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.     

Levels and temporal trends of PCDD/PCDFs and non-ortho PCBs in ringed seals from East Greenland

The levels and temporal trend of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and non-ortho substituted PCBs (c-PCBs, i.e. CB77, CB126 and CB169) were determined in ringed seal blubber from central East Greenland collected in 1986, 1994, 1999 and 2003, respectively. Since 1986 the concentrations of PCDDs, PCDFs and c-PCBs all show a decreasing trend. The annual decreases were estimated to 5.2% and 5.3% for pg/g WHO-TEQ ww of PCDD/Fs and c-PCB, respectively. The annual median concentrations of PCDDs ranged from 5.4 to 24.4 pg/g WHO-TEQ ww and those of PCDFs from 2.5 to 5.1 pg/g WHO-TEQ ww. Compared to PCDD/Fs concentrations in ringed seals from other Arctic areas the levels of PCDD/Fs found in 1986 were the highest recorded. The annual median concentrations of c-PCBs decreased 24.2 to 9.1 pg/g WHO-TEQ ww. The levels of c-PCBs observed in 1986 are similar to levels found in ringed seals from Svalbard in 1990 and from eastern Hudson Bay in 1989–1992. The dominant and most TEQ-contributing PCDD congener was 1,2,3,7,8-PeCDD. CB126 was the dominating and most TEQ-contributing c-PCB congener. The concentrations of PCDDs, PCDFs and c-PCBs were highly significantly inter-correlated. Principal component analysis of the PCDD/PCDF congeners and c-PCBs was performed to analyse the pattern of compounds during time.     

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.     

ANAEROBIC DECHLORINATION OF PCBs IN SEDIMENTS OF KINNICKINNIC RIVER, WISCONSIN

1 INTRODUCTION Polychlorinated biphenyls (PCBs) have been used for several decades in a variety of industrial applications such as for transformers, capacitors, and hydraulic fluids (Rachdawong and Christensen, 1997). Because of their stability and desirable hydraulic and dielectric properties, PCBs were used extensively. However, later it became clear that they can be toxic and can have deleterious reproductive effects on biota and humans. They may also display dioxin-like toxicity…     

Concentrations of PCBs in coastal mangrove sediments of Hong Kong

The concentrations of polychlorinated biphenyls (PCBs) in surface sediments of ten mangrove sites in Hong Kong were determined by Congener-specific and Arcolor methods. Spatial variations were found between mangrove sites and within the same site, indicating that the sediment samples were heterogeneous and total PCBs concentrations in mangrove sediments should be normalised to compensate for natural variability and for identifying serious anthropogenic contamination. In addition to total organic carbon, Al, Fe and Mn were possible normalisers. Based on PCB/normaliser ratio and 95% prediction limits of scatter plots between total PCB and normaliser, all mangrove sites were not seriously contaminated by human activities. The estimated total PCBs concentrations (quantified by Congener-specific method) for most sediment ranged from 0.5 to 5.8 ng g(-1) (dry weight, n = 92). However, very high concentrations of PCB were found in sub-samples from Yi O, Tolo Pond and Lai Chi Wo, suggesting that these samples represented the PCB contaminated "hot spots".     

Seasonal variation of polychlorinated biphenyl concentrations in the southern part of the Baltic Sea

The impact of seasonal fluctuations in forcing factors such as atmospheric concentration, temperature, and biological productivity on the concentration of polychlorinated biphenyls (PCBs) in the surface water of the southern part of the Baltic Sea was investigated. Water samples were collected on eight cruises over 2 years. A clear seasonal variability in dissolved PCB concentrations was observed with higher levels in summer than in winter and spring. This was attributed to changes in atmospheric concentrations and water temperature, based on measurements showing the PCB levels in the atmosphere and surface water to be close to a partitioning equilibrium. Concentrations in the suspended particulate material (SPM) fraction were also variable, and when the quotient of the organic carbon normalised concentration in SPM and the dissolved concentration was calculated (i.e., the bioaccumulation factor (BAF)), a seasonal pattern was observed which was consistent with kinetic limitations on partitioning into particles caused by plankton growth. However, seasonal variability in the partitioning properties of the SPM may also contribute to this variability.     

Enrichment of organochlorine contaminants in the sea surface microlayer: An organic carbon-driven process

Over 50 seawater samples from two different sites—Barcelona (Spain) and Banyuls-sur-Mer (France)—were analyzed in order to study the extent and postulate the processes driving the enrichment of hydrophobic organic pollutants in the sea surface microlayer (SML). A number of individual polychlorinated biphenyl (PCB) congeners (41) were measured to study their partitioning between the particulate (fraction > 0.7 μm) and the dissolved + colloidal phases (fraction < 0.7 μm), with the latter being differentiated into estimated dissolved and colloidal phases. In addition, several organochlorine pesticides were also measured, namely, HCB, α-HCH, γ-HCH, 4,4′-DDE, 4,4′-DDD and 4,4′-DDT. The presence of PCB congener profiles found in the SML suggests a dynamic coupling with the atmosphere in Banyuls sampling site, whereas offshore Barcelona the presence of highly chlorinated congeners was due to persistent sediment resuspension. The average PCB concentration in the SML dissolved + colloidal phase were higher in Banyuls (7.8 ng L^{− 1}) than in Barcelona (3.6 ng L^{− 1}) samples, but in the particulate phase concentrations were higher in Barcelona (3.2 ng L^{− 1}) to that of Banyuls (1.4 ng L^{− 1}). However, PCB concentrations in the SML generally also showed large variability. Enrichment factors of PCBs and other organochlorine compounds in the SML with respect to the underlying water column ranged from 0.2 to 7.4. This may be explained for both the dissolved + colloidal and particulate phases by the enrichment in the SML of organic carbon (OC) as discerned from particle–water and colloid–water partitioning.