多氯联苯污染沉积物质量评价研究进展

介绍了多氯联苯污染沉积物质量评价的研究进展，其中，简单介绍了多氯联苯的有关概况及环境行为、沉积物质量评价方法及基准研究进展；最后，重点介绍了包括多氯联苯在内的憎水性有机物污染沉积物质量评价的研究现状及存在问题。     

环境中多氯联苯醚的污染现状及研究进展

多氯联苯醚(PCDEs)作为工业氯酚或氯代苯氧乙酸的生产副产物在环境介质中广泛存在。PCDEs与多氯联苯(PCBs)和多氯代二苯并呋喃(PCDFs)的化学结构具有一定相似性,属于潜在的持久性有机污染物,生态风险较高。相对于PCBs和PCDFs,广大学者对PCDEs污染水平、生物毒性以及人体暴露风险的研究相对较少。为了提高对PCDEs研究的重视程度,综述了近年来PCDEs的研究状况,详细讨论了PCDEs的结构性质、来源、形成机理、降解规律、生物毒性以及在生物体、环境介质中的暴露水平,并对未来PCDEs的研究方向做出预测。     

多氯联苯污染沉积物质量评价研究进展

介绍了多氯联苯污染沉积物质量评价的研究进展 ,其中 ,简单介绍了多氯联苯的有关概况及环境行为、沉积物质量评价方法及基准研究进展 ;最后 ,重点介绍了包括多氯联苯在内的憎水性有机物污染沉积物质量评价的研究现状及存在问题。     

沈阳市多氯联苯流失、污染及防治对策的研究

本研究在对沈阳市有关多氯联苯及其制品使用、保管及流失的调查基础上,应用研究建立的分析监测方法,对沈阳市环境及有关污染源环境的空气,土壤及水质的污染水平进行了分析与评价,对大量可疑设备和废液进行了鉴定,对综合防治沈阳市多氯联苯污染的途径进行了探讨,以上研究结果将为彻底解决沈阳市历史遗留的多氯联苯污染问题起到促进作用。     

中国主要排放源的非故意产生六氯苯和多氯联苯大气排放清单探讨

六氯苯和多氯联苯是被列入<斯德哥尔摩公约>附件C中要求采取减排控制措施的非故意产生持久性有机污染物,目前尚没有关于它们在中国的排放清单方面的研究报道.参考日本环境省基于实测数据编制的排放因子,计算了以2008为基准年的中国主要排放源的非故意产生六氯苯和多氯联苯大气排放清单.结果表明,由主要行业产生的六氯苯年排放量为528 704 g,多氯联苯的年排放量为7 762 615 g.对于六氯苯,主要排放源依次为水泥行业(42.356%)、电炉炼钢(27.549%)、钢铁烧结过程(14.731%)和初级铜冶炼(7.774%);对于多氯联苯,水泥行业占了排放量的90%以上.上述排放源应当在制订其减排战略和行动计划时予以关注和优先考虑.     

多氯联苯(PCB)分析方法的研究——土壤、底泥中多氯联苯水蒸汽蒸馏—气相色谱定量法

最近经我们调查研究与分析测定,发现我国也有多氯联苯的污染,尤其是土壤,底泥。因此,本工作首先研究建立土壤、底泥中多氯联苯的分析测定方法。 多氯联苯是各种氯化联苯的混合物,理论上多达210种异构体,已经确证102种,加之它的物化性质类似有机氯农药,在分析测定时互相有干扰,给分析工作带来很大困难。 关于多氯联苯分析测定方法的研究报     

自然水体中主要有毒有机物的研究进展

介绍了主要有毒有机物多环芳烃(PAHs)、多氯联苯(PCBs)、有机氯农药(OCPs)在环境中的危害及其来源,着重评述了近年来中国自然水体中和沉积物中该类污染物的研究进展,指出新的检测技术的开发、有毒有机物的生殖毒性和生态环境风险影响方法学的研究及污染区域污染控制、消减及修复是今后该领域的工作重点.     

