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.     

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.     

Residues of PCDD,PCDF, and PCBs in some marine organisms in Lake Temsah,Ismailia, Egypt

Residues of PCDDs/F, non-ortho, mono-ortho PCBs, and other PCBs were monitored in the tissues of mullet fish, bolti fish, bivalves and crab taken from Lake Temsah, at Ismailia, Egypt.

Results showed that 2,3,7,8 Tetra CDD and 1,2,3,7,8 Penta CDD were the most frequently detected PCDD congeners. Similarly, 2,3,7,8 Tetra CDF, 1,2,3,7,8 Penta CDF and 2,3,4,7,8 Penta CDF were the most frequently detected PCDF congeners. No relationship was apparent between the concentrations of detected PCDDs congeners and the degree of chlorination, except with crab samples in which an increase in the chlorination coincided with a decrease in the concentrations of the congeners.

In PCDF congeners, detected residues have had a reversed relationship with chlorination increase. In PCDD congeners, Octa CDD had the highest detected concentrations in the two fish species, while in the bivalves and crab, 2,3,7,8 Tetra CDD had the highest concentrations. The mullet fish had the highest total PCDDs concentration, at 0.398?pg/g fresh weight, followed by crab at 0.395?pg/g fresh weight, then bivalves and bolti fish at 0.187 and 0.062?pg/g fresh weight, respectively. In all the examined organisms, the total concentrations of PCDFs were much higher than the total concentrations of the PCDD congeners. The WHO–TEQ values were 11.92, 39.12, 25, and 3.6?pg/g fresh weight, for mullet fish, bolti fish, bivlaves and crab, respectively. The concentration of the mono-ortho congeners CB 118 was the highest detected of all non-ortho and mono-ortho PCBs congeners, with values of 0.382, 0.022, 0.231 and 0.357?ng/g fresh weight, in mullet fish, bolti fish, bivalves and crab, respectively. The WHO–TEQ concentrations were 0.799, 0.003?pg/g fw, 0.05?pg/g fresh weight, 0.676?pg/g, and 0.799?pg/g fresh weight, for the same species, respectively. The total concentration of PCBs 28, 52, 95, 99, 101, 105, 110, 118, 138, 146, 149, 151, 153, 170, 177, 180, 187 were 6.86?ng/g fresh weight for mullet fish, 0.2?ng/g fresh weight, for bolti fish, 2.72?ng/g fresh weight for bivalves and 2.8?ng/g fresh weight for crab, respectively.     

PCBs,PCDDs and PCDFs in soil samples from uncontrolled burning of waste electrical material for metal reclamation

PCDDs, PCDFs and PCBs have been analysed in soil samples where waste electrical equipment has been burned directly on the ground in three locations of Burgos (Spain). High levels of PCDDs, PCDFs and PCBs were detected in the centre of combustion sites. The results show PCB levels between 0.824 and 1.240 μg/g, and PCDDs and PCDFs levels between 8.73–36.37 ng/g and 12.79–50.95 ng/g. The I‐TEF values between 2.96–9.15 for dioxins and furans indicate that these soils are heavily polluted and may represent a risk for human and animal health.     

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.     

Polychlorinated biphenyls,polycyclic aromatic hydrocarbons and alkylphenols in sediments from the Odra River and its tributaries,Poland

Concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), nonylphenol (NP) and octylphenol (OP) were measured in sediments collected during June–August 1998 along the Odra River and its tributaries (Warta, Obrzyca, Barycz, Kaczawa and Bóbr Rivers) in Poland. In addition, raw and treated sewage sludge collected from Gdańsk, Poland, were analyzed for the target compounds. Concentrations of PCBs in sediments varied widely, ranging from 2.7 to 412?ng/g, on a dry weight basis (dry wt). PAHs were the predominant compounds in sediments with concentrations ranging from 150 to 19?000?ng/g, dry wt. The distribution of concentrations of PAHs was more homogenous than that of PCBs. NP concentrations in sediments ranged from <1 to 762?ng/g, while that of OP from <1 to 9.8?ng/g, dry wt. Measured concentrations of target analytes in sediments of the Odra River and its tributaries were comparable to or greater than those reported for riverine sediments in other eastern European countries. Concentrations of total PCBs, PAHs and NP in raw and treated sewage sludge collected from a sewage treatment plant in Gdańsk, Poland, were in the ranges of 203–284, 11?720–13?880 and 6760–99?600?ng/g, dry wt, respectively. Primary treatment of sewage did not appear to reduce PCB or PAH concentrations, although NP and OP concentrations were much less in treated sludge than in raw sludge. This is one of a few studies that document concentrations of PCBs, PAHs and NP in sediments of the Odra River and its tributaries in Poland.     

