Polychlorinated biphenyls in surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in East China Sea

The spatial distribution and source of polychlorinated biphenyls (PCBs) in 30 surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in Eastern China were analysed. Total concentrations of PCBs ranged from 9.33 to 19.60 ng g⁻¹ dry weight for all the sampling stations. The observed PCB levels were lower than those in areas of high urbanisation or contamination in the bay. Low-chlorinated PCBs, dominated by tri-PCB, were identified as the prevalent contaminate of surface sediments, and the top three PCB congeners were lighter chlorinated congeners (PCB 8, PCB 18 and PCB 28). These results were in agreement with the fact that tri-PCB compounds are the dominant contaminants in China. The result of the principal component analysis revealed that all samples were similar in composition to Aroclor 1242, suggesting they might originate from electrical capacitors and transformers. The levels of PCBs were significantly correlated with the total organic carbon in the sediments.     

现代黄河三角洲土壤中多氯联苯来源解析研究

对现代黄河三角洲22个表层土壤样品中类二英类多氯联苯（PCBs）进行双毛细管柱GC-ECD结合MS测试,并对所得数据进行主成分分析,在同系物水平上解析了现代黄河三角洲土壤中PCBs污染的类型、来源、贡献率和同系物组成.结果表明,现代黄河三角洲土壤中PCBs污染存在4类污染源：第1类污染是由地表径流带来的非点源污染,来自黄河沿岸企业的工业生产和使用,其贡献率为49.6％,同系物组成与国产PCBs相似,且与Aroclor1221相对应;第2和第3类同属点源污染,来自沿海地区的油田开采活动,贡献率分别为15.0％和10.1％,第2类同系物组成与Aroclor1221和Aroclor1242叠加的结果类似,第3类与Aroclor1260相似;第4类污染是由大气污染导致的非点源污染,来自大气的干、湿沉降,其贡献率为8.4％,同系物组成与Aroclor1242、Aroclor1248和Aroclor1260叠加的结果类似.     

Monofluorinated analogues of polychlorinated biphenyls (F-PCBs): synthesis using the Suzuki-coupling, characterization, specific properties and intended use

An improved method, a palladium-catalyzed cross-coupling reaction the so-called Suzuki-coupling, was used to synthesize 19 monofluorinated analogues (F-PCBs) of polychlorinated biphenyls (PCBs), including analogues of PCBs 28, 52 and 81. The coupling of chlorinated and/or fluorinated isomers of aryl boronic acids with bromo- and/or iodobenzenes gave the desired F-PCB congeners in good to excellent yields. The self-coupling product of the aryl boronic acids was the major impurity, but this limitation could be minimized. The influence of ortho-substitution by chlorine on the reaction time was studied in detail. The F-PCBs were characterized by means of ¹H and ¹⁹F NMR and mass spectrometry (MS). F-PCBs show remarkably similar characteristics in many aspects to those of the corresponding non-fluorinated parent PCBs. Since fluorine is generally resistant to degradation, once incorporated into a substrate it functions as an indelible label that can be used to monitor structures and dynamics. F-PCBs may prove their usefulness as markers and tracers in mechanistic and toxicological studies. The aim of further research will be to test the suitability of fluorine as a sensitive probe in a broad range of applications, including synthesis, analytical, mechanistic and toxicological studies.     

The variability of polychlorinated biphenyls levels in urban soils from five European cities

The concentration of PCBs in topsoils from five European cities was assessed and the highest levels were found in Glasgow (Scotland), followed by Torino (Italy), Aveiro (Portugal), Ljubljana (Slovenia) and Uppsala (Sweden). All cities showed the presence of local sources in addition to diffuse contamination from global atmospheric transport. The association of general soil parameters with PCBs in Glasgow and with heavier congeners in Torino and Ljubljana indicates that retention of these compounds is occurring. The profiles obtained resemble Aroclor 1254 and 1260, which are important local sources. Nevertheless, differences in PCB profiles were observed among cities, due to the combined effects of the age of the contamination (which determines the time available for volatilisation and degradation), different sources of PCBs and differences in climate (which influence volatilisation and deposition).     

