为肝脏、肌肉、心脏、睾丸和脑,最低的为肺、胃和肾脏;PCBs同系物和同族物在海豚不同组织中的分布特征相似,同系物中以PCB101＋113和PCB153所占总量的百分比最大,在10．25％-51．70％之间;在同族物中以含在同族物中以5个氯原子和6个氯原子的PCBs为主,所占百分比均在23．53％-60．06％之间;运用二蛞哄毒性当量（TEQ）评价了中华白海豚不同组织中PCBs的毒性,其TEQs范围为55．9—68191．0pg／g,其中皮肤TEQs含量最高。TEQs主要来自非邻位取代的PCBs,占总量的74．15％-99．62％,其中来自PCB126的占34．11％-96．5I％。与世界其他海域海豚的PCBs污染水平相比,成年中华白海豚受PCBs污染严重,其体内的PCBs含量和毒性当量均已超出安全浓度范围,对其健康已造成威胁。     

Organochlorine and butyltin residues in deep-sea organisms collected from the western North Pacific,off-Tohoku,Japan

Organochlorine (OCs) and butyltin (BTs) residues were determined in deep-sea organisms collected from the western North Pacific, off-Tohoku, Japan. Among OCs, concentrations of polychlorinated biphenyls (PCBs) and DDTs (DDTs and its metabolites) were the highest in deep-sea organisms (maximum concentrations of 6700 and 13,000 ng/g lipid wt, respectively). Chlordane compounds (CHLs) were the next most abundant OCs, and hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were the lowest. BTs were also detected at maximum concentrations of 570 ng/g wet wt. Concentrations of PCBs, CHLs and BTs in deep-sea organisms collected from the western North Pacific, off-Tohoku, were generally lower than those in deep-sea and shallow water organisms from Japanese coastal waters. On the other hand, considerable variations in the concentrations of OCs were found among deep-sea organisms analyzed. Several carnivorous fishes such as snubnosed eel, lanternshark and grenadiers accumulated some OCs such as PCBs, DDTs and CHLs at high concentrations of up to a few μg/g levels. In addition, the residue pattern of OCs and BTs in fishes showed a specific trend according to the sampling depth; higher concentrations of PCBs, DDTs and CHLs and lower concentrations of HCHs, HCB and BTs were found in fishes collected from greater depth (1000 m) compared to those from shallower waters. This trend is consistent with the results of our earlier study on mesopelagic myctophid fishes. Results of this study suggest vertical transport of hydrophobic OCs such as PCBs, DDTs and CHLs and its accumulation in benthic deep-sea organisms.     

沉积物样品中干扰物的去除及多种持久性有机污染物气相色谱分析

建立了沉积物样品中17种有机氯农药和8种多氯联苯持久性有机污染物的气相色谱分析方法。针对沉积物样品基质复杂、含有大量硫干扰的特点,重点研究了前处理技术。采用加速溶剂提取(ASE)技术提取样品中的有机污染物,比较了加入铜粉后ASE在线除硫和超声波提取除硫的效果。结果表明,加入铜粉ASE提取不能完全去除硫的干扰,需进一步采用超声波提取10 min除硫才能大大减少杂质对目标化合物的干扰。沉积物样品中的色素类及小分子干扰物质采用凝胶渗透色谱结合固相萃取技术进行净化,满足了气相色谱-电子捕获检测器分析的要求。25种化合物的平均添加回收率为68%～131%,方法精密度(RSD,n=6)小于22.3%,检出限为0.10～0.51μg/kg。建立的样品前处理技术净化彻底,适合用于不同地区、不同类型的沉积物样品气相色谱分析。     

南中国海海水中有机氯农药和多氯联苯的含量及分布特征

近年来,随着沿海化工生产基地的大量投入运营及海上危险化学品运输业的日益增长,海洋生态环境受到严重威胁,我国海洋环境中持久性有机污染物如有机氯农药及多氯联苯在近海环境中普遍检出。为了对南中国海水体中持久性有机污染物的污染现状有所了解,本文利用气相色谱-电子捕获检测器(GCECD)对南中国海海水中的15种有机氯农药和多氯联苯进行测定,两类化合物各检出6种。采用外标法进行定量分析,结果显示:调查海域表层海水中有机氯农药和多氯联苯类化合物的浓度范围分别为0~92.30ng/L和1.16~76.24 ng/L,200 m层海水中分别为0~69.85 ng/L和0~49.63 ng/L,500 m层海水中分别为0~56.68 ng/L和0~26.47 ng/L。由此可看出,该海域有机氯农药和多氯联苯的含量分布特征大致呈现为:表层200 m层500 m层,原因可能是污染源主要来自周围地表径流或大气输入,且随着时间的推移污染物吸附于悬浮体由表层向下层迁移。与国内外相关海洋环境中有机农药及多氯联苯含量水平相比较,南中国海海水中有机农药和多氯联苯的含量低于国内大部分水域,但高于国外已知海洋水体中的含量。南中国海中有机农药和多氯联苯含量和分布特征的取得为下一步对海洋环境的研究和保护工作提供了基础数据。     

水产品中多氯联苯残留量的气相色谱法测定

研究并建立了水产品中的7种多氯联苯残留的气相色谱检测方法,用该方法对鱼、虾、贝、蟹、甲鱼等多种水产动物中多氯联苯的残留量进行了分析测定。结果表明,7种多氯联苯的峰面积与其质量浓度在1.0～200ng／mL范围内呈线性关系,相关系数均大于0．999。鳕鱼和牡蛎样品中添加1.0ng／g的多氯联苯标准液时,多氯联苯的回收率为81．33％～85．33％;相对标准偏差为7．33％～9．21％。方法的测定低限为0．3ng／g。另外,通过优化前处理方法,使用硅胶净化柱,缩短了样品的前处理时间,减少了试剂消耗,提高了回收率。     

气相色谱-串联质谱技术分析地质调查植物样品中持久性有机污染物的优势

对于复杂基质的样品,采用气相色谱法、气相色谱-质谱法( GC - MS)不能满足当前痕量水平分析的要求,串联质谱已发展成一种有机分析测试的成熟技术可应用于地质调查样品分析.本文建立了气相色谱-串联质谱技术( GC - MS - MS)分析植物样品中有机氯农药及多氯联苯的方法,通过对植物样品(圆白菜、菠菜、胡萝卜、橘子)分析,系统比较了GC- MS-MS与气相色谱-电子捕获检测器(GC-ECD)和气相色谱-选择离子-质谱( GC - SIS - MS)三种分析技术的检出限、定性定量分析结果,确认了分析方法的适用性.GC- MS-MS方法的检出限为0.03～0.29 ng/g,大部分化合物均低于GC -ECD的检出限,是GC - SIS -MS检出限的0.4倍.GC- MS-MS分析表明,圆白菜不含反式-氯丹,排除了GC-ECD的假阳性检出;检测胡萝卜等基质复杂、净化困难的样品,GC- MS-MS也表现出良好的定性定量能力;检出低含量水平样品菠菜含有0.26 ng/g六氯苯,而气相色谱未检出,表明GC- MS-MS显著提高了分析灵敏度,能够对样品中低含量的化合物进行准确定量.在三种分析技术中,GC- MS-MS在样品的准确定性、复杂基质样品分析灵敏度、低含量水平准确定量等方面都具有独特的优势,同时能够应用于复杂样品检测结果的确证.