Polychlorinated biphenyls in the Kupa River, Croatia, Yugoslavia

The presence of polychlorinated biphenyls (PCBs) was investigated in samples of water, suspended particles, sediments and fish from the Kupa river, Croatia, Yugoslavia, along a river stretch extending up to 10 km upstream and 200 km downstream of the primary contaminated karst region. Contamination was due to improper disposal of industrial waste discharge. The PCB levels detected in the samples collected downstream ranged from 1 to 52 ng 1⁻¹ for water, from 50 to 190 μg kg⁻¹ for suspended particles and from 8 to 39 μg kg⁻¹ for the sediment. A wide range of PCB concentrations, from 0.1 to 42.3 μg g⁻¹, which were measured in edible portions of different fish confirmed a long-term contamination of the river with PCBs. As the Kupa may be classified among low to moderately contaminated waters, it is essential that the investigations of the presence and behaviour of PCBs in the river and its environment be continued.     

Polychlorinated phenols,guaiacols and catechols in environment

Emissions, bioaccumulation and possible food chain enrichment of polychlorinated phenols, guaiacols and catechols have been studied by analyses of water, snow, ash, benthic animal, fish and bird samples in Finland. Seventeen individual compounds were analyzed using authentic reference model compounds and internal standard by GC/ECD. Although the enrichment potential of the studied compounds appeared to be lower than that of the chlorinated hydrocarbons, they proved to be very general pollutants and some of them showed specific bioaccumulation to certain species and high persistency thus forming environmental hazards.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls in the general population in Finland

We measured adipose tissue concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs), and polychlorinated biphenyls (PCBs) in 420 general Finns living in southern Finland. The mean (median) concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ were 29.0 (24.1) and 20.7 (16.7) pg g-1 fat, respectively. The concentrations clearly correlated with age. Expressing the concentrations as a function of subject's ages revealed that the exposure of Finns has declined over the last 30 years. A downward gradient was found in the concentrations from the Baltic Sea coast to inland areas in Finland, and this was assessed to be due to consumption of the Baltic Sea fish, especially Baltic herring. Linear regression models for natural logarithm WHO(PCDD/F)-TEQ, natural logarithm WHO(PCB)-TEQ, and natural logarithm WHO(total)-TEQ, explained 70%, 69%, and 72% of the variability, respectively. Age, lactation, place of residence, and fish consumption frequencies were significant predictors in the models.     

Polychlorinated naphthalenes in sediments from the Venice and Orbetello lagoons, Italy

The purpose of this study was to evaluate the contamination caused by polychlorinated naphthalenes in two polluted Mediterranean lagoons. Surface sediment samples from Venice and Orbetello lagoons were analysed using HRGC-HRMS. The levels of the sum of mono- to octa-CN ranged from 0.03 to 1.51 ng/g. Differences in PCN levels were observed as a function of the sampling site, with levels at the industrial sites exceeding those at the control sites. Although the PCN patterns and profiles resembled one another in different sediment samples, they differed considerably when compared with those in the technical PCN formulation Halowax 1014.     

Phenanthrene degradation in Arthrobacter sp. P1-1: initial 1,2-, 3,4- and 9,10-dioxygenation, and meta- and ortho-cleavages of naphthalene-1,2-diol after its formation from naphthalene-1,2-dicarboxylic acid and hydroxyl naphthoic acids

Arthrobacter sp. P1-1, isolated from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Hilo, HI, USA, can decompose phenanthrene (40 mg l⁻¹) completely within 7 days. A detailed phenanthrene metabolism map was constructed based on metabolite analysis and replacement cultures. Initial dioxygenation occurs on 1,2-, 3,4-, and 9,10-C of phenanthrene, dominantly on 3,4-C positions. Rapid accumulation of 5,6- and 7,8-benzocoumarin suggests that phenanthrene-1,2- and -3,4-diols mainly undergo meta-cleavage. However, a trace amount of o-carboxyvinylnaphthoates and diphenic acid indicates a limited extent of ortho-cleavage of the diols. Naphthalene-1,2-diol, as a common and converged metabolite, was formed from 1-[(E)-2-carboxyvinyl]-2-naphthoic acid, naphthalene-1,2-dicarboxylic acid, and 1-hydroxy-2-naphthoic acid in separate culture tests. Naphthalene-1,2-diol is then degraded in a dominant phthalic acid pathway and a minor salicylic acid pathway. Several metabolites of phthalic acid were found, while no salicylic acid metabolites were detected. The strain P1-1 likely has a very diverse set of PAH-degrading enzymes or the enzymes having relaxed substrate-specificity.     