土壤中多氯联苯分析方法研究进展

文中综述了多氯联苯的分析技术及其研究进展。介绍了样品前处理技术如索氏萃取法、超声萃取法、微波辅助萃取、超临界流体萃取、加速溶剂萃取等在土壤样品中多氯联苯分析中的应用;阐述了气相色谱、液相色谱、气质联用技术在土壤样品中多氯联苯的检测,并对土壤中未来多氯联苯检测技术的发展提出了展望。     

PCDD, PCDF, PCB and PBDE concentrations in breast milk of mothers residing in selected areas of Slovakia

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs) in 33 breast milk samples collected in 2006-2007 from primipara mothers close to four industrial areas of Slovak Republic were determined. The total PCDDs/PCDFs and dl-PCBs expressed as TEQ based on WHO TEFs 1998 in breast milk samples varied from 5.0 to 51.8 pg g⁻¹ fat (median: 13.1 pg g⁻¹ fat; mean: 18.0 pg g⁻¹ fat). The measurements of seven PBDE congeners (IUPAC No. 28, 47, 99, 100, 153, 154, and 183) were performed for the first time in human milk from Slovakia. PBDE levels ranged between 0.22 and 1.62 ng g⁻¹ fat, with median and mean value of 0.43 ng g⁻¹ fat and 0.57 ng g⁻¹ fat respectively. No statistically significant differences were observed between studied areas in total PBDE concentrations.Furthermore, this study presents first results concerning the daily intake (DI) of PCDDs/PCDFs and dioxin-like compounds for the most vulnerable breast-fed infant population in Slovakia. The total PCDD/PCDF and dl-PCB DI for an infant during the first 2 months of life was estimated in a range from 14.4 to 230 pg TEQ kg⁻¹ b.w., with a median value of 58.9 pg TEQ kg⁻¹ b.w.. The DI values substantially exceeded the tolerable daily intake (TDI) 1-4 pg TEQ kg⁻¹ b.w. recommended by WHO. The dietary infant intake concerning PBDEs was estimated to be between 0.69 and 7.1 ng kg⁻¹ b.w. d⁻¹, with median value of 1.7 ng kg⁻¹ b.w. d⁻¹.     

Concentration of DL-PCBs in fish from market of Parma city (north Italy): estimated human intake

The concentrations of 12 congeners of non-ortho and mono-ortho dioxin-like polychlorinated biphenyls (ΣDL-PCB) were measured in 30 fish samples from Parma markets by GC/MS technique. The samples were randomly purchased, choosing the species commonly found in supermarkets. The concentration of DL-PCBs estimated remained under the fixed Italian limit of 4 pg g⁻¹ ww WHO-TEQ (World Health Organization-Toxic Equivalent) in the major part of the samples, so the situation seems to be not at a level sufficient to pose a risk to human health of the Parma population. The medium daily intake for DL-PCBs for Italian consumers (Parma) was also estimated. This value generally resulted minor than 2 pg g⁻¹ ww WHO-TEQ kg⁻¹ body weight, exceeding only in four cases: eel, smooth hound, starry smooth hound and tuna.     

Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland

Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg⁻¹ lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.     

A national survey of polybrominated diphenyl ethers (PBDEs) and indicator polychlorinated biphenyls (PCBs) in Chinese mothers' milk

Seven polybrominated diphenyl ethers (PBDEs) congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154 and BDE-183) and six indicator polychlorinated biphenyls (PCBs) congeners (CB-28, CB-52, CB-101, CB-138, CB-153 and CB-180) were measured in 24 pooled human milk samples comprised of 1237 individual samples from 12 provinces in China. The samples were taken to estimate the background body burden of general population and assess nursing infant exposure via human milk in China. The median concentrations of ∑₇PBDEs and ∑₆PCBs were 1.49 and 10.50 ng g⁻¹ lipid weight (lw), respectively. BDE-28, BDE-47 and BDE-153 were predominant PBDE congeners accounting for nearly 70% of ∑₇PBDEs. As for indicator PCBs, CB-153 was the most abundant congener, followed by CB-138. In our study, there was no significantly statistical relationship between concentrations of PBDEs in milk samples and maternal age as well as dietary habits. ∑₇PBDEs did not correlate to ∑₆PCBs in Chinese mothers’ milk. The human exposure to indicator PCBs in China was found to be significantly determined by maternal age, dietary habits and geographical factors. It is suggested that Chinese general population is probably exposed to PBDEs with multiple sources and pathways. The estimated daily intakes (EDI) of BDE-47, BDE-99 and BDE-153 for the Chinese nursing infant were much lower than corresponding threshold reference values suggested by USEPA.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0-23 (mean: 13, median: 14) and 2.7-20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16-326 (mean: 107, median: 100) and 12-252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.