Application of water as a solvent in microwave-assisted extraction for analysis of PCBs and CBzs in fly ash

Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE.     

Importance of REP values when comparing the CALUX bioassay results with chemoanalyses results Example with spiked vegetable oils

Differences between chemical activated luciferase gene expression (CALUX) bioassay and chemoanalyses results are observed.This paper shows that calculations of the TEQ values using REP values instead of WHO TEF values give different results. The REP values do affect the results obtained by the CALUX technique. These differences are more marked for the dioxin like PCB compounds (CALUX TEQ values are lower than WHO TEQ values) than for the dioxin compounds (CALUX TEQ values are higher than WHO TEQ values).The CALUX results were compared with the concentrations of the congeners’ spiked into the oil.     

An overview of laboratory performance studies conducted by the IAEA for marine pollution studies of metals and organic contaminants

Aspects of the International Atomic Energy Agency (IAEA) Analytical Quality Control Services (AQCS) for marine environmental studies are discussed, focusing on recent laboratory performance studies (LPS) and the production of reference materials for trace metals and organic compounds in various marine matrices. The IAEA has organized seventeen global interlaboratory studies for a range of organic contaminants. Of note has been the inclusion of numerous polychlorinated biphenyl congeners (PCBs) and some sterols of anthropogenic origin. Concurrently, there have been eleven worldwide intercomparison exercises for trace metals in the marine environment, most of which included methylmercury. Although such interlaboratory studies can help improve performance in individual laboratories and regional laboratory networks, the results reveal that problems remain in the determination of some metals and many organic contaminants.     

Individual determination of ortho and non-ortho substituted polychlorobiphenyls (PCBs) in sediments by high performance liquid chromatographic pre-separation and gas chromatography/ECD detection

Summary An analytical procedure for the individual determination of ortho and non-ortho PCB congeners in sediments, using high performance liquid chromatography (HPLC) preseparation and gas chromatography/ECD detection, is described. Gas chromatography/FTIR spectrometry (GC/FTIR) and gas chromatography/mass spectrometry (GC/MS) were employed for individual congener identification and determination. Sample extraction, clean-up of extract and selective elution procedures were optimized by using reference certified marine sediment samples. Recovery and precision were typically 83% and 16% respectively at 2 ng/g of total PCB content. The proposed procedure, tested by analyzing real sediment samples, showed a reproducibility better than 20% at 13 ng/g PCB level.     

Performances and limitations of the HRMS method for dioxins, furans and dioxin-like PCBs analysis in animal feedingstuffs: Part I: Results of an inter-laboratory study

The European strategy for dioxin monitoring of the food chain has defined high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS) method as the confirmatory method that can provide reliable and comparable results at sub-parts per trillion (ppt) level. This paper describes the first inter-laboratory study on dioxins, furans and dioxin-like PCBs by HRGC/HRMS method in animal feedingstuffs. Two different statistical approaches (ISO 5725 and Cofino’s statistics) were used for the statistical evaluation. For this particular study, the performances of the HRGC/HRMS method seem to be congener-independent in repeatability and reproducibility conditions over a concentration range covering more than four orders of magnitude. Results clearly show the effect of precision loss below 0.1 ppt level per congener in repeatability conditions and below 0.2 ppt level per congener in reproducibility conditions. LODs reported by the laboratories give median values of 0.02 ng/kg for most of the toxic congeners. Relative standard deviation between the laboratories’ mean values using upper-bound approach for TEQ calculation is 6.2%, more than twice the maximum level set at 0.75 ng TEQ/kg of product.     

鱼油中多氯联苯分析的前处理改进研究

采用凝胶渗透色谱法去除鱼油样品中大部分油脂及其他大分子杂质 ,并使用合成硅酸铝镁载体 (Florisil)填充的固相萃取小柱进一步去除剩余的油脂和其他杂质 ,利用分段SIM的GC/MS定性 /定量分析 ,结果表明 ,所用的净化方法可有效地去除油脂及各种对GC/MS分析产生影响的杂质 ,且所用溶剂毒性小 ,方法回收率和重复性均较好 ,具有良好的应用价值。     

PCBs的超(亚)临界水催化氧化及还原裂解

简要分析了多氯联苯(PCBs)的来源及其对环境构成的危害,介绍了PCBs在超（亚）临界水中的反应及其处理效果。分别从超临界水氧化、超临界水裂解及亚临界水还原三个方面阐明了超临界反应过程中PCBs降解的反应路径和降解效率,解释了共溶剂（甲醇、苯）、碱催化剂（Na₂CO₃、NaOH）、氧化剂（NaNO₃、NaNO₂）等对PCBs脱氯和分解的增效作用机理。发现在超临界水氧化与超临界水裂解条件下CH3OH对PCBs降解反应的促进机制有所不同,碱催化剂通过中和反应过程中产生的HCl生成NaCl沉淀导致体系中Cl的含量降低,从而促进脱氯反应的进行。对反应器防腐、处理的经济性方面略作讨论,在总结上述研究工作的基础上提出了PCBs的超临界反应处理技术未来发展的若干研究方向。     

京杭大运河（徐州）表层沉积物中多氯联苯分布特征研究

为确保南水北调东线工程的调水水质,掌握京杭大运河（徐州）中多氯联苯的污染特征,本研究利用气相色谱—电子俘获检测(GC-ECD)法对京杭大运河（徐州）的七个断面取得的表层沉积物中的12种PCBs同系物进行定量分析测定。研究显示,沉积物中的PCBs的浓度范围在16.55 ng/g～114.31ng/g,均值为47.44 ng/g。其中,邳州段的三个断面平均含量最高,并出现了研究区的最高值。在利用潜在生态危害指数法和加拿大环境委员会制定的SQG评价方法对其进行了初步风险评价后,两种评价方法结果都显示,京杭大运河（徐州）表层沉积物中的PCBs已呈现出明显的生态风险。     

Analysis of PCBs in Biotic Matrices by Two-Dimensional GC-ECD

Abstract

The suitability of three GC-ECD systems for the separation of a model mixture containing various congeners of PCBs together with persistent chlorinated aromatics (pesticides and their metabolites, industrial chemicals) was tested. Analyses were performed on two parallel capillaries, the stationary phase of one of them was always in routine practice very common 5% phenyl-methylpolysiloxane, the second one was either 50% phenylmethylpolysiloxane or 7% phenyl-7% cyanopropyl-methylpolysiloxane. The number of unresolved (coeluted) analytes was significantly reduced in these systems and thus unbiased quantitation of PCBs and other components used for regulation was possible. The utilization of this type of multidimensional chromatography for rapid and reliable analysis of real samples (fish oil, human fat) was documented.     

Radioimmunoassay of PCBs in Milk and Blood

A radioimmunoassay was developed capable of determining Aroclor 1260 in milk at levels of from 20 to 80 ppb and in blood from 2 to 16 ppb. The values obtained by radioimmunoassay correlate well with those determined by gas-liquid chromatography (r² = 0.96 for milk and 0.99 for blood) but were lower. Antiserum was produced in rabbits and was specific for 2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl. It cross-reacted with congeners and isomers in Aroclor 1254 and 1260 to the extent that a 20% decrease in binding was observed with 0.1 ng of either mixture. The method requires preliminary cleanup of the extract on alumina and utilizes 25 % dimethyl sulfoxide in the assay medium to promote solubilization of the substrates.