Polychlorinated biphenyls in sediments of the Tam Giang-Cau Hai Lagoon, Central Vietnam

The Tam Giang-Cau Hai Lagoon, the largest in south east Asia, suffers from a great anthropogenic pressure and appears subject to a process of progressive environmental deterioration. To establish causes, history and trends of lagoon contamination, sediment samples representing three major parts of the systems were sampled and analysed for porosity, organic carbon, total nitrogen, delta(13)C, grain size, radiotracers and PCBs. PCB surficial concentrations range from 10.2 to 24.5 microg kg(-1), and maximum values are close to NOAA ERL guidelines. The downcore distribution of PCBs shows two well defined peaks in the core from Tam Giang (25.5 and 16.2 microg kg(-1)), whereas the sediment from Cau Hai is characterised by a maximum at the surface. Therefore, present trends indicate that contamination is still increasing or slightly decreasing. The prevailing congeners are 3-CB and 4-CB, hence recent PCBs appear to be mostly originated by Aroclor 1016- and 1242-like mixtures, with some samples influenced also by Aroclor 1248. Present sources seem to be similar everywhere and probably they are widespread all over the territory of the Thua Thien-Hue province.     

Polychlorinated biphenyls in sediments of the Venice Lagoon

Twenty-four surficial sediment samples, representing different environments within the Venice Lagoon, were analyzed for polychlorinated biphenyls (PCBs) in order to assess degrees of pollution, sources, areal distribution, and potential risk for the environment. Concentrations in surficial sediments range from 2 to more than 2049 microg kg(-1) dw. The maximum is probably due to the discharge of industrial wastes into the Brentella Canal, within the first Industrial Area. Lagoon samples are 11-205 times less contaminated, being influenced by pollutants stored in the canals only occasionally. Congener profiles distinguish PCBs in two main categories. The baseline pollution is probably due to a variety of sources within the lagoon system, whereas less chlorinated PCBs were discharged into the Brentella Canal. Our estimates suggest that, due to high concentrations, toxic equivalents (TEQs) of PCBs are comparable to those relative to PCDD/Fs for the least contaminated samples, whereas they are lower in case of heavy PCDD/F contamination.     

Polychlorinated dibenzo-p-dioxins, -dibenzofurans, and biphenyls in domestic animal food stuff and their fat

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzo-p-dioxins (PCDFs) and dioxin-like coplanar PCBs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) were measured in domestic animal related samples such as feed ingredient, mixed feed and animal fat from Japan. The mean concentration of total PCDDs, PCDFs and coplanar PCBs in fish oil was 17000pg g-1 lipid wt, which 9- to 30-fold greater than that from other animal originated ingredients. Mixed feed for chicken and chicken fat contained greater total PCDDs, PCDFs, coplanar PCBs concentrations (190 and 2100pg g-1 lipid wt) compared to those for pig (120 and 320pg g-1 lipid wt). WHO-TEQs were ranged 0.39-13, 0.15-0.22 and 0.73-2.8pg g-1 lipid wt for ingredients, mixed feeds and animal fats, respectively. Greater biomagnification factor was noticed for congeners 1,2,3,7,8-PeCDD, 1,2,3,6,7,8-HxCDD, 2,3,7,8-TCDF and 1,2,3,4,7,8-HxCDF in chicken and pig fat. Biomagnification factors for both mono- and non-ortho coplanar PCBs were greater in chicken fat compared to those in pig fat.     

