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.     

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/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.     

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     

分子电性距离矢量用于多氯代二苯并呋喃光解半衰期的QSPR研究（Molecular Electronegativity Distance Vector（MEDV）Applied to Quantitative Structure-Property Relationship Study on Photolysis Half-Lives of PCDFs）

多氯代二苯并呋喃(PCDFs)是一种典型的持久性有机污染物(POPs),光解是其在环境中转化的主要途径.以分子电性距离矢量(Molecular Electronegativity Distance Vector,MEDV)为参数,应用多元线性回归(Multiple Linear Regression,MLR)和偏最小二乘回归(PLSR)对48种PCDFs在云杉针叶和飞灰表面的光解半衰期(t1/2)进行模拟分析,均获得由2个变量所建的定量结构-性质相关(QSPR)模型.多元线性回归结果:建模相关系数(R)分别为0.860和0.836,标准偏差(SD)分别为0.052和0.053,交互检验复相关系数(Rcv)分别为0.839和0.807,外部检验相关系数(Qex)t分别为0.939和0.853;偏最小二乘回归结果:建模相关系数(R)分别为0.857和0.829,交互检验复相关系数(Rcv)分别为0.849和0.807.结果表明,MEDV能较好地表征该类分子的结构信息,所建QSPR模型具有良好的稳定性和预测能力.     

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.     

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．     

五氯酚及其钠盐中氯代二恶英类分析

采用ＨＰＬＣ和ＧＣ／ＭＳ的方法，对国产ＰＣＰ及其钠盐中的ＰＣＤＤｓ，ＰＣＤＦｓ进行了分析。测定了所有２，３，７，８－取代同系物。此外，还根据各ＣＤＤｓ，ＣＤＦｓ的毒性当量因于ＴＥＦｓ，计算了其毒性当量Ｉ－ＴＥＱｓ，分别为１４２，９２ｎｇ．ｇ＾－１。在前述基础上，仨算了由于ＰＣＰ及其钠盐的应用，引起的ＰＣＤＤｓ，ＰＣＤＦｓ环境输入。约为２４０ｋｇ／ａ。     

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.     

Characteristics of the stabilized/solidified municipal solid wastes incineration fly ash and the leaching behavior of Cr and Pb

Fly ash is a hazardous byproduct of municipal solid wastes incineration (MSWI). An alkali activated blast furnace slag-based cementitious material was used to stabilize/solidify the fly ash at experimental level. The characteristics of the stabilized/solidified fly ash, including metal leachability, mineralogical characteristics and the distributions of metals in matrices, were tested by toxic characteristic leaching procedure (TCLP), X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometer (SEM-EDS) respectively. Continuous acid extraction was utilized to extract metal ions and characterize their leaching behavior. The stabilization/solidification procedure for MSWI fly ash demonstrates a strong fixing capacity for the metals by the formation of C-S-H phase, hydrated calcium aluminosilicate and ettringite. The stabilized/solidified fly ash shows a dense and homogeneous microstructure. Cr is mainly solidified in hydrated calcium aluminosilicate, C-S-H and ettringite phase through physical encapsulation, precipitation, adsorption or substitution mechanisms, and Pb is mainly solidified in C-S-H phase and absorbed in the Si-O structure.     

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     

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.     

Levels and patterns of polychlorinated biphenyls in residues from incineration of established source-classified MSW in China

Municipal solid waste (MSW) source-classified collection represents an advancement in resource cycling and secondary pollution control in China. Comparative experiments were performed to assess the levels and patterns of polychlorinated biphenyls in bottom ash, fly ash from boiler, and fly ash from bag filter from an MSW incineration plant with source-classified collection of MSW. Polychlorinated biphenyls were concentrated in the bag filter fly ash and in the bottom ash. The total amount of polychlorinated biphenyls was much lower than in fly ashes and bottom ash from traditional mixed waste incineration. Total concentration of coplanar polychlorinated biphenyls and toxic equivalent quantities were also reduced. Due to variations of feed waste, complete combustion, including continuously high incineration temperature, low CO concentrations and high air excess ratio were observed. Incineration temperature showed a negative correlation, while CO concentration showed a positive correlation with total and coplanar polychlorinated biphenyls, indicating that the latter can be reduced by controlling combustion conditions related to properties of feed waste.     