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。     

规模化养殖场畜禽粪便发酵还田负荷估算及风险评价——以四川省邛崃市为例

以邛崃市为研究对象,结合其规模化畜禽养殖量、畜禽粪便排放量以及农作物氮肥需求量等,对研究区域耕地畜禽粪便最大氮负荷量进行了估算,将其与畜禽粪便发酵副产物沼渣沼液还田产生的实际氮负荷量进行比较,由此对现有养殖规模下的环境风险进行了评价.结果表明,当前邛崃市除孔明乡、火井镇、回龙镇受到沼渣沼液还田污染以外,其他各养殖区域沼渣沼液还田尚未造成明显污染.因此,邛崃市规模化养殖还存在较大的发展空间,但必须从实际出发,合理规划,才能实现农业和环境的可持续发展.     

国外消息

能“吃”多氯联苯的细菌日本千叶政府研究实验室的一位科学家Furukawa已发现了两种能“吃”高毒性和化学性能稳定的多氯联苯的细菌。成功地探索了这些细菌如何     

Formation of polychlorinated diphenyl ethers from condensation of chlorophenols with chlorobenzenes

BACKGROUND AND AIMS: Polychlorinated diphenyl ethers (PCDEs), which are among the members of persistent organic pollutants, and PCDEs have been determined in a number of environmental samples. The main possible sources are the technical production of chlorinated phenols and all processes of incomplete combustion. PCDEs were observed in the fly ash from a municipal waste incinerator (MWI). It was speculated that the condensation of chlorophenols with chlorobenzenes occurred via PCDEs to form polychlorinated dibenzofurans (PCDFs). Nevertheless, PCDEs formation from condensation of chlorophenols with chlorobenzenes has not been confirmed by experimental observation. The objective of this paper is to investigate the formation mechanism of PCDEs from the condensation of chlorophenols with chlorobenzenes. The results are expected to be helpful in understanding the formation of PCDEs and in controlling and abating PCDEs emissions from MWI. METHODS: The pyrolysis of pentachlorophenol (PCP) and/or polychlorobenzenes (PCBz) was carried out in a sealed glass tube. The reaction products were extracted and purified with K2CO3 solution. The samples were concentrated and then cleaned up on an alumina column. GC/MS was used for identification and quantification of reaction products. RESULTS AND DISCUSSION: The results showed that the pyrolysis of hexachlorobenzene (HCB) at 340 degrees C for 6 h led to the formation of decachlorodiphenyl ether (DCDE) (2.41 microg/mg) and octachlorodibenzo-p-dioxins (OCDD) (0.24 micropg/mg), while the pyrolysis of PCP yielded DCDE (13.08 microg/mg) and OCDD (180.13 microg/mg). In addition, the amount of DCDE formation from the pyrolysis of the mixture of PCP and HCB was 4.65 times higher than the total amount of DCDE formation from the pyrolysis of HCB and PCP, respectively. This indicated that PCP and HCB were prone to condensation and formation of DCDE. DCDE was the main congener of PCDEs from condensation of PCP with HCB at 340, 400 and 450 degrees C. A small amount of nonachlorodiphenyl ether (NCDE) was formed by dechlorination reaction at 450 degrees C. The condensation of PCP with 1,2,4,5-tetrachlorobenzene (Cl4Bz) formed 2,2',3,4,4',5,5',6-octachlorodiphenyl ether (OCDE). Small amounts of heptachlorodiphenyl ether (HpCDE) and hexachlorodiphenyl ether (HxCDE) were detected at 450 degrees C. Meanwhile, polychlorinated dibenzo-p-dioxins (PCDDs) and PCDFs were detected from the condensation of PCP and PCBz. CONCLUSIONS: Experimental studies clarified the behavior of the formation of PCDEs from condensation of polychlorophenols and PCBz. The condensation of polychlorophenols with PCBz formed PCDEs through elimination of HCl between polychlorophenols and PCBz molecules. Another pathway of PCDEs formation was elimination of H2O between two polychlorophenol molecules. In addition, dechlorination processes had caused the specific homologous pattern of PCDEs under higher temperatures.     

Use of a column leaching test to study the mobility of chlorinated HOCs from a contaminated soil and the distribution of compounds between soluble and colloid phases

An equilibrium and recirculation column test for hydrophobic organic chemicals (ER-H test) was used to study the leaching behaviour of chlorophenols (CPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) from contaminated soil. A 50% increase in the pore water velocity was shown to have little or no effect on the mobility of CPs, PCDEs, PCDFs and PCDDs. The standard deviations of truly dissolved compounds, CPs, were between 19% and 65% between the tests. However, the repeatability of the ER-H test decreased with increases in the hydrophobicity of the studied compounds; the standard deviations for PCDEs, PCDFs and PCDDs ranged from 53% to 110%, 57% to 77% and 110% to 130%, respectively. The influence of colloids on the release of these compounds was also examined. Up to 30% of the CPs in the soil were leached, of which 1-3% were associated with colloids. The PCDEs, PCDFs and PCDDs were found to be preferably associated with the particulate fraction of the leachate, and less than 0.2% of these compounds were mobilised.     

