多溴二苯并-对-二恶英和多溴二苯并呋喃(PBDD/Fs)具有与多氯二苯并-对-二恶英和多氯二苯并呋喃(PCDD/Fs)相似的结构和毒性,广泛存在于多种环境介质和生物体中,已经引起了广泛的关注.本文讨论了溴代阻燃剂(BFRs)生产和处理、电子垃圾拆...多溴二苯并-对-二恶英和多溴二苯并呋喃(PBDD/Fs)具有与多氯二苯并-对-二恶英和多氯二苯并呋喃(PCDD/Fs)相似的结构和毒性,广泛存在于多种环境介质和生物体中,已经引起了广泛的关注.本文讨论了溴代阻燃剂(BFRs)生产和处理、电子垃圾拆解和热处理、垃圾焚烧和金属冶炼等工业热过程中PBDD/Fs排放水平及生成机制.其中,PBDD/Fs在BFRs产品中的含量较高,范围为0.257—49.605μg.g-1,在电子垃圾热解处理中气相和固相的含量分别可达到57 ng TEQ.kg-1和19000 ng TEQ.kg-1,而在冶金过程烟道气中的含量范围是0.14—1.5 ng TEQ.m-3.本文还总结了PBDD/F分析方法研究进展,包括样品前处理和仪器分析方法,提出了目前影响准确定量PBDD/Fs的因素以及相关的解决措施.归纳了当前环境介质和生物体及食品中PBDD/Fs的存在水平,指出电子垃圾热处理、垃圾焚烧等工业热过程已导致周边环境和生物体内PBDD/Fs的浓度增高.最后,介绍了国外与PBDD/Fs相关的控制措施和政策法规.展开更多
为了探明固废焚烧炉烟道气中PCDD/Fs和PBDD/Fs的浓度、分布特征和二者之间的相关性,用气相色谱/高分辨质谱测定2,3,7,8位氯代和溴代二恶英（PCDD/Fs和PBDD/Fs）。两者的总毒性当量浓度在A厂分别为0.043～1.20,0.00056～0.010 ng I-TEQ/m...为了探明固废焚烧炉烟道气中PCDD/Fs和PBDD/Fs的浓度、分布特征和二者之间的相关性,用气相色谱/高分辨质谱测定2,3,7,8位氯代和溴代二恶英（PCDD/Fs和PBDD/Fs）。两者的总毒性当量浓度在A厂分别为0.043～1.20,0.00056～0.010 ng I-TEQ/m^3,在B厂分别为0.024～0.069,0.0034～0.0043 ng I-TEQ/m^3。A厂的PCDD/Fs以PCDFs为主,B厂相对浓度最大的是OCDD。影响PCDD/Fs的浓度和分布可能主要为垃圾含氯量和空气净化设施。PBDD/Fs都主要含PBDFs。两厂的PCDD/Fs和PBDD/Fs浓度具有较好的相关性。展开更多
A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, w...A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).展开更多
This review compiles information on PCDD/F-and PCB-contaminated eggs from 20 years of global egg monitoring around emission sources in four continents conducted by the International Pollutants Elimination Network(IPEN...This review compiles information on PCDD/F-and PCB-contaminated eggs from 20 years of global egg monitoring around emission sources in four continents conducted by the International Pollutants Elimination Network(IPEN)and Arnika as well as a compilation of data from scientific literature.IPEN monitored 127 pooled egg samples including samples from 113 chicken flocks at potential PCDD/F-and PCB-contaminated sites around priority sources listed in the Stockholm Convention(e.g.waste incinerators,metal industries,cement plants,and open burning).99(88%)of pooled egg samples were above the EU maximum limits for PCDD/Fs(2.5 pg PCDD/F-TEQ/g fat)or the sum of PCDD/Fs and dioxinlike PCBs(5 pg PCDD/F-PCB-TEQ/g fat).Children consuming such eggs exceed the tolerable weekly intake(TWI).This demonstrates that close to 90%of these areas were not safe for the production of free-range eggs.Sixteen out of the 113 egg samples(14%)were contaminated above 50 pg TEQ/g fat and exceeded the EU maximum limit more than 10 times.From the 26 pooled egg samples around incinerators 24(92%)exceeded the limit with a mean of 43.1 pg TEQ/g fat(2.6e234 pg TEQ/g).All 21 egg samples around metal industries(4.4e112.6 pg TEQ/g fat)were above limits with mean concentration of 26.0 pg TEQ/g fat.Also all 7 egg samples measured at e-waste recycling sites were above limits(mean 308 pg TEQ/g fat).In 58(51%)pooled egg samples the PCB-TEQ was above 5 pg TEQ/g fat exceeding the EU maximum limit with dioxin-like PCBs alone.This highlights the role of commercial PCBs for global contamination with dioxin-like compounds.It was discovered that around metal industries,shredder plants,open burning sites of e-waste and dump sites,a high share of contamination was caused by dl-PCBs.This clearly shows severe PCB release from the end-of-life management of PCB-containing equipment in developing countries.Also highly contaminated eggs were found at many sites where plastic was incinerated.The highest contaminated egg sample ever measured came from an e-waste site in Ghana and had 856 pg TEQ/g fat plus 300 pg TEQ from brominated dioxins(PBDD/Fs).Other extreme PCDD/F contaminations of eggs were found at a chlor-alkali site(514 pg TEQ/g fat),Agent Orange contaminated areas in Vietnam(490,249 and 246 pg TEQ/g fat)and e-waste sites(568 and 520 pg TEQ/g fat).Where DR CALUX®bioassay revealed higher TEQ compared to measured PCDD/F-PCB-TEQ in IPEN studies,polybrominated PBDD/F were also measured and detected up to 300 pg TEQ/g fat at e-waste sites.One positive outcome from the IPEN studies is that all 10 pooled supermarket eggs in developing countries were below regulatory limit.Policy recommendations are made including:a systematic assessment of areas around PCDD/Fs and PCBs sources;measures for reduction of exposures of populations;urgent control of emission sources including PCB equipment,the open burning of plastic,and the use of plastic as fuel in boilers/incinerators in developing countries without air pollution control.Furthermore,soil limits need to be re-assessed and lowered for free-range poultry.展开更多