六六六热解废渣中2,3,7,8—取代PCDDs和PCDFs的测定

采用ＨＰＬＣ和ＧＣ／ＭＳ法对六六六热解废渣中的ＰＣＤＤｓ和ＰＣＤＦｓ进行了测定，使用此种方法，于废渣中检出了所有２，３，７，８－取代的同系物。此外，还根据各ＣＤＤｓ，ＣＤＦｓ的毒性当量因子ＴＥＦｓ，计算了废渣的毒性当量ＴＥＱｓ，约为６１２－９２４μｇ／ｇ。分析表明，ＯＣＤＤ是含量最丰富的导构体，而１，２，３，４，６，７，８－ＨｐＣＤＤ，１，２，３，４，６，７，８－ＨｐＣＤＦ和１，２，３，４，７，８     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

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’.     

多氯苯生产中有机氯化物的分析

在气相色谱和色谱-质谱分析的基础上,对以六六六为原料生产多氯苯的两种工艺的产品及废渣进行了分析。结果表明:伴随多氯苯的生成,尚有多种氯化物产生。在水解生产工艺中,产品和废渣中有微量PCDDs和PCDFs,但产品中还有少量PCBs。在热解工艺中,废渣内发现大量的PCBs,PCDDs和PCDFs,最毒的异构体,2,3,7,8-TCDD含量高达24ppm。     

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.     

中国东海抹香鲸体内多氯联苯的组成特征及毒性当量

用气相色谱-质谱联用仪测定了一只中国东海海域抹香鲸(Physeter macrocephalus)皮脂24种多氯联苯(PCBs)同系物的含量,并分析了其组成特征以及国际毒性当量.结果表明,东海海域抹香鲸皮脂PCBs的湿重含量为1.12μg.g-1;PCBs同族体中以含6和5个氯原子的化合物为主,高氯代PCBs占总量的92.10%;PCBs同系物中以PCB153、PCB138、PCB101和PCB149居多,分别占到PCBs总量的21.28%、15.97%、10.29%和10.23%;抹香鲸皮脂的TEQs含量为1663.07 pg.g-1,其毒性主要来自PCB126,其次是PCB123和PCB118;初步推断中国东海海域的抹香鲸受PCBs污染程度较轻.     

Distribution of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, dioxin-like polychlorinated biphenyl and polycyclic aromatic hydrocarbons in the sediment of Temsah lake, Suez Canal, Egypt

Lake Temsah is one of the main wetlands in the Suez Canal region, and the main source for fish for the area. The lake is the end-point of several wastewater effluents. In the present study, residues of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyl (PCB) and polycyclic aromatic hydrocarbons (PAH) were monitored in the sediment of the lake. Samples were collected from six different sampling stations around the lake using a box-corer sampler, then kept frozen. Samples were extracted and cleaned up before residue determination was conducted using an HRGC/HRMS. An HP 6890 plus gas chromatograph was coupled to a Micromass Autospec Ultima mass spectrometer operating in EI mode at 35 eV and with a resolution of 10.000 (5% valley). PCDDs and PCDFs were detected in all sediment samples collected from various sampling stations. Results showed some progressive increase in PCDDs concentrations relevant to increase in chlorination. In the PCDD group of congeners, 1, 2, 3, 4, 6, 7, 8, 9 octa-CDD had the highest detected concentrations in all samples, while 2, 3, 7, 8 tetra-CDD showed the lowest concentrations. The World Health Organization toxicity equivalents ranged from 0.387 to 11.20 ng kg^-1 d.w. For PCDD homologues, hexa-CDD was the most dominant homologue in all sediment samples analysed. Regarding dioxin-like PCBs, results showed that IUPAC No. 118 congener, 2, 3, 4, 4, 5, pentachlorobiphenyl was the most concentrated of all detected congeners, with concentrations ranging between 0.039 and 43.201 µg kg^-1. For polycyclic aromatic hydrocarbons, benzo(b+k+j)fluoranthene had the highest concentrations in almost all sampling stations. However, fluorene was the smallest detected concentration in almost all stations. This result would indicate that PAH contamination of the lake seems to be coming from one main source in all sampling stations. The present work is the first record of PCCDs, PCCFs, and dioxin-like PCBs in the Temsah lake. The concentrations of the contaminants monitored in this study, especially those of PAHs, are rather alarming. Efforts should be made to stop point sources that contaminate the lake.