Contents and origin of polychlorinated diphenyl ethers (PCDE) in salmon from the Baltic Sea, Lake Saimaa and the Tenojoki river in Finland

The presence of 26 congeners of polychlorinated diphenyl ethers (PCDEs) was investigated in salmon from three locations in Finland. In addition to salmon, one chlorophenol wood preservative (Ky-5) and one fly ash sample were analyzed for PCDEs. Concentrations of PCDE congeners in salmon muscle measured by high resolution gas chromatography/low resolution mass spectrometry ranged from < 0.02 to 2.4 ng/g fresh weight. The major components of tetra- to octachlorinated PCDEs in salmon were one TeCDE (22′44′-), two PeCDEs (22′44′5- and 23′44′5-) and three HxCDEs (22′44′56′-, 22′44′55′- and 22′344′5-). The Baltic salmon caught from the Simojoki River had higher levels of PCDEs than the Atlantic salmon from the Tenojoki River or salmon from Lake Saimaa in South-Finland. Same PCDE congeners which were abundant in the wood preservative were also detected in salmon, whereas PCDE congeners in the fly ash were different from those in salmon or in Ky-5.     

Influence of iron and copper oxides on polychlorinated diphenyl ether formation in heterogeneous reactions

Polychlorinated diphenyl ether (PCDE) has attracted great attention recently as an important type of environmental pollutant. The influence of iron and copper oxides on formation of PCDEs was investigated using laboratory-scale flow reactors under air and under nitrogen at 350 °C, a temperature corresponding to the post-combustion zone of a municipal solid waste incinerator. The results show that the 2,2′,3,4,4′,5,5′,6-otachlorodiphenyl ether (OCDE) formed from the condensation of pentachlorophenol (PCP) and 1,2,4,5-tetrachlorobenzene (Cl₄Bz) is the predominant congener formed on the SiO₂/Fe₂O₃ surface with and without oxygen. This indicated that HCl elimination between PCP and 1,2,4,5-Cl₄Bz molecules formed 2,2′,3,4,4′,5,5′,6-OCDE in the presence of Fe₂O_3. On the other hand, decachlorodiphenyl ether, nonachlorodiphenyl ether, and OCDE were the dominant products on the SiO₂/CuO surface without oxygen, although the 2,2′,3,4,4′,5,5′,6-OCDE was the dominant product on the SiO₂/CuO surface with oxygen. Therefore, the presence of Fe₂O₃ and CuO influences the formation and homologue distribution of PCDEs, which shifted towards the lower chlorinated species. Fe₂O₃ can promote both the condensation and dechlorination reaction without oxygen_. On the contrary, with oxygen, Fe₂O₃ suppresses the condensation of chlorobenzene and chlorophenol to form PCDEs and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). CuO can increase the formation of lower chlorinated PCDEs and PCDDs without oxygen. In conclusion, the different fly ash components have a major influence on PCDE emissions.     

Mobility of chloroaromatic compounds in soil: case studies of Swedish chlorophenol-contaminated sawmill sites

This paper summarizes recent studies on the environmental fate of chloroaromatic compounds in chlorophenol (CP)-contaminated soil and groundwater at Swedish sawmill sites. Relative proportions of CPs, polychlorinated phenoxy phenols (PCPPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were determined in preservatives, particulate organic matter (POM), dissolved organic matter (DOM), groundwater, and particles filtered from groundwater. All compound classes were found in the different compartments. The fraction of PCPPs, PCDEs, PCDDs, and PCDFs had increased in the soil samples relative to the proportions in the preservatives. This increase showed correlation with the hydrophobicity, that is, PCDDs had the largest increase. Similar correlation was found between hydrophobicity and the importance of partitioning to POM over DOM. The more water soluble compound group, CP, was found equally distributed between POM and DOM. For PCPPs, PCDEs, PCDDs, and PCDFs, the relative partitioning to POM increased with increased hydrophobicity. Despite the relative partitioning towards POM, compared with DOM, cotransport with DOM and suspended colloidal fractions was found to substantially increase the transport of these compounds in the groundwater samples.     

