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。     

Polychlorinated dibenzo-p-dioxins （PCDDs） and dibenzofurans （PCDFs） in surface sediment and bivalve from the Changjiang Estuary, China

Surface sediments and bivalves were collected from the Changjiang Estuary in December 2003 and November 2004, respectively. Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in these samples were measured with high-resolution chromatography (HRGC)/High Resolution Mass Spectrometer (HRMS). The concentrations of total PCDD/Fs and toxic equivalent (TEQ) were 169.83±119.63 and 0.81±0.36 pg/g dry weight (dw) in sediments, and 580.33±240.17 and 7.24±3.65 pg/g dw in bivalves. The homolog compositions of PCDD/Fs were similar among samples, the most abundant congener was octa-chlorinated dibenzo-p-dioxin (OCDD) and then octa-chlorinated dibenzofuran (OCDF) and 1,2,3,4,6,7,8-hepta-chlorinated dibenzo-p-dioxin (HpCDD). The herbicide pentachlorophenol (PCP) and sodium pentachlorophenol (Na-PCP) were proved the main source of PCDD/Fs in this area.     

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。     

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in harbor sediments from Sea Lots, Port-of-Spain, Trinidad and Tobago

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in nearshore marine surficial sediments from three locations in Trinidad. Sediments were sampled at Sea Lots on the west coast, in south Port-of-Spain Harbor, south of Sea Lots at Caroni Lagoon National Park, and on Trinidad’s east coast at Manzanilla. Total PCB concentrations in Sea Lots sediments ranged from 62 to 601 ng/g (dry weight {dw}), which was higher than at Caroni and Manzanilla, 13 and 8 ng/g dw, respectively. Total OCP concentrations at Sea Lots were ranged from 44.5 to 145 ng/g dw, compared with 13.1 and 23.8 n/g (dw), for Caroni and Manzanilla respectively. The concentrations of PCBs and of some OCPs in sediments from Sea Lots were above the Canadian interim sediment quality guidelines. To date, this data is the first report on the levels of PCBs and other organochlorine compounds from Trinidad and Tobago.     

沈阳市细河周边农田土壤和大气中有机氯农药和多氯联苯初步研究

在2010年5月调查了沈阳市细河沿岸表层土壤中有机氯农药(OCPs)和多氯联苯(PCBs)的污染现状,评价土壤中OCPs残留的生态风险。沈阳细河沿岸表层土壤中HCHs浓度范围分别为2.32～15.90 ng/g,平均浓度为8.99ng/g。DDTs浓度范围分别为9.06～111.6 ng/g,平均浓度为37.08 ng/g。7种PCBs异构体总平均浓度为1.01ng/g,大部分采样点OCPs和PCBs未超过国家土壤环境质量标准,推断近期可能有林丹的使用但没有新的DDTs污染源输入,但个别地点土壤中的DDTs残留浓度对生态系统健康构成了潜在的威胁。大气蒸汽态HCHs浓度为18.97 ng/m3;DDTs浓度为42.27 ng/m3;PCBs浓度为20.59 ng/m3。研究表明大气长距离传输对该区域的OCPs污染也有较为明显的影响。初步运用逸度概念模型进行分析,发现HCHs和DDTs的逸出方向为从土壤向大气挥发。     

加速溶剂萃取-气相色谱/气相色谱-质谱法测定土壤中7种多氯联苯

建立了土壤样品中7种多氯联苯(PCB 28、PCB 52、PCB 101、PCB 118、PCB 138、PCB 153、PCB 180)的分析方法。土壤样品通过加速溶剂萃取、磺化法结合Florisil固相萃取小柱净化、电子捕获检测器气相色谱分析测定,并结合气相色谱-质谱进一步确证。结果表明,方法回收率为80.06%～100.28%,相对标准偏差(RSD,n=6)为1.01%～6.28%,检出限为0.15～0.50μg/kg。用优化的方法测定复杂基质的土壤样品中多氯联苯,具有提取效率高、净化效果好、结果准确可靠、对环境污染小等优点。     

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。     

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。     

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.     

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.