Article 5 of the Stockholm Convention requires that each Party shall take measures to reduce the releases from anthropogenic sources of unintentional persistent organic pollutants(UPOPs),with the goal of their continu...Article 5 of the Stockholm Convention requires that each Party shall take measures to reduce the releases from anthropogenic sources of unintentional persistent organic pollutants(UPOPs),with the goal of their continuing minimization and,where feasible,their ultimate elimination.A major source of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)and other unintentional POPs releases,both in China and worldwide,is the metal industry in particular secondary metal industries such as copper smelting.More than 50%of the global secondary copper production is now in China and high levels of PCDD/Fs are released from these operations with the national inventory of China reporting a total of 1133.8 g toxic equivalents(TEQ)yr1.Consequently the Global Environment Facility(GEF)is supporting the project‘UPOPs Reduction through best available techniques and best environmental practices(BAT/BEP)in the secondary copper production sector’in China compromising>50%of the global secondary copper production.As part of this project,information on relevant UPOPs from the metal industry have been reviewed and is presented here.This information should also be useful for other(developing)countries for controlling UPOPs releases from metal industries.This review and the information it contains provides a robust resource for policy makers,the industry and researchers to improve secondary copper production to BAT/BEP standards in relation to the reduction of PCDD/Fs and other UPOPs release.The contents include the details required to assist the understanding of the formation of chlorinated UPOPs along with their brominated and brominated-chlorinated analogues.It reviews the international sources of information on BAT/BEP,including the integrated approach considered in the European BAT Reference document,and shows how this can be used to achieve an overall reduction of pollutant releases from the industry.The current national standards of PCDD/F limits to air,water and solid residues have been compiled and are also included.Challenges which need to be addressed,such as the current international lack to consider brominated and mixed bromo-chloro PXDD/Fs which might be more environmentally significant than PCDD/Fs in some facilities e are also discussed.The study includes a brief description of the steps China has taken to change the national regulatory framework and to improve the sustainability of its secondary metal industry.The Stockholm Convention BAT/BEP guidelines recommend consideration of integrated pollution prevention and control and sustainable production as general principles which parties may incorporate when applying the BAT/BEP guidelines and guidance.This holistic approach is considered in the current project and in the improvement of the pilot facilities and will also be considered in the replication of experiences in other facilities.Using this approach ensures the implementation of the Stockholm Convention can contribute to integrated pollution prevention and control,the development of a circular economy and consequently to genuinely sustainable development thus contributing to different sustainable development goals(SDGs).It is hoped this approach will be adopted in other developing and transition economies and thus help to achieve improvements of the secondary metal industry globally.展开更多