Polychlorinated biphenyls and particulate organic/elemental carbon in the atmosphere of Chesapeake Bay,USA

Polychlorinated biphenyls (PCBs) and particulate organic/elemental carbon (OC/EC) differ as to sources, but are both elevated in major urban areas leading to loadings of proximate terrestrial and aquatic systems. Because of the dramatic difference in speciation, sources, and sinks of these compunds, gas+particulate phase PCBs and particulate OC/EC were measured in urban Baltimore, MD and over Chesapeake Bay at 4 and 12 h frequencies in July 1997. Gas phase ∑PCBs averaged 1180 pg m⁻³ for Baltimore and 550 pg m⁻³ for northern Chesapeake Bay. PCB homolog distributions in the gas phase differed between the land and over-water sites whereby the trichlorobiphenyls were higher in Baltimore compared to Chesapeake Bay. Autocorrelation analysis yielded a diurnal cycle for gas phase PCBs at Baltimore with the lowest concentrations observed during the day. Particulate organic and elemental carbon constituted 12.4% (17.4% organic matter) and 2.8% of total suspended particles (TSP) in Baltimore, and 15.0% (21.0% organic matter) and 5.3% over the Chesapeake Bay, respectively. Variability in PCB concentrations was not related to the variability in OC/EC concentrations. OC/EC ratios suggest that particulate organic carbon was mostly primary aerosol. Emissions of both classes of compounds into the Baltimore atmosphere and vicinity are major sources to the Bay.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paddy soils and river sediments in Akita, Japan

Paddy soils and sediments from the Yoneshirogawa, Omonogawa, and Koyoshigawa River Basins in Akita were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The levels and compositions in those samples including soils from non-agricultural areas (non-agricultural soils) were investigated using isomer-specific analysis to determine characteristic sources. The PCDD/PCDF compositions in the samples were compared with respect to possible sources. The PCDD/PCDF concentrations in paddy soils were much higher than those in the non-agricultural soils and much higher than those found in other parts of Japan. Although PCDD/PCDFs were ubiquitous in sediments from river sources to mouths of the respective river basins, those concentrations were much lower than those from paddy soils and non-agricultural soils, and from other parts of Japan. Comparison of PCDD/PCDF homologues and isomer compositions for samples indicated that compositions of paddy soils and sediments, except for those from river sources, had similar characteristics to PCDD/PCDFs originating from impurities in herbicides, 2,4,6-trichlorophenyl 4-nitrophenyl ether (CNP) and pentachlorophenol (PCP), and that compositions of river-source sediments and non-agricultural soils resembled those of atmospheric depositions. Results of statistical analyses suggest that PCDD/PCDF contamination of paddy soils and sediments is attributable mainly to three sources: CNP, PCP, and atmospheric deposition. Results of this study also demonstrate that CNP and PCP are not only important contaminants of local areas of Japan, but that they exist throughout Akita, in northern Japan. We therefore conclude that PCDD/PCDF pollution caused by those compounds has a widespread influence on paddy soils and river sediments in Japan.     

Residues of lindane, HCH isomers and HCB in the soil after lindane application

The dynamics of the disappearance of lindane, HCH isomers and HCB in soil after lindane application were studied, as well as the phenomenon of lindane bioisomerization to HCH isomers. The disappearance of the compounds studied depended on their volatilization into the atmosphere, plant absorption and degradation. During the experiment, lindane was bioisomerized in very small amounts to alpha-, beta-, delta-HCH and HCB, but not to epsilon-HCH. The limited magnitude of this phenomenon indicates that bioisomerization does not contribute to the contamination of food and the environment with HCH isomers that has been observed.     