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。     

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.     

Dioxine in Lagerstätten-Tonen

In dominantly kaolinite-type, natural clay minerals, we found PCDDs at considerable levels (TEQ-values up to several hundred ng/kg). Contrary to expectations, PCDFs were not detected at all. The PCDD-contamination is most likely “natural” and not of anthropogenic origin.     

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.     

Metal binding capacity of soft acid,organic‐rich waters

Organic carbon from one stream and two ponds in South Carolina was fractionated into five nominal molecular diameter fractions by ultrafiltration. The concentrations associated with and binding capacity for Ca, Cd, Cu and Pb were determined for each fraction. The distribution of organic carbon among ultrafilter fractions varied from water to water, with the largest percentage occurring in the smaller fractions. Calcium was associated with each of the fractions isolated from each of the three waters, indicating Ca is bound to organics in all fractions, however, more than 99% of the Ca which passed the smallest ultrafilter was removed by cationic exchange resin. Each fraction bound more Ca than Cd, Cu or Pb except in a few cases where Pb binding was greater. All of the organic fractions had their Ca++ binding sites saturated. Calcium was not an effective competitive ion against Cd, Cu or Pb for organic binding sites. The total Cu binding capacity was less than that of Ca or Pb but similar to that of Cd. Naturally occurring organics bound more Pb than Cd or Cu but less than Ca. Saturation of Cu binding sites was less than 20% in most ultrafilter fractions except that with a nominal molecular weight of between 10,000 and 300,000 where the percent of saturation was as much as 60%. Approximately 50% of the Cu was removed onto anionic exchange resin in two waters while more than 90% was removed from water with a high organic content. Percent saturation of Cd and Pb binding sites ranged from 0.091% to 5.4% and 0.059% to 1.5%, respectively. All ions tested effectively competed with Cd, Cu or Pb for some but not all binding sites, indicating that organic binding sites were heterogeneous. A generalized order of metal‐organic stabilities based on competition for binding sites is Al>Cd>Pb>Cu>Ni = Mg=Zn = Mn>Ca. Both Cd+2 and Al+3 effectively out competed Pb++ and Cd and Pb out competed Cu for most organic binding sites.     

Control of chlorinated aromatic compounds from a municipal solid waste incinerator using limestone addition

In this study, limestone powder was directly added to synthetic MSW, which was fed into a small‐scale fluidized bed incinerator. The concentration of CBzs and CPs in the flue gas were measured before and after a secondary combustion air injection. Finally, the PCDDs and PCDFs concentrations were also measured in the flue gas after the secondary combustion zone. The CaCO₃ added to synthetic MSW not only controls HCl in the flue gas, but suppresses the formation of chlorinated aromatic compounds like CBzs, CPs, PCDDs, and PCDFs. The main mechanisms to control the formation of chlorinated aromatic compounds was more likely related to the suppression of catalytic capability of flyash than the HCl reduction in the flue gas. However, the NO concentration was increased by catalytic reaction of limestone in the fluidized bed.     