Desorption of sediment-associated polychlorinated dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and hydroxydiphenyl ethers from contaminated sediment

The transport and bioavailability of sediment-associated contaminants are often controlled by the contaminants' desorbing behaviour. This study examines the desorption kinetics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), diphenyl ethers (PCDEs) and hydroxydiphenyl ethers (HO-PCDEs) from the highly contaminated River Kymijoki sediment in Finland. The desorption kinetics data were generated using Tenax((R)) extraction, and a first-order three-compartment kinetic model was fitted to the data. The desorption data was compared to the previously published accumulation data from this same location to investigate the relationship between the rapidly desorbing fraction (F(r)) and biota-sediment accumulation factors (BSAFs) as well as semipermeable membrane device sediment accumulation factors (SSAFs). The PCDDs, PCDFs, PCDEs and HO-PCDEs were tightly attached to sediment particles and formed a large very slowly desorbing fraction (F(vs)). Rapidly desorbing fractions (F(r)) varied between 0.8% and 8% of total amount in sediment. The size of the desorbing fraction was congener-specific and F(r) decreased with the increasing lipophilicity of congeners. The size of the F(r) was unable to explain the small variation in the BSAFs of Lumbriculus variegatus but may help to explain the observed variation in the SSAFs. To our best knowledge, this study is the first effort to investigate the desorption of PCDDs, PCDFs, PCDEs and HO-PCDEs in field-contaminated sediments. The major finding that the very slow desorption of these chemicals will continue years, provides essential information for the modern risk assessment process.     

Use of the metastable atom bombardment (MAB) ion source for the elimination of PCDE interference in PCDD/PCDF analysis

The analysis of polychlorinated dioxins and furans (PCDDs/PCDFs) can produce erroneous results when polychloro diphenyl ethers (PCDEs) are present because they fragment and rearrange under electron ionization to give isobaric ions with PCDFs. Mass information must be generated to indicate the occurrence of possible PCDEs but uncertainty still exists if a PCDE congener has the same retention time as a PCDF congener. The metastable atom bombardment (MAB) ion source does not transfer enough energy to PCDE upon ionization to fragment the molecular ion, thus eliminating the need for PCDE tracking in PCDF analysis. Experiments were conducted with different gases, representing different ionization energies, to demonstrate that PCDE interference can be eliminated from PCDF analysis.     

Vapour pressures, aqueous solubilities, Henry's law constants, partition coefficients between gas/water (Kgw), n-octanol/water (Kow) and gas/n-octanol (Kgo) of 106 polychlorinated diphenyl ethers (PCDE)

Modelling the environmental fate of persistent organic pollutants like polychlorinated diphenyl ethers (PCDE) requires the knowledge of a number of fundamental physico-chemical properties of these compounds. We report here the physico-chemical properties of 106 PCDEs, which are over 50% of all possible congeners. Vapour pressures P(OL), water solubilities S(H2O), and n-octanol/water partition coefficients K(OW) were determined with chromatographic methods. With these experimental data the Henry's law constants H, gas/water K(GW) and gas/n-octanol K(GO) partition coefficients were calculated. Vapour pressures and water solubilities and n-octanol/water partition coefficients of the PCDEs are close to those of similar groups of organochlorine compounds like polychlorinated biphenyls (PCBs) and dibenzofurans (PCDFs). A similar environmental fate can be predicted and was partially already been observed.     

植物修复--大面积低剂量放射性污染的新治理技术

放射性污染是当今难以治理的环境污染问题,对于大面积低剂量的放射性污染,植物修复是种较适用的新型治理技术.系统阐述了植物修复技术的概念与内容,对放射性污染植物修复技术研究现状与进展、植物修复的优缺点进行了重点评述,并对这技术在未来放射性污染治理中的应用与研究提出了建议.     

水体中卤代芳烃污染状况及降解途径研究进展

介绍了卤代芳烃对水环境所造成的污染和危害 ,并对水体中该类污染物降解技术研究进展进行了综述。着重介绍了光降解及光催化技术、化学氧化法、氢解还原和辐射降解等技术在该领域的有关研究。