文摘多溴二苯并-对-二恶英和多溴二苯并呋喃(PBDD/Fs)具有与多氯二苯并-对-二恶英和多氯二苯并呋喃(PCDD/Fs)相似的结构和毒性,广泛存在于多种环境介质和生物体中,已经引起了广泛的关注.本文讨论了溴代阻燃剂(BFRs)生产和处理、电子垃圾拆解和热处理、垃圾焚烧和金属冶炼等工业热过程中PBDD/Fs排放水平及生成机制.其中,PBDD/Fs在BFRs产品中的含量较高,范围为0.257—49.605μg.g-1,在电子垃圾热解处理中气相和固相的含量分别可达到57 ng TEQ.kg-1和19000 ng TEQ.kg-1,而在冶金过程烟道气中的含量范围是0.14—1.5 ng TEQ.m-3.本文还总结了PBDD/F分析方法研究进展,包括样品前处理和仪器分析方法,提出了目前影响准确定量PBDD/Fs的因素以及相关的解决措施.归纳了当前环境介质和生物体及食品中PBDD/Fs的存在水平,指出电子垃圾热处理、垃圾焚烧等工业热过程已导致周边环境和生物体内PBDD/Fs的浓度增高.最后,介绍了国外与PBDD/Fs相关的控制措施和政策法规.
文摘为了探明固废焚烧炉烟道气中PCDD/Fs和PBDD/Fs的浓度、分布特征和二者之间的相关性,用气相色谱/高分辨质谱测定2,3,7,8位氯代和溴代二恶英（PCDD/Fs和PBDD/Fs）。两者的总毒性当量浓度在A厂分别为0.043～1.20,0.00056～0.010 ng I-TEQ/m^3,在B厂分别为0.024～0.069,0.0034～0.0043 ng I-TEQ/m^3。A厂的PCDD/Fs以PCDFs为主,B厂相对浓度最大的是OCDD。影响PCDD/Fs的浓度和分布可能主要为垃圾含氯量和空气净化设施。PBDD/Fs都主要含PBDFs。两厂的PCDD/Fs和PBDD/Fs浓度具有较好的相关性。
基金supported by the National Natural Science Foundation of China(No.21777172)the Collaborative Project supported by Chinese Academy of Sciences and Hebei Academy of Sciences(No.181602)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2016038)
文摘A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).
文摘This review compiles information on PCDD/F-and PCB-contaminated eggs from 20 years of global egg monitoring around emission sources in four continents conducted by the International Pollutants Elimination Network(IPEN)and Arnika as well as a compilation of data from scientific literature.IPEN monitored 127 pooled egg samples including samples from 113 chicken flocks at potential PCDD/F-and PCB-contaminated sites around priority sources listed in the Stockholm Convention(e.g.waste incinerators,metal industries,cement plants,and open burning).99(88%)of pooled egg samples were above the EU maximum limits for PCDD/Fs(2.5 pg PCDD/F-TEQ/g fat)or the sum of PCDD/Fs and dioxinlike PCBs(5 pg PCDD/F-PCB-TEQ/g fat).Children consuming such eggs exceed the tolerable weekly intake(TWI).This demonstrates that close to 90%of these areas were not safe for the production of free-range eggs.Sixteen out of the 113 egg samples(14%)were contaminated above 50 pg TEQ/g fat and exceeded the EU maximum limit more than 10 times.From the 26 pooled egg samples around incinerators 24(92%)exceeded the limit with a mean of 43.1 pg TEQ/g fat(2.6e234 pg TEQ/g).All 21 egg samples around metal industries(4.4e112.6 pg TEQ/g fat)were above limits with mean concentration of 26.0 pg TEQ/g fat.Also all 7 egg samples measured at e-waste recycling sites were above limits(mean 308 pg TEQ/g fat).In 58(51%)pooled egg samples the PCB-TEQ was above 5 pg TEQ/g fat exceeding the EU maximum limit with dioxin-like PCBs alone.This highlights the role of commercial PCBs for global contamination with dioxin-like compounds.It was discovered that around metal industries,shredder plants,open burning sites of e-waste and dump sites,a high share of contamination was caused by dl-PCBs.This clearly shows severe PCB release from the end-of-life management of PCB-containing equipment in developing countries.Also highly contaminated eggs were found at many sites where plastic was incinerated.The highest contaminated egg sample ever measured came from an e-waste site in Ghana and had 856 pg TEQ/g fat plus 300 pg TEQ from brominated dioxins(PBDD/Fs).Other extreme PCDD/F contaminations of eggs were found at a chlor-alkali site(514 pg TEQ/g fat),Agent Orange contaminated areas in Vietnam(490,249 and 246 pg TEQ/g fat)and e-waste sites(568 and 520 pg TEQ/g fat).Where DR CALUX®bioassay revealed higher TEQ compared to measured PCDD/F-PCB-TEQ in IPEN studies,polybrominated PBDD/F were also measured and detected up to 300 pg TEQ/g fat at e-waste sites.One positive outcome from the IPEN studies is that all 10 pooled supermarket eggs in developing countries were below regulatory limit.Policy recommendations are made including:a systematic assessment of areas around PCDD/Fs and PCBs sources;measures for reduction of exposures of populations;urgent control of emission sources including PCB equipment,the open burning of plastic,and the use of plastic as fuel in boilers/incinerators in developing countries without air pollution control.Furthermore,soil limits need to be re-assessed and lowered for free-range poultry.
基金the National Key Research and Development Project of China(2019YFC1805600)the Global Environment Facility(Project 5383)the contributions are highly appreciated.
文摘Article 5 of the Stockholm Convention requires that each Party shall take measures to reduce the releases from anthropogenic sources of unintentional persistent organic pollutants(UPOPs),with the goal of their continuing minimization and,where feasible,their ultimate elimination.A major source of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)and other unintentional POPs releases,both in China and worldwide,is the metal industry in particular secondary metal industries such as copper smelting.More than 50%of the global secondary copper production is now in China and high levels of PCDD/Fs are released from these operations with the national inventory of China reporting a total of 1133.8 g toxic equivalents(TEQ)yr1.Consequently the Global Environment Facility(GEF)is supporting the project‘UPOPs Reduction through best available techniques and best environmental practices(BAT/BEP)in the secondary copper production sector’in China compromising>50%of the global secondary copper production.As part of this project,information on relevant UPOPs from the metal industry have been reviewed and is presented here.This information should also be useful for other(developing)countries for controlling UPOPs releases from metal industries.This review and the information it contains provides a robust resource for policy makers,the industry and researchers to improve secondary copper production to BAT/BEP standards in relation to the reduction of PCDD/Fs and other UPOPs release.The contents include the details required to assist the understanding of the formation of chlorinated UPOPs along with their brominated and brominated-chlorinated analogues.It reviews the international sources of information on BAT/BEP,including the integrated approach considered in the European BAT Reference document,and shows how this can be used to achieve an overall reduction of pollutant releases from the industry.The current national standards of PCDD/F limits to air,water and solid residues have been compiled and are also included.Challenges which need to be addressed,such as the current international lack to consider brominated and mixed bromo-chloro PXDD/Fs which might be more environmentally significant than PCDD/Fs in some facilities e are also discussed.The study includes a brief description of the steps China has taken to change the national regulatory framework and to improve the sustainability of its secondary metal industry.The Stockholm Convention BAT/BEP guidelines recommend consideration of integrated pollution prevention and control and sustainable production as general principles which parties may incorporate when applying the BAT/BEP guidelines and guidance.This holistic approach is considered in the current project and in the improvement of the pilot facilities and will also be considered in the replication of experiences in other facilities.Using this approach ensures the implementation of the Stockholm Convention can contribute to integrated pollution prevention and control,the development of a circular economy and consequently to genuinely sustainable development thus contributing to different sustainable development goals(SDGs).It is hoped this approach will be adopted in other developing and transition economies and thus help to achieve improvements of the secondary metal industry globally.
