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.     

大石围天坑群土壤中有机氯农药的分布与富集特征

选择典型的岩溶地区广西乐业大石围天坑群为研究区,采集不同岩溶地形的土壤,利用 GC-ECD 气相色谱仪测定六六六(HCHs)和滴滴涕(DDTs)两种有机氯农药的浓度.结果表明,大石围天坑群地表土壤、天坑绝壁土壤、天坑底部土壤以及地下河(洞穴)土壤中的 HCHs 和 DDTs 平均浓度分别为0.06 ng/g 和0.02 ng/g、0.31 ng/g 和0.27 ng/g、0.96 ng/g 和0.28 ng/g 以及0.14 ng/g 和0.10 ng/g.研究区土壤中有机氯农药总检出率为:天坑地表<天坑绝壁<天坑底部<地下河(洞穴),随高程降低而增高;有机氯农药(OCPs = HCHs + DDTs)浓度的空间分布特征为:天坑底部>天坑绝壁>地下河(洞穴)>天坑地表,天坑底部 OCPs 浓度明显高于顶部;因此,大石围天坑呈现明显的有机污染物“冷陷阱效应”     

土壤和沉积物中22种有机氯农药和8种多氯联苯的气相色谱分析

近年来地下水、土壤和沉积物等介质中有机氯农药和多氯联苯分析方法的改善主要集中在样品前处理和分析测试条件等方面,而探讨布点、采样等方面的整套方法较少。本文建立了一套适用性较广的气相色谱法同时测定土壤和沉积物中22种有机氯农药和8种多氯联苯,方法检出限为0.09~0.48 ng/g,平均空白回收率为58.7%~133.7%。针对布点、采样、运输、保存、提取、净化、浓缩、仪器测试、数据处理和提交报告整个过程阐述了方法的有效性和实用性;并对提取、净化、测试等多个环节提供了两种或更多的选择,使方法具有更大的灵活性。本文提出,布点前应根据踏勘样品和前人资料考虑采集不同深度的样品;样品的布点、采集和制备均需选择样品,它们共同决定了样品的代表性;分析方法要灵活运用,对于很少检出的目标化合物可采用允许共峰但分析快速的方法,如果有检出再采用针对性的方法分别测定;样品的测定序列不应为了节约分析成本而过于简单。     

Assessing the spatial variability,level and source of organic chemical contaminants in bivalve fishing grounds on the Galician coast (NW Spain)

Polychlorinated biphenyls, organochlorine pesticides, organotin compounds and triazines were quantified in sediments and bivalves collected in four areas on the Galician coast. One or several species were analysed at each site depending on their availability, including mussels (Mytilus galloprovincialis), cockles (Cerastoderma edule), clams (Venerupis pullastra and Ruditapes decussatus) and razor shells (Ensis siliqua). The general spatial distribution of contaminants was consistent in spite of the different sources of contamination. High inter-species variability was also observed. M. galloprovincialis and V. pullastra showed the highest levels of contaminants and intra-spatial variability, which highlights them as suitable species to be used as sentinel organisms. The area of O Burgo showed some worrisome results: PCB sediment concentrations were within the range that could cause biological effects. Also the level of heptachlor observed in V. pullastra was above limits accepted on edible seafood. Finally TBT concentration in mussels correlated with concentrations causing imposex in snails.     

微量注射器中有机氯农药和多氯联苯类化合物的残留与清洗研究

微量注射器越来越多地用于转移微量液体,但是微量注射器中有机化合物的残留可能造成的交叉污染易被忽视。本文系统地研究了微量注射器中有机氯农药类和多氯联苯类化合物的残留和清洗效果。结果表明,三个品牌的微量注射器清洗的难易不同,在选择微量注射器时应根据实验结果选择满足实验要求的类型;正己烷清洗液的体积与稀释倍数成正比,原因在于0.1 mL、0.2 mL、0.5 mL和1 mL第一针清洗液洗出的化合物质量接近,清洗液体积甚至与洗出化合物的量负相关,因此选用体积最小的0.1 mL效果和成本优势最大;相同浓度的有机氯农药类和多氯联苯类化合物清洗效果接近,原因可能是这两类化合物的理化性质相近;不同浓度的标准溶液需要清洗的次数不同,浓度越高的标准溶液需要清洗的次数越多。本文总结出三条清洗规律:①1 mL微量注射器中的残留量约为吸取量的1%左右;②第一针洗出化合物的量超过残留量的90%;③随着清洗次数的增加,呈现清洗效果越来越差、稀释倍数越来越小的趋势。根据这些规律,可以针对不同浓度的不同化合物采取相应的清洗措施,在标准溶液配制和气相色谱仪方法设置过程中更有效地预防污染和节约成本。     

珠江虎门潮汐水道难降解有机污染物入海通量研究

对采自虎门潮汐水道狮子洋4个采样点表层水样中的多环芳烃、有机氯农药进行了定量分析.洪、枯水期水体中多环芳烃总量(颗粒相和溶解相)分别是786～964 ng/L、11 360～19 603 ng/L;有机氯农药总量分别是9.68～26.29 ng/L、41.65～96.23 ng/L.根据4个采样点洪、枯水期有机污染物浓度的平均值估算多环芳烃、有机氯农药的年均入海通量.初步估算结果显示:多环芳烃的总入海通量(溶解相和颗粒相)为438.4×103 kg/a,其中颗粒相是52.5×103 kg/a;16种优控多环芳烃的入海通量为247.9×103 kg/a.有机氯农药的总入海通量是2.6×103kg/a,其中六六六的入海通量为1.1×103 kg/a,滴滴涕类的入海通量为0.3×103kg/a,其它有机氯农药的入海通量为1.2×103 kg/a.     

