Predicting the transportation tendency and potential reservoirs of dioxins by compartment distribution coefficient

We assessed the transportation tendency of dioxins and predict locations at high risk for dioxin pollution. A new parameter, the compartment distribution coefficient D_C, was created to account for the tendency of dioxins to preferentially accumulate in particular compartments. It was obtained by a model using levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in four countries: Japan, the United States, the United Kingdom, and Australia. The comparison with the temporal and spatial variation of D_C indicated whether the location release or long-range transportation caused the changes. This study showed that PCDD/Fs have the greatest tendency to remain in soil among studied media. A higher D_C value in Australia may indicate that this location is a potential future reservoir source of dioxins.     

Polybrominated diphenyl ether (PBDE) levels in the blood of pure vegetarians (vegans)

Intake of many persistent organic pollutants (POPs) including dioxins, dibenzofurans and PCBs is almost exclusively from gastrointestinal ingestion of animal fats in the diet. With polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), no consensus exists at present as to the extent of intake from food, from indoor dust or other routes of intake. Vegans, or pure vegetarians, were previously found to have low body burden of dioxins and dibenzofurans in blood. Data reported here for the first time show a trend towards lower PBDE levels with longer time periods without ingestion of food of animal origin in 8 adult residents of the United States. A stronger relationship between lower PBDE levels and time without meat, specifically, is consistent with substantial PBDE intake from meat relative to fish or dairy products in Americans. These vegans had somewhat lower PBDE levels with a range 12.4–127 and a median 23.9?ppb than published reports of US general population samples which had a range of 4–366 and median of 26?ppb. Our findings suggest that food of animal origin may be a major but not the sole contributor to human body burden of PBDEs.     

Detailed analysis of PCBs and PCDD/Fs impurities in a dielectric oil sample （ASKAREL Nr 1740） from an imported transformer in China

Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil （ASKAREL Nr 1740） in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry （HRGC/HRMS）. The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners （i.e., # 153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181） account for more than 50% of the total PCB concentrations. Total concentration ofPCDDs, PCDFs and dioxin-like PCBs （DL-PCBs） was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF 〉 HxCDFs 〉 HpCDFs 〉 PeCDFs 〉 TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners （i.e., #118, #156, #157） accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.     

Study on polychlorinated dibenzo‐p‐dioxins and dibenzofurans in rivers and estuaries in Osaka Bay in Japan

In order to search the source of polychlorinated dibenzo‐p‐dioxins (PCDDs) and dibenzofurans (PCDFs) in blue mussel in Osaka bay, sediments from Osaka bay and from rivers running near an urban municipal incinerator were analysed for PCDDs, PCDFs and PCBs. The river and estuary sediments were all found to be contaminated with PCDDs at average levels of 9.8 and 12ppb on the dry basis, PCDFs of 7.8 and 5.1 ppb, and PCBs of 1600 and 1300ppb, respectively. The two sediments contained similar profiles of specific isomers and congeners of PCDDs and PCDFs with each other. In addition, there was observed positive close correlations between PCDD and PCDF levels in the two specimens as well as fly ash from urban municipal incinerators. These allow the conclusion that the main source of the two chemicals in Osaka bay is fly ash from waste incineration.     

Prevention of dioxins de novo formation by ethanolamines

Two inhibitors, triethanolamine (TEA) and monoethanolamine (MEA), were tested for their ability to prevent the de novo formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) on sinter plant fly ash. The amounts of both PCDDs and PCDFs, formed by thermal treatment of the fly ash, decreased when inhibitors were added. Up to 90% reduction of the PCDD/Fs formation was reached when 2 wt % monoethanolamine was mixed with fly ash. The temperatures tested, 325 and 400 °C, did not affect the inhibition activity. However, a longer reaction time, 4 h instead of 2 h, gave higher percentages of PCDD/Fs reduction. The laboratory results show that ethanolamines reduce the dioxins formation on sinter plant fly ash under various conditions of temperature and reaction time. Moreover, factory tests performed in parallel at a sinter plant are in good agreement with the laboratory experiments, thus confirming that the use of ethanolamine inhibitors is an appropriate technique for the prevention of dioxins emissions from sintering processes. Electronic Publication     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part V†: Hypotheses and summary

The hypotheses on the de novo syntheses of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo‐p‐dioxins (PCDDs), based on known literature, are presented. Polychlorinated benzenes and polychlorinated phenols are probably key intermediates.

In the present article, hypotheses that may account for the presence of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs) in the effluents from municipal and industrial incinerators are put forward. These hypotheses are based on the previously surveyed literature (Ref. 203–206) and experimental results on laboratory scale and thermodynamic calculations are considered. The interconnections of various reaction steps are speculative and no technological information was added to account for conditions in real incinerators. Conclusion of the discussions on the related subject matter, presented in the Parts I‐IV (Ref. 203–206), are also described in this paper.     

PCDD/DFs and coplanar PCBs in fly ash samples from various types of incinerators in Taiwan

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/DFs) and coplanar polychlorinated biphenyls (Co‐PCBs) were determined in fly ash samples from municipal solid waste (MSW), medical waste (MW), and electricity power plant incinerators in Taiwan. The average concentrations of PCDD/DFs and Co‐PCBs are 7.02 ng‐TEQ/g and 1.06 ng‐TEQ/g, respectively. The contributions to total TEQ are 24% from PCDDs, 64% from PCDFs, and 12% from Co‐PCBs, indicating that PCDFs generate the highest environmental impact and MSW and MW incinerators are potential Co‐PCBs contaminating sources. The levels of PCDD/DFs and Co‐PCBs found in ash samples increase from petroleum‐fired, coal‐fired, large municipal solid waste, small medical waste, to small municipal solid waste incinerators, and are generally lower than those from incinerators built earlier. All fly ash samples analyzed in this study were considered hazardous materials. More research is suggested to establish the relationship between the amounts of PCDD/DFs and Co‐PCBs in fly ash and in flue gas.     

Distribution,seasonal variation and inhalation risks of polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins and dibenzofurans,polychlorinated biphenyls and polybrominated diphenyl ethers in the atmosphere of Beijing,China

Spatial distribution, seasonal variation and potential inhalation risks of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were investigated in the atmosphere of Beijing, using passive air samplers equipped with polyurethane foam disks. Concentrations of ΣPCDD/Fs, ΣPCBs and ΣPBDEs ranged from 8.4 to 179 fg WHO₂₀₀₅-TEQ/m³, 38.6–139 and 1.5–176 pg/m³, respectively. PCDFs showed higher air concentrations than those of PCDDs, indicating the influence of industrial activities and other combustion processes. The non-Aroclor congener, PCB-11, was detected in air (12.3–99.4 pg/m³) and dominated the PCB congener profiles (61.7–71.5% to ∑PCBs). The congener patterns of PBDEs showed signatures from both penta-BDE and octa-BDE products. Levels of PCDD/Fs, PCBs and PBDEs at the industrial and residential sites were higher than those at rural site, indicating human activities in urban area as potential sources. Higher air concentrations of PCDD/Fs, PCBs and PBDEs were observed in summer, which could be associated with atmospheric deposition process, re-volatilization from soil surface and volatilization from use of technical products, respectively. Results of inhalation exposure and cancer risk showed that atmospheric PCDD/Fs, dioxin-like PCBs and PBDEs did not cause high risks to the local residents of Beijing. This study provides further aid in evaluating emission sources, influencing factors and potential inhalation risks of the persistent organic pollutants to human health in mega-cities of China.     

草浆漂白过程中二噁英类生成机理探讨

本文以氯苯、氯酚、二苯并二噁英（DBD）和二苯并呋喃（DBF）为PCDD/Fs前生体,模拟工业草浆漂白条件,探讨了次氯酸盐和氯气漂白苇浆过程中二噁英类的生成机制,研究表明,在苇浆中加入二噁英类前生体如DBD/F,其氯化产物与在木浆中有所区别,在实验条件下,二噁英类的生成量分别为:15μg PCDDs·mg~（-1）DBD。1.5μg PCDFs·mg~（-1）DBF。     

Isomer‐specific determination and toxic evaluation of potentially hazardous coplanar PCBs,dibenzofurans and dioxins in the tissues of “Yusho” PCB poisoning victim and in the causal oil

In the light of new discoveries on the extremely toxic non‐ortho coplanar 3,3’,4,4'‐tetra‐ (T₄CB), 3,3’,4,4’,5‐penta‐(P₅CB) and 3,3'4,4’,5,5'‐hexachlorobiphenyl (H₆CB) and their mono‐ and di‐ortho analogs, tissue samples of a Yusho poisoning victim and Yusho causal oils were subjected to a thorough congener/isomer‐specific investigation for polychlorinated biphenyls (PCBs), polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo‐p‐dioxins (PCDDs). Among the many PCB congeners detected in Yusho oil, non‐ortho coplanar T₄CB constituted 3.1%, P₅CB‐0.17% and H₆CB‐0.0072% in total PCBs. Their concentrations in liver and adipose tissue were 130–700 (T₄CB), 54–720 (P₅CB) and 50–380 (H₆CB) pg/g on wet weight basis. The observed concentrations in adipose tissue were two to four fold higher than that detected in unexposed individuals. Among the PCDFs identified, toxic 2,3,7,8‐substituted isomers including 2,3,4,7,8‐P₅CDF were the dominant ones. Tetra‐ through hepta‐CDDs were detected in the oil, whereas octa‐CDD was the dominant isomer in the patient. A comparison with KC‐400 revealed enrichment of coplanar PCBs in Yusho oil along with toxic PCDFs. Enrichment was highest for 3,3'4,4'5,5'‐H₆CB followed by 3,3’,4,4'5‐P₅CB. A comparative toxic evaluation of these chemical groups in Yusho patient's adipose tissue based on “2,3,7,8‐T₄CDD Toxic Equivalent Analysis” revealed accountable toxic contribution from coplanar PCBs. This analysis also confirmed that 2,3,4,7,8‐P₅CDF was the principal causative agent in Yusho poisoning.     

电子垃圾拆解对台州氯代/溴代二噁英浓度和组成的影响

电子垃圾拆解会导致有毒有害污染物向大气的排放,造成环境污染的产生。为了解电子垃圾拆解及废旧金属再生活动对拆解地及邻近地区空气质量的影响,对台州峰江金属再生园区附近及对照区路桥市区大气中(气态和颗粒态)氯代二噁英(PCDD/Fs)、溴代二噁英(PBDD/Fs)的含量、同系物组成及气/固分配规律进行了研究,通过相关性分析探讨了PCDD/Fs和PBDD/Fs的可能来源。结果显示,金属再生园区冬季采样期间17种2,3,7,8-PCDD/Fs和8种2,3,7,8-PBDD/Fs的平均浓度分别为212.2 pg·m-3和17.6 pg·m-3,夏季采样期间的平均浓度分别为84.5 pg·m-3和5.4 pg·m-3,均显著高于对照点。夏季采样期间对照点处于再生园区的下风向,其二噁英浓度高于冬季,说明其受到了金属再生园区的明显影响。基于相关性分析的结果,塑料焚烧是金属再生活动中氯代和溴代二噁英的主要来源。初步的暴露风险评价表明,金属再生园区附近居民每日摄入的二噁英含量远远超过世界卫生组织规定的人体每日耐受量(1~4 pg W-TEQ·kg-1·d-1)。上述研究结果为规范电子垃圾拆解活动提供了基础数据。     

High dechlorination of PCBs catalysed by carbon under mild conditions

This article reports high dechlorination of toxic polychlorinated biphenyls (PCBs) under mild conditions. PCBs are priority pollutants acting as endocrine disruptors, human carcinogens and environmental estrogens. Previous remediation methods involving high temperature and pressure have drawbacks such as high cost, de novo dioxins synthesis and difficult recovery of vaporized PCBs. On the other hand, dechlorination methods using mild conditions show the problem of catalyst deactivation. Here, activated carbon was used for the first time as catalyst to dechlorinate 2,4,5 trichlorobiphenyl. High dechlorination, of 87%, was achieved under mild conditions. 2,4,5 trichlorobiphenyl was treated at 40–150°C with calcium hydroxide, sodium hydroxide and sulfur in mixed water and organic solvents. Dechlorination products were biphenyl, orthohydroxy biphenyls, 2,4 dihydroxy biphenyls and biphenyl-2-thiol. Dichlorobiphenyl and orthochlorobiphenyls were found in trace quantities. We found that carbon particles catalysed dechlorination by substitution reactions and suppressed further chlorination. Dechlorination at biphenyl ortho position was preceded by substitution reaction by hydroxyl and thiol ions. Moreover, in the absence of carbon, dechlorination was lower and substituted products were not observed. These findings may be applied at industrial scale to remediate PCB-contaminated waste.     

Dioxin-/Furan-‘Verbrennungsprofile’ in Abgasen aus Hochtemperaturprozessen

Different mechanisms operating downstream from high temperature processes lead to the formation of polychlorinated dibenzo(p) dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Independent of the level of concentration, these mechanisms lead to comparable PCDD/F patterns, as has been observed from the proportion of single congeners to the total of 17 2,3,7,8-Cl-substituted congeners or to the individual homologous groups related to the sum of the homologous tetra to octa CDD/F groups. A comparison of these so-called “combustion profiles” with the congeners Heats of Formation (HoF), as calculated via semiempirical molecular orbital methods, may provide an idea of the course of thermodynamical forced reaction.     

Dioxin-/Furan-“Verbrennungsprofile” in Abgasen aus Hochtemperaturprozessen

Different mechanisms downstream from high temperature processes lead to the formation of polychlorinated dibenzo(p) dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Independent from any concentrations, these mechanisms cause comparable PCDD/F patterns, the percentage proportion of single congeners or homologous groups related to the total of 17 2,3,7,8-Cl-substituted congeners or with respect to the sum of the homologous groups tetra to octa CDD/F. The characteristics of these so-called “combustion profiles” can help to interpret corresponding data from burning and melting facilities, such as municipal waste incinerators, coal power plants, sintering plants, metal finishing facilities, cement kilns, crematoria, hazardous waste incinerators and landfill gas burners     

Dioxion-/Furan-’Verbrennungsprofile’ aus Hochtemperaturprozessen

Present knowledge assumes that different mechanisms acting downstream in high temperature processes lead to the formation of polychlorinated dibenzo(p)dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Concerning the 17 2,3,7,8-Cl-substituted PCDD/F congeners in particular, there is new evidence for a single-step reaction type (recently reported in this publication series, of. also parts 1 and 2). A formation based on a combination of the several mechanisms, which have been proposed and discussed since 1985, becomes more and more unlikely. Qualitatively the PCDD/F formation downstream from high temperature processes depends rather on a thermodynamically forced single reaction step, and on pure statistical distribution quantitatively. This may be a new ‘Thermostat Synthesis’ instead of ‘de novo’.     

不同垃圾焚烧炉产生的PCDD/Fs和PCBs同类物的分布

要应用高分辨气相色谱一质谱联用技术，测定了3种垃圾焚烧炉产生的飞灰中17种PCDD／Fs和12种共平面PCBs的浓度及毒性当量，比较了PCDD／Fs和PCBs同类物分布的差异．结果表明，流化床焚烧炉和炉排焚烧炉产生的PCDD／Fs多于PCBs，而气化熔融焚烧炉产生的PCBs多于PCDD／Fs；产生的PCBs对总毒性当量的贡献都比较小；3种焚烧炉产生的PCDD／Fs同类物具有相似的浓度分布；流化床焚烧炉和炉排焚烧炉产生的PCBs同类物具有相似的浓度分布，而气化熔融焚烧炉产生的PCBs同类物分布与其他两种焚烧炉差别较大．     

Levels and congener profiles of PCDD/Fs and dioxin-like PCBs in Baltic wild salmon (Salmo salar)

Baltic salmons were caught from two Latvian rivers during the spawning seasons of 2010 and 2011 for the determination of seventeen 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (PCBs). A partially automated clean-up procedure was used for sample preparation, followed by capillary gas chromatography hyphenated to high-resolution mass spectrometry. The concentrations of PCDD/F&;PCB-TEQ ranged from 6.6 to 18.2?ng?kg^?1 fresh weight and this confirms the previous reports of relatively high concentrations of PCDD/Fs, and especially of dioxin-like PCBs in Baltic wild salmon, in most samples exceeding maximum recommended levels (MRLs) in toxicity equivalency quotients (PCDD/F-PCB-TEQ) of the World Health Organization (WHO 1998) according to EC COMMISSION REGULATION No 1881/2006. The results suggest that high consumption of Baltic wild salmon could entail the risk of exceeding the TDI for adults and teenagers. Extra care must be taken when Baltic wild salmon is included in childrens's diet to avoid exceedance of the recommended TDI of 4?pg?kg^?1 body weight for this group.     

