Disposition of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in two Norwegian epibenthic marine food webs

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of halogenated hydrocarbons, comprising 210 different, theoretically possible congeners. They are relatively hydrophobic and persistent to biodegradation, thereby rendering them subject to bioaccumulation. This study was conducted in Frierfjord and Eidangerfjord in the Grenland fjord system, Norway, heavily polluted by PCDD/PCDF discharges from the magnesium production at Herøya from 1951 to 2001. Pooled samples of surface-sediments and the following organisms were collected for the Frierfjord and Eidangerfjord study areas: common shrimp (Crangon crangon), polychaetes (mainly Nereis diversicolor), shore crab (Carcinus maenas), cod (Gadus morhua), flounder (Platichthys flesus), trout (Salmo trutta), herring (Clupea harengus), benthic amphipods and zooplankton. Concentrations of 2,3,7,8-PCDD/Fs were quantified in pooled samples for all species. The relative abundances of stable isotopes of nitrogen (δ¹⁵N) were evaluated in the organisms as a measure of chemically-derived trophic level. Contrary to earlier studies on other persistent organochlorines, it was found that the concentrations of PCDD/Fs declined with increasing trophic level. Principal Component Analysis (PCA) also showed differences between species in the pattern of PCDD/Fs. Higher chlorinated congeners constituted lower percentages of the PCDD/F-concentrations higher in the food chain as compared to lower trophic levels. In general, congener patterns did not differ between fjords. Infauna (polychaetes) and zooplankton had congener patterns most similar to the pollution source. The results indicate lower accumulation of higher chlorinated congeners in species at higher trophic levels (fish), presumably due to low membrane permeability (high molecular size) and possibly slow transport through intestinal aqueous phases because of low aqueous solubility.     

水体沉积物中有毒有机污染物的监测研究进展

介绍了水体沉积物中有毒有机污染物监测的预处理技术,重点评述了我国水体沉积物中主要有毒有机污染物多环芳烃、多氯联苯和有机氯农药的监测研究现状,认为水体沉积物中有毒有机污染物研究领域今后发展的重点和方向是广泛开展国内主要河流、湖泊、海洋的监测研究和其在水体环境中的迁移及转化机理、生殖毒性以及污染消减与修复技术研究;加强新型预处理技术及其与大型仪器联用技术的研究;尽早建立水体沉积物中有毒有机污染物的监测方法标准及污染评价标准。     

湖鲟(Acipenser fulvescens)早期生命阶段对2,3,7,8-四氯二苯并-p-二恶英和3,3'4,4'5-五氯联苯的敏感性研究

自20世纪中叶以来,五大湖区的水生食物网就已受到多氯联苯化合物(PCBs)的污染。对于长寿命鱼类,如湖鲟(Acipenser fulvescens),由于缺乏该物种的相对敏感性信息,一直无法确定其PCB暴露的风险。本文的研究目标就是评估湖鲟早期生命阶段对3,3''4,4''5-五氯联苯(PCB-126)或2,3,7,8-四氯二苯并-p-二恶英(TCDD)暴露的敏感性。死亡率、生长、形态和组织病理学、游泳能力和活动水平都被用作评估终点。心包和卵黄囊水肿、管状心脏、卵黄囊出血和体长较小是TCDD和PCB-126暴露中最常见的病理症状,早在受精4 d后就开始出现,其中许多的病理都以一种剂量依赖的方式发生。湖鲟体内PCB-126和TCDD的半致死剂量分别为5.4 ng/g egg(95%置信区间,3.9-7.4 ng/g egg)和0.61 ng/g egg (0.47-0.82 ng/g egg)。由此产生的PCB-126的相对强度因子(0.11)远大于世界卫生组织对鱼的估计值(毒性当量因子=0.005),这表明目前的风险评估可能低估了PCB对湖鲟的毒性。在受精60 d后,从半致死剂量中幸存的湖鲟的游泳活性和耐力均有所下降。阈值和半数效应毒性值表明,与在北美发现的另一种鲟鱼属Scaphirhynchu相比,湖鲟对PCB和TCDD更为敏感。事实上,在大湖区和其他地方的湖鲟种群都容易受到PCB/ TCDD诱导,使胚胎发育受到影响,游泳能力下降。
精选自Tillitt, D. E., Buckler, J. A., Nicks, D. K., Candrl, J. S., Claunch, R. A., Gale, R. W., Puglis, H. J., Little, E. E., Linbo, T. L. and Baker, M. (2017), Sensitivity of lake sturgeon (Acipenser fulvescens) early life stages to 2,3,7,8-tetrachlorodibenzo-P-dioxin and 3,3′,4,4′,5-pentachlorobiphenyl. Environmental Toxicology and Chemistry, 36: 988–998. doi: 10.1002/etc.3614
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3614/full
     

Organochlorine pesticides and polychlorinated biphenyls in riverine runoff of the Pearl River Delta, China: assessment of mass loading, input source and environmental fate

A large-scale sampling program was conducted to simultaneously collect water samples at the eight major riverine runoff outlets of the Pearl River Delta (PRD), South China to assess the importance of riverine runoff in transporting anthropogenic pollutants from terrestrial sources to the coastal ocean. The concentrations of ∑₂₁OCPs (sum of 21 OCP components) and ∑₂₀PCBs (sum of 20 PCB congeners) were 2.57-41.2 and 0.12-1.47 ng/L, respectively. Compositional distributions of DDTs suggested the possibility of new input sources in the study area, but contributions from dicofol seemed considerably low. The annual inputs of ∑₂₁OCPs and ∑₂₀PCBs were 3090 and 215 kg, with those of total HCHs and DDTs being 1110 and 1020 kg, respectively. A mass balance consideration indicated that riverine runoff is the major mode carrying OCPs from the PRD to the coastal ocean, and the majority of OCPs is further dissipated to open seas.     

