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.     

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.     

Hydrothermal treatment of MSWI fly ash for simultaneous dioxins decomposition and heavy metal stabilization

Researches on the hydrothermal treatment of municipal solid waste incineration (MSWI) fly ash were conducted to eliminate dioxins and stabilize heavy metals. In order to enhance decomposing polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) during hydrothermal process, a strong reductant carbohydrazide (CHZ) is introduced. A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature; CHZ was spiked into solution according to specially defined dosage. Experimental results showed that under the temperatures of 518 K and 533 K, the decomposition rates of PCDDs/PCDFs were over 80% and 90%, respectively, by total concentration. However, their toxic equivalent (TEQ) decreased only slightly or even increased due to the rising in concentration of congeners 2, 3, 7, 8-TCDD/TCDF, which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process. Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results. Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.     

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.     

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’.     

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.     

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.     

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     

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．     

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。     

Abstracts to forthcoming papers

Soil and sediments collected at a former chlor‐alkali plant in coastal Georgia (United States), revealed the presence of PCDF concentrations as great as 82.3 ng/g, dry wt. PCDF congener profile in soil was typical of “chlorine pattern”; with elevated proportions of OCDF and HpCDF. Concentrations of PCDFs declined gradually by 44‐fold at a distance of about 500 m along the contamination gradient. Of PCDDs/DFs, 2,3,7,8‐substituted PCDFs accounted for 94–98% of the TCDD‐like activity, which declined by 25‐fold, corresponding with the reduction of total PCDF concentrations. Concentrations of PCDDs in sediments were as great as 17 ng/g, with an elevated contribution from OCDD. The magnitude of decline in PCDD concentrations with distance from the source was less pronounced than that for PCDFs. PBDDs and PBDFs were not detected. Polybrominated biphenyl ether (PBBE) and monobromo‐heptachloro dibenzo‐p‐dioxins and dibenzofurans (PXDDs/DFs) were found, though, at low concentrations. Their spatial distribution was similar to those of PCDDs.     

Levels and congener distributions of PCDDs,PCDFs and dioxin-like PCBs in environmental and human samples: a review

The term “dioxins” is often used in a confusing way. In toxicological considerations—and also in the present report—the term is used to designate the PCDDs, the PCDFs and the coplanar (“dioxin-like”) PCBs, since these classes of compounds show the same type of toxicity. Because of the large number of congeners, relevant individual congeners are assigned with a toxic equivalency factor (TEF) that relate their toxicity to that of tetrachlorodibenzo-p-dioxin (TCDD) (2,3,7,8-TCDD) and are to be evaluated as dioxins. Each concentration of an individual congener in a mixture is multiplied with its TEF, and the resulting TCDD equivalents are added up and expressed as WHO-endorsed toxic equivalents (WHO-TEQ). Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are mainly the by-products of industrial processes (such as metallurgical processing, bleaching of paper pulp, and the manufacturing of some herbicides and pesticides) but they can also result from natural processes like volcanic eruptions and forest fires. Waste incineration, particularly if combustion is incomplete, is among the largest contributors to the release of PCDDs and PCDFs into the environment. Due to their persistence, PCDDs, PCDFs and PCBs are part of the so-called persistent organic pollutants group of compounds that also include some chlorinated pesticides. Since they have a high lipophilicity and resist transformation, they bio-accumulate in animal and human adipose tissues. Consumption of food is considered as the major source of non-occupational human exposure to PCDD/Fs with foodstuffs from animal origin accounting for more than 90% of the human body burden. With meat, dairy, and fish products being the main contributors. The aim of the present review was to summarize experimental data regarding dioxin emissions from contaminated and uncontaminated biological and environmental samples, from the available literature. The information will be presented chronologically with respect to distribution in human milk, serum; food, water, air, soils and sediments.     

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.     

Improvement of sampling and analytical methods for polychlorinated dibenzo‐p‐dioxins and dibenzofurans in environmental samples and its quantitative evaluation

Sampling of PCDDs/Fs in flue gas from a MSW incinerator was conducted using a modified apparatus of the 5 train method, which has been widely used for the sampling of PCDDs/Fs emission. In the atmosphere a high volume air sampler with special packings was used. Collection efficiencies of PCDDs/Fs were more than 98% for both samplers, using ¹³C₁₂—PCDD reference standard isomers. It was suggested that these sampling methods were adaptable for the measurements of PCDDs/Fs at sources and in the environment. To validate the applicability of existing methodologies on the PCDD/F determination, interlaboratory comparisons were undertaken. From high resolution GC/MS analysis, 2,3,7,8‐TCDD concentrations in reference ash samples were 0.052±0.013 ng/g as comparable results between the laboratories. In addition, the daily intakes of PCDDs/Fs for exposed persons in the MSW incineration facilities in Japan were estimated ranging of 0.053 to 0.28 pg/kg/day by the international toxic equivalent calculations.     

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.     

