碱催化脱氯技术处理氯代新POPs研究及示范工程

以硫丹作为氯代新POPs的代表,通过实验室小试研究,探讨反应温度、NaOH和石蜡油投加量对硫丹在NaOH/石蜡油碱催化反应体系中的去除和脱氯效率(RE和DE)的影响,并寻找出最优条件,开展示范工程研究.实验室小试结果表明,反应温度、NaOH投加量和石蜡油投加量对硫丹脱氯效率的影响要大于对其去除率的影响.当温度为250℃,硫丹和NaOH及石蜡油的质量比为1:3:6和1:3:10时,反应3h后,硫丹去除率和脱氯效率分别达到99.99%和99%以上.采用硫丹和得克隆两种氯代有机物开展示范工程研究,中试设备处理能力达到15kg/批次,在250~300℃下反应3~10h后,对硫丹和得克隆的去除效率均达到99.9%以上,表明硫丹和得克隆被有效分解.示范工程的成功实施为我国履行斯德哥尔摩公约提供技术支持.     

土壤中持久性有机污染物的提取技术研究

文章介绍了持久性有机污染物的分析检测方法,指明了研究土壤中持久性有机污染物的必要性.将国内最常用的两种提取方法--索式提取和超声波提取进行比较,结果表明了索式提取的方法更适合从土壤中提取多种持久性有机污染物,提取剂和洗脱剂可选比例1:1的丙酮和石油醚,回收率可在70%～90%之间;而超声波提取的方法比较适合从土壤中提取个别的持久性有机污染物,如op′-DDT 和pp′-DDT,节省实验时间,试剂使用量少,回收率也可在50%以上.     

类脂复合吸附剂去除水中微量七氯和环氧七氯的研究

研制了一种新型类脂-活性炭复合吸附剂,研究了其对水中痕量持久性有机污染物--七氯和环氧七氯的吸附行为.实验结果表明,该新型复合吸附剂对七氯和环氧七氯有较强的吸附性能,反应48 h后,对初始浓度为20μg·L-1的七氯和环氧七氯的去除率分别为98.79%和98.08%;吸附等温线符合弗兰德里希模型;吸附动力学符合准二阶动力学模型.该复合吸附剂对亲脂性较强的七氯具有较快的初始吸附速率、较大的平衡吸附量和较高的去除率.相同实验条件下,类脂-活性炭复合吸附剂对七氯和环氧七氯的吸附速率和去除效果均优于传统吸附材料活性炭.     

The effect of export to the deep sea on the long-range transport potential of persistent organic pollutants

BACKGROUND: Export to the deep sea has been found to be a relevant pathway for highly hydrophobic chemicals. The objective of this study is to investigate the influence of this process on the potential for long-range transport (LRT) of such chemicals. METHODS: The spatial range as a measure of potential for LRT is calculated for seven PCB congeners with the multimedia fate and transport model ChemRange. Spatial ranges for cases with and without deep sea export are compared. RESULTS AND DISCUSSION: Export to the deep sea leads to increased transfer from the air to the surface ocean and, thereby, to lower spatial ranges for PCB congeners whose net deposition rate constant is similar to or greater than the atmospheric degradation rate constant. This is fulfilled for the PCB congeners 101, 153, 180, and 194. The spatial ranges of the congeners 8, 28, and 52, in contrast, are not affected by deep sea export. With export to the deep sea included in the model, the spatial ranges of the heavier congener are similar to those of the lighter ones, while the intermediate congeners 101 and 153 have the highest potential for long-range transport. CONCLUSIONS: Transfer to the deep ocean affects the mass balance and the potential for LRT of highly hydrophobic chemicals and should be included in multimedia fate models containing a compartment for ocean water.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Aufnahmepfade von POPs in Biota

Zusammenfassung  POPs (persistente organische Schadstoffe), die an aquatischen Sedimenten binden, k?nnen zurück in Nahrungsnetze gelangen und so zu einem Risiko für aquatische Organismen werden. Dabei kann die Bioakkumulation solcher Substanzen in endobenthischen, sedimentfressenden Invertebraten (z.B. aquatische Oligochaeten) eine gro?e Rolle spielen. Diese Würmer dienen vielen benthivoren Fischen als Nahrung. Letztere nehmen über diesen Weg sedimentgebundene Chemikalien auf und k?nnen hierbei deutlich h?here K?rperkonzentrationen (body residues) erreichen als durch die Anreicherung aus der Wasserphase. Die angereicherten Rückst?nde k?nnen im weiteren Verlauf der Nahrungskette an Glieder h?herer trophischer Ebenen weitergegeben werden. Zur standardisierten Bestimmung der Bioakkumulation und — magnifikation wurde eine einfache, zwei trophische Stufen umfassende Labornahrungskette etabliert. Diese bestand aus dem endobenthischen Oligochaeten Tubifex tubifex und dem Dreistachligen Stichling (Gasterosteus aculeatus) als Pr?dator. Die Experimente wurden mit ¹⁴C-markiertem Hexachlorbenzol in dotiertem künstlichem Sediment und rekonstituiertem Wasser durchgeführt. Um den Einfluss benthischer Beuteorganismen zu quantifizieren, wurden die Fische gegenüber dotiertem Wasser bzw. Sediment (Biokonzentration), vorexponierten Würmern (Biomagnifikation) und Kombinationen dieser Aufnahmepfade exponiert. HCB wurde entlang der Labornahrungskette deutlich angereichert. Es konnte gezeigt werden, dass die Exposition gegenüber der Kombination s?mtlicher Aufnahmepfade zu deutlich h?herer Anreicherung in den Fischen führte als im Falle einzelner Expositionspfade. Der Vergleich der Einzelergebnisse lie? den Schluss zu, dass neben dem freien Wasserk?rper die kontaminierte Nahrung der Hauptaufnahmeweg für den Fisch war. Bei der Bewertung von POPs wie HCB hinsichtlich Biomagnifikation und ‘secondary poisoning’ sollten daher Nahrung und Sediment als Expositionspfade unter Verwendung von Nahrungsketten-modellen und/oder Labortests st?rker berücksichtigt werden. Reter Spr?rlein war bis Januar 2000 als Ingenieur für Umweltverfahrenstechnik bei der ECT Oekotoxikologie GmbH besch?ftigt und für die HPLC-analytische Aufarbeitung der experimentellen Proben verantwortlich.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

持久性有机污染物在食物链中积累与放大研究进展

研究持久性有机污染物(Persistent organic pollutants,POPs)在食物链中的积累与放大是进行环境风险评估和有效污染控制的生态学基础.本文综述了POPs的基本特征,POPs在食物链中的生物积累与放大的机制、影响因素以及POPs在食物链中积累与放大的模型等的研究进展.国外学者对POPs在水生食物链的积累与放大方面研究较多,并提出了较为完善的预测模型,而有关POPs在陆生食物链中的生物积累与放大的研究报道较少.大部分学者并未对完整食物链进行过系统而完整的研究.与国外相比,国内学者对POPs在水生陆生食物链中的生物积累、生物放大和预测模型探讨较少.目前POPs对环境和人体健康危害越来越严重,开展对POPs在食物链中积累、放大及相关预测模型更深入更完整的研究,已成为当前生态学和环境科学研究的重点课题和前沿领域.