土壤中25种有机氯农药和多氯联苯的气相色谱分析方法研究

研究了土壤中17种有机氯农药和8种多氯联苯组分的气相色谱分析方法。采用加速溶剂萃取技术提取,优化了萃取条件。提取液用固相萃取技术进行净化,采用20 mL含3%(体积分数)甲苯的正己烷-乙酸乙酯(体积比8∶2)进行淋洗,得到很好的净化效果。方法检出限在0.06~0.27μg/kg,线性范围在1.38~55.2 ng/mL,目标化合物的平均添加回收率在65%~97%,相对标准偏差(RSD,n=6)小于17.11%。方法快速、灵敏、准确,适合批量样品的分析。     

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides in water columns from the Pearl River and the Macao harbor in the Pearl River Delta in South China

Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) were measured in suspended particles and dissolved phase from the Baiertang water column and the Macao water column samples as collected from the Guangzhou channel of the Pearl River and the Macao harbor, where the sediments were heavily contaminated with organic pollutants. Total OCPs concentration varies from 23.4 to 61.7 ng/l in Baiertang water column and from 25.2 to 67.8 ng/l in Macao column, while total PAHs concentration varies from 987.1 to 2878.5 ng/l in the Baiertang water column and from 944.0 to 6654.6 ng/l in the Macao column. The vertical distribution profiles of pollutants and the partition of pollutants between particles and dissolved phases indicate that the sediments in Baiertang act as an important source of selected pollutants, and the pollutants in water of this region were mainly originated from the release and re-suspension of contaminants residing in the sediments. The sediments in Macao harbor act as a reservoir for organochlorine pesticides, such as DDTs mainly introduced by river inflow from Xijiang and PAHs input by brackish water from the Lingdingyang estuary. Combustion of fossil fuels and petroleum input are the main sources of PAHs in the Macao water column, while combustion of fossil fuels and coal is responsible for the PAHs in the Baiertang water column. The ratios of DDT/(DDD+DDE) for the Macao water column samples demonstrate that such chemicals were input into this region in recent times.     

Field validation of antioxidant enzyme biomarkers in mussels (Perna viridis) and clams (Ruditapes philippinarum) transplanted in Hong Kong coastal waters

Green-lipped mussels, Perna viridis, and Manila clams, Ruditapes philippinarum were sourced from “clean” sites in the Hong Kong region, depurated in a laboratory using uncontaminated filtered seawater for 8 days, and transplanted to a suspected gradient of chemically polluted sites in Hong Kong. After 14- and 28-days of field exposure, several antioxidant parameters including glutathione S transferase (GST), catalase (CAT), glutathione peroxidase (GPx), and glutathione (GSH) were quantified in gill and hepatopancreas tissues. Whole body tissue concentrations of polycyclic aromatic hydrocarbons (PAHs), petroleum hydrocarbons (PHCs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) were determined in pooled site samples. Chemical analyses indicated that: (a) clams had higher levels of PAHs, PHCs, DDTs and PCBs, whereas mussels had higher hexachlorocyclohexane (HCHs) and there was no difference between species for dieldrin and remaining OCs; (b) Kat O should not be continued as a “clean” reference site for Hong Kong, because of the levels of contaminants measured and (c) PAH concentrations in the current survey were similar to those previously measured. Toxicological conclusions were: (a) antioxidant responses were different between species; (b) CAT and GST have highest utility in clams for field use in Hong Kong, whereas CAT in both gill and hepatopancreas tissue showed most potential in mussels; (c) significant induction of antioxidant responses over day 0 (excluding GPx in both tissues, and GST in mussel hepatic tissue); (d) groups of contaminants do not consistently induce antioxidant responses and (e) organochlorines and PCBs correlated significantly with CAT and GST in clam hepatopancreas and with CAT in mussel gill and hepatic tissue. Multivariate statistical techniques indicated little relationship between the site patterns for antioxidant responses and the contaminant gradients identified in body burden analysis.     

Environmental and pollution condition of the huizache-caimanero lagoon, in the north-west of Mexico

The fish and shrimp production of the Huizache-Caimanero Lagoon, located on the Mexican Pacific, has been decreasing in recent years, which may be due to environmental and pollution conditions. Therefore, water and sediment samples were analysed to quantify nutrients, pesticides, and coliform bacteria. The results indicated that the system is polluted considerably during the rainy season due to continental runoff carrying municipal and agricultural wastes, thereby increasing coliform pollution and nitrate concentrations. This is less apparent for phosphates and pesticides. We conclude that pollution and environmental changes are important causes decreasing production; recent studies have reported biochemical and physiological alteration in aquatic organisms exposed to similar levels of pesticides as reported here. During the rainy season, coliform levels are above permissible levels established by sanitary regulations, and are thus pose a risk to public health.