Polychlorinated-dibenzo-p-dioxins, -dibenzofurans and -dioxin-like polychlorinated biphenyls in aquatic organisms from lake Kasumigaura,Japan

Polychlorinated-dibenzo-p-dioxins (PCDDs), -dibenzofurans (PCDFs) and -dioxin-like polychlorinated biphenyls (DLPCBs) were determined in aquatic wildlife of Kasumigaura Lake (KUL), Japan from 1978 to 2001. Two plankton species elucidated several fold greater concentrations (2400–7800) than small tiger fish (310–6500), shrimp (160–1100), and three large fish namely, black bass (120–240), carp (94–120) and mullet (54) on pg/g fat. PCDD homologues were predominant accumulants with >68–<95% contribution and remaining was shared by PCDFs. Accumulation, non-ortho DLPCBs in plankton (3500–9200), shrimp (1600–8600) and small fish (2000–8800) and large fish (1300–3900) on ng/g fat basis were several orders magnitude greater than PCDD/DFs. The mono-ortho DLPCBs in large fish species were 23?000–83?000?ng/g fat and which it is accounted 94.3–95.9% the total dioxin-like PCBs accumulation. Temporal trends of PCDDs, PCDFs, non-ortho PCBs and TEQ in shrimp and small tiger fish were varied. The mullet had minimum toxic equivalency “TEQ” (14?pg?TEQ/g) followed by plankton Neomysis intermedia (25?pg?TEQ/g), small tiger fish (mean: 33, ranges 14–66?pg?TEQ/g), plankton Cyclopus vicinus (34?pg?TEQ/g), carp (mean: 35, ranges 32–38?pg?TEQ/g), shrimp (mean: 38, ranges 11–68?pg?TEQ/g) and black bass (mean: 59, ranges 38–79?pg?TEQ/g) on fat basis. In all the samples, PCDD was predominant TEQ contributor followed by PCDFs and DLPCBs. The contribution of mono-ortho DLPCBs to the total TEQ was 0.52–0.92 in large fish.     

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.     

PCDD/Fs emission, risk characterization, and reduction in China’s secondary copper production industry

Secondary copper production is one of the key polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) emission sources in China, but research and data on this issue are rare. In 2004, when the Stockholm Convention entered into force in China, PCDD/Fs emissions from secondary copper production contributed to 32.2% of the total release. In this paper, PCDD/Fs emission dynamics from secondary copper industry were discussed and cumulative risks were characterized. From 2004 to 2009, industrial policies played an indirect role in PCDD/Fs reduction, but its effects are still limited. The Yangtze River Delta, Pearl River Delta and central regions were among the top three of dioxin emissions from secondary copper production in China. Shanghai, Shandong, Zhejiang, and Jiangxi had comparatively higher accumulated risk and were recommended as the priority regions for promoting PCDD/Fs emission control in China. From 2009 to 2015, the PCDD/Fs emission dynamics in the secondary copper industry were presented through simulation. PCDD/Fs emission equations were established, resulting in the recommendation of control technology conversion rate at 30% for small scale smelters and 51%–57% for large and medium-sized enterprises in 2015. In conclusion, both indirect policy and direct control technology retrofitting should be integrated for more effective PCDD/Fs emission reduction in secondary copper industry.     

Polychlorinated dibenzo p-dioxins and dibenzofurans emissions in a primary copper smelter in China

Metallurgical production is the largest polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) emission source in China. However, PCDD/F monitoring and research are rarely conducted on primary metallurgical production. In this study, a demonstration primary copper smelter in China was selected to investigate PCDD/F characteristics and control. Samples were collected from major PCDD/F release points in the smelter process (fly ashes and waste water sludge). Specific analysis of PCDD/F congeners was carried out using a high resolution gas chromatography/high resolution mass spectrometry method. The results showed that PCDD/Fs might be unintentionally produced in the primary copper smelter processes, with sample concentrations of 180–6110 pg/g dry wt; highly chlorinated PCDD/F homologues were predominant. The toxicity of all the samples was calculated to be 120 pg WHO TEQ/g, fly ashes from the refining process furnaces air pollution control device and sludge were hazardous waste with higher PCDD/F toxicity. Both precursor formation and de novo synthesis were found to contribute to PCDD/F formation in the smelter process. PCDD/F characteristics and formation were compared with reported secondary copper smelters. Life-cycle control of PCDD/F was proposed for retrofitting of this smelter and for similar plants in China's primary copper production sector, including control at the PCDD/F formation, removal and disposal stages.     

危险废物焚烧设施二噁英类排放特征及周边土壤污染调查

调查了13座不同类型的危险废物焚烧设施及二噁英类排放模式及部分设施土壤的污染水平.结果表明,排放浓度同焚烧处理量没有显著的关系.4—6氯代PCDD/Fs和7—8氯代PCDD/Fs呈现出了不同的排放特征.4—6氯代PCDF/PCDD比值为60.58±1.98(95%置信区间),较通用的总PCDF/总PCDD比值更适于描述危险废物焚烧设施二噁英排放的特征.使用PCA及聚类分析方法将设施排放模式归类为3种模式.分布模式同焚烧设施炉型、处理量以及尾气处理方式等因素相关性并不显著.2,3,4,7,8PeCDF对I-TEQ的贡献为35%—45%,并与I-TEQ具有很高的相关性.厂区土壤中二噁英浓度水平约为8—14ngI-TEQ.kg-1,周边土壤浓度为1—4ngI-TEQ.kg-1左右,均处于较低水平,调查设施周边土壤的使用目前尚无明显风险.危险废物设施对周边土壤的环境风险需要进一步评估.