Polychlorinated dibenzo-p-dioxins,dibenzofurans and polychlorinated biphenyls in polar bear,penguin and south polar skua

Concentrations of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (DFs) and non- and mono-ortho-substituted polychlorinated biphenyls (dioxin-like PCBs) were measured in livers of polar bears from the Alaskan Arctic and in eggs of Adelie penguin and south polar skua and weddell seal liver, fish and krill from Antarctica. This is one of the first reports to document the concentrations of PCDDs/DFs in polar bear livers from Alaska, and in penguin and skua eggs from Antarctica. Concentrations of total PCDD/DFs in livers of polar bears ranged from 8 to 66 (mean: 26) pg/g, on a lipid weight basis. Concentrations of total PCDD/DFs in Antarctic samples were in the increasing order on a lipid weight basis; weddell seal liver (8.9 pg/g) < fish (11-17 pg/g) < krill (27 pg/g) > penguin eggs (30 ng/g) > seal liver (57 ng/g) > fishes (6.2 ng/g) > krill (0.9 ng/g). Concentrations of 2378-tetrachlorodibenzo-p-dioxin equivalents (TEQs) calculated based on the WHO TEFs were higher in the eggs of polar skua (mean: 344: range: 220-650 pg/g, lipid wt.) from Antarctica than in polar bear livers from Alaska (mean: 120; range: 69-192 pg/g). In general, concentrations of PCDFs were greater than those of PCDDs in polar organisms. 23478-PeCDF is one of the dominant congener found in several samples. Concentrations of TEQs in polar bear livers and skua eggs were close to those that may cause adverse health effects. Dioxin-like PCBs, particularly, non-ortho coplanar PCBs were the major contributors to TEQ concentrations in penguin and skua eggs whereas mono-ortho PCBs accounted for a major portion of TEQs in polar bear livers.     

土壤中多氯联苯分析方法研究进展

文中综述了多氯联苯的分析技术及其研究进展。介绍了样品前处理技术如索氏萃取法、超声萃取法、微波辅助萃取、超临界流体萃取、加速溶剂萃取等在土壤样品中多氯联苯分析中的应用;阐述了气相色谱、液相色谱、气质联用技术在土壤样品中多氯联苯的检测,并对土壤中未来多氯联苯检测技术的发展提出了展望。     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in marine mammals in the Canadian North

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in pooled samples of ringed seal (Phoca hispida) blubber, beluga (Delphinapterus leucas) blubber and polar bear (Ursus maritimus) liver and fat from several areas throughout the Canadian north and compared to mean PCB and HCB levels in the same samples. All seal samples, and all but one polar bear sample, had detectable 2,3,7,8-TCDD at concentrations ranging from 2 to 37 ng/kg, but TCDD was not found in beluga blubber (< 2 ng/kg). All seal samples and one of three beluga samples contained 2,3,7,8-TCDF at levels of 2 to 7 ng/kg, but TCDF was not found in any bear sample. TCDF must therefore be cleared rapidly by polar bears. No other PCDF congeners were found at detection limits of 4 to 8 ng/kg. OCDD concentrations in seal blubber and polar bear samples ranged from not detected (< 8 ng/kg) to 43 ng/kg. No apparent biomagnification of TCDD, OCDD or TCDF occurred from seal to bear fat, similar to previous findings for DDT, and unlike SigmaPCBs and HCB which biomagnified 6- to 17-fold. Highest concentrations of 2,3,7,8-TCDD and OCDD in seals and bears were found in the central Canadian Arctic Archipelago, and lowest were found in Hudson Bay, the reverse of PCB concentration distribution. The reason for higher levels of TCDD and OCDD in the Arctic than in the sub-Arctic is suggested to be trans-polar movement of aerosols with combustion-related origins in Eurasia. Levels of 2,3,7,8-TCDF were more evenly distributed throughout the North, and were positively correlated with PCB, but not with HCB or 2,3,7,8-TCDD levels in seals.     

Synthesis of halogenated diphenyl ethers and dibenzofurans - A discussion of specific isomers available

Synthetic routes for the preparation of halogenated diphenyl ethers and dibenzofurans are reviewed, and isomers reported in the literature are listed. In addition, the routes preferred for the synthesis of specific chlorinated isomers - especially from the point of view of an unambiguous structural assignment - are discussed in detail. The route recommended for chlorinated diphenyl ethers is the coupling of biaryliodonium salts with phenols, and for chlorinated dibenzofurans the palladium acetate-promoted cyclization of diphenyl ethers. Chlorinated isomers of diphenyl ethers and dibenzofurans which are available via these routes are listed. Furthermore, the synthesis of a new octachlorodiphenyliodonium salt and its