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     

Long-distance transport of Hg, Sb, and As from a mined area, conversion of Hg to methyl-Hg, and uptake of Hg by fish on the Tiber River basin, west-central Italy

Stream sediment, stream water, and fish were collected from a broad region to evaluate downstream transport and dispersion of mercury (Hg) from inactive mines in the Monte Amiata Hg District (MAMD), Tuscany, Italy. Stream sediment samples ranged in Hg concentration from 20 to 1,900 ng/g, and only 5 of the 17 collected samples exceeded the probable effect concentration for Hg of 1,060 ng/g, above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in Tiber River sediment varied from 0.12 to 0.52 ng/g, and although there is no established guideline for sediment methyl-Hg, these concentrations exceeded methyl-Hg in a regional baseline site (<0.02 ng/g). Concentrations of Hg in stream water varied from 1.2 to 320 ng/L, all of which were below the 1,000 ng/L Italian drinking water Hg guideline and the 770 ng/L U.S. Environmental Protection Agency (USEPA) guideline recommended to protect against chronic effects to aquatic wildlife. Methyl-Hg concentrations in stream water varied from <0.02 to 0.53 ng/L and were generally elevated compared to the baseline site (<0.02 ng/L). All stream water samples contained concentrations of As (<1.0–6.2 μg/L) and Sb (<0.20–0.37 μg/L) below international drinking water guidelines to protect human health (10 μg/L for As and 20 μg/L for Sb) and for protection against chronic effects to aquatic wildlife (150 μg/L for As and 5.6 μg/L for Sb). Concentrations of Hg in freshwater fish muscle ranged from 0.052–0.56 μg/g (wet weight), mean of 0.17 μg/g, but only 17 % (9 of 54) exceeded the 0.30 μg/g (wet weight) USEPA fish muscle guideline recommended to protect human health. Concentrations of Hg in freshwater fish in this region generally decreased with increasing distance from the MAMD, where fish with the highest Hg concentrations were collected more proximal to the MAMD, whereas all fish collected most distal from Hg mines contained Hg below the 0.30 μg/g fish muscle guideline. Data in this study indicate some conversion of inorganic Hg to methyl-Hg and uptake of Hg in fish on the Paglia River, but less methylation of Hg and Hg uptake by freshwater fish in the larger Tiber River.     

Perfluorinated compounds in a coastal industrial area of Tianjin,China

Perfluorinated compounds (PFC) in water, sediment, soil, and biota from the coastal industrial area of Tianjin, China, were measured to provide baseline information and to determine possible sources and potential risk to wildlife. Perfluorooctanesulfonate (PFOS) was the predominant PFC with maximum concentrations of 10 ng/L in water, and 4.3, 9.4, and 240 ng/g dw in sediment, soil, and fish, respectively. Perfluorooctanoate (PFOA) concentration in water ranged from 3.0 to 12 ng/L. Perfluoroundecanoate (PFUnA) and Perfluorododecanoate (PFDoA) were detected in solid matrices, respectively, at concentrations of 相似文献   

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.     

Soxhlet extraction parameters’ influence on the recovery of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) from a sediment,and artifact formation of PCDD

Soxhlet extraction of polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/F) from sediment was studied using a designed experimental set‐up. Three variables were studied: three solvent combinations n‐hexane/methanol, dichloromethane/acetone and toluene/methanol; two extraction times, 8 and 16 h, and addition of bulk substances (sodium carbonate). The extraction efficiency was almost identical in all extractions, with the exception of extraction where toluene/ methanol was combined with sodium carbonate. In these samples a major effect was observed, due to formation of Hx‐, Hp‐ and OCDD isomers. Composition of formed PCDD was similar to PCDD isomers found in pentachlorophenol products.     

Aliphatic and polycyclic aromatic hydrocarbon contamination in surface sediment of the Chitrapuzha River,South West India

Distribution (seasonal and spatial) of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in surface sediments of the Chitrapuzha River, Cochin, India, was investigated using gas chromatography. Significantly high concentrations prevailed during the pre-monsoon season with the industrial zones of the river appearing to be hot spots with particularly elevated levels of the hydrocarbons. AHCs ranged between 7754 and 41,173?ng/g with an average of 25,256?ng/g, while total PAHs varied from 5046 to 33,087?ng/g. n-Alkane indices and PAH diagnostic ratios point to petroleum contamination in the sediments. The significance of PAHs in the sediments was explored using universally accepted interpretation tools. Observed levels of PAHs in sediments of Chitrapuzha are likely to cause adverse effects on biota.     

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。