Polychlorinated -dibenzo-p-dioxins/furans and -dioxin-like biphenyls in eggs of common terns from lime island,St. Mary's river,Michigan, USA

Population collapse of common tern (Sterna hirundo) from Lime Island in the St. Mary's River, Michigan, USA were related to the 2,3,7,8-chlorine substituted dioxins, furans, dioxin-like PCBs, and other possible factors using unhatch egg target contaminant analysis. The most toxic congeners, 2,3,7,8-TCDD/DF was found in all samples at noticeable concentrations. Magnitude of sum 2,3,7,8-PCDD/DFs were within the range of 39–93?pg/g wet wt. Dioxin-like PCBs were within the range of 360–1230?ng/g wet wt. Great Toxic Equivalent Quantity (TEQ) contributions by 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, and dioxin-like PCBs such as CB-77, CB-126 and CB-105 are considered greatly due to their influence of poor embryo development and consequent damage of embryos of common terns in egg injection studies. However, other organochlorines, heavy metals, and/or synergistic effects also taken in to account. On the whole, TEQs in the tern eggs were greater than the Lowest-Observable-Adverse Effect Level (LOAEL) for bald eagle (Haliaeetus leucocephalus) embryos observed in British Columbia, Canada. Concentrations of dioxin-like PCBs, dioxins, furans in the St. Mary's River food chain are at levels for concern for nesting colonial waterbirds. Eventually, the possible movements of analyzed chemicals downstream from a man-made flood event are discussed.     

利用EIA法快速筛查垃圾焚烧飞灰和烟气中的二恶英毒性水平

基于CAPE技术公司的兔子复合克隆抗体的二恶英(PCDD/F)酶免疫分析试剂盒,建立了快速检测垃圾焚烧飞灰和烟气中PCDD/F毒性(TEQ值)的方法.试剂盒的最低检测限为3.3pg·tube-1(即3.3pgTEQ每EIA试管),线性检测范围为10～30pg·tube-1.样品经甲苯索氏抽提后过硅胶柱连接小碳柱净化处理,TCDD/F的回收率大约为50%,与原飞灰PCDD/F分布模式相比净化处理后样品中的TCDD/F含量明显降低.用净化处理后的飞灰溶液作标准溶液,绘制PCDD/F剂量-效应关系曲线,定量分析了2个飞灰样品和2个烟气样品的TEQ浓度,结果表明分析样品的TEQ实测值(HRGC/HRMS分析获得)与预测值(标准曲线计算值)的相对偏差(Rd)均小于15%,说明用该方法定量分析垃圾焚烧飞灰和烟气中PCDD/F毒性是可行的.     

Influence of the polychlorinated biphenyl preparation Aroclor 1242® on color changes of the fiddler crab Uca pugilator

The melanin in the melanophores of specimens of the fiddler crab, Uca pugilator, exposed to 2, 4, and 8 ppm solutions of the polychlorinated biphenyl (PCB) preparation, Aroclor 1242^®, became less dispersed than in untreated specimens. This effect was dose-dependent. It was probably due to the PCB itself and not to polychlorinated dibenzofurans which are contaminants of commercial PCBs. The decreased melanin dispersion appeared to be related to a decrease in the rate of release of melanin-dispersing hormone from eyestalk neuroendocrine cells into the hemolymph. Eyestalks of crabs kept for 4 days in Aroclor 1242 contained 4 times as much melanin-dispersing hormone as did control crabs. When injected into isolated legs, did hemolymph from control crabs. Aroclor 1242 did not appear to have a direct effect on the pigment-dispersing mechanism of the melanophores.