Altitude profiles of total chlorinated paraffins in humus and spruce needles from the Alps (MONARPOP)

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. CPs were analyzed in humus and needle samples, which were taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) at sampling sites of 7 different altitude profiles in the Alps. Gas chromatography combined with electron ionization tandem mass spectrometry (EI-MS/MS) was used for the determination of total CPs (sum of short, medium and long chain CPs). CPs were found in all samples; the concentrations varied between 7 and 199 ng g⁻¹ dry weight (dw) and within 26 and 460 ng g⁻¹ dw in humus and needle samples, respectively. A clear vertical tendency within the individual altitude profiles could not be ascertained. Within all altitude profiles, elevated concentrations were observed in humus samples taken between 700 and 900 m and between 1300 and 1500 m. In the needle samples no similar correlation could be observed due to higher variation of the data.     

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea

Background, aim, and scope  The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. Materials and methods  Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. Results  Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. Discussion  The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. Conclusions  The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. Recommendations and perspectives  In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Organochlorine pesticides and polychlorinated biphenyl residues in reared and wild Dicentrarchus labrax from the Mediterranean Sea (Sicily, Italy)

The aim of this research was to compare the levels of organochlorine pesticides and PCBs in samples of Dicentrarchus labrax living in the Straits of Messina with samples cultivated in cages in the Mediterranean Sea. Muscles and liver tissues sampled over the months, within the same year, were analyzed. The quantitative determination of the organochlorine compounds was performed by GC-ECD and confirmed with GC–MS. The results showed that the concentrations of DDTs in muscles and livers as such of reared sea bass were in the range 0.2–1.3 μg/kg and 9.6 –48.4 μg/kg, respectively. In wild fish the concentrations of DDTs were very much lower: 0.1 μg/kg in muscles, 5.1–9.0 μg/kg in livers. Total PCBs levels were higher in cultivated sea bass than in wild fish; the concentration ranges were 5.3–59.7 μg/kg and 74.4–267.4 μg/kg in muscle and liver of reared samples, respectively, and 1.1–1.5 μg/kg and 63.2–109.4 μg/kg in muscle and liver of wild samples, respectively.     

Reductive dechlorination of polychlorinated dibenzo-p-dioxins by zerovalent iron in subcritical water

A new method for reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) and remediation of contaminated soils is described that uses zerovalent iron as the dechlorination agent and subcritical water as reaction medium and extractive solvent. It is found that the zerovalent iron can be applied for stepwise dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) on various matrixes in subcritical water. By using iron powder as matrix higher chlorinated congeners were practically completely reduced to less than tetra-substituted homologues. A significant part of residual OCDD, when it was spiked in to soils, and formed less chlorinated congeners are extracted with water in the given conditions. The solubility of OCDD was increased by a 4–6 orders over its solubility at ambient conditions. The new method of contentious-flow extraction is described.     

PCBs和PBDEs的生物效应及人体健康影响的研究现状

环境中的多氯联苯(PCBs)和多溴联苯醚(PBDEs)通过食物链,可以在水生生物实现生物积累。而人类食用这些含有污染的食品,可以造成对人体的健康危害的摄食暴露,导致癌症、内分泌失调等疾病,并影响生育能力和儿童智力发育。但由于生物体内在因素的复杂性,PCBs和PBDEs在生物体内的代谢、放大等机制仍不明确,有待进一步的研究。     

Why biota still accumulate high levels of PCB after removal of PCB contaminated sediments in a Norwegian fjord

Accumulation of polychlorinated biphenyls (PCBs) in blue mussels (Mytilus edulis) and semipermeable membrane devices (SPMDs) was still high after the removal of PCB contaminated sediments from a Norwegian fjord by dredging. The accumulation of low chlorinated PCB congeners with a low octanol water-partitioning coefficient (K_ow) in blue mussels and SPMDs was higher than for the highly chlorinated congeners with a high K_ow. The accumulation of low chlorinated congeners was also higher in a lightly contaminated area compared to a highly contaminated area. That dredging the contaminated sediments was unsuccessful in lowering PCB levels in the biota may be for the following reasons: (1) Due to the low solubility of PCBs in the water it is possible that a decrease in the sediment concentration of PCB would leave the water concentrations of PCB unchanged. (2) Removal of the fine organic sediments may also play an important role, since a seabed with coarse inorganic material has a lesser ability to bind PCB. (3) The dredging may whirl up fine contaminated particles that eventually settles on the seabed producing a thin contaminated sediment layer that determine the water concentration. (4) Bioaccumulation in blue mussels and in the SPMDs occurs mostly from PCB dissolved in the water column. Since the water concentration of PCB is unchanged by the dredging, the accumulation in SPMDs and mussels is the same as before dredging. Further monitoring need to be carried out to report the long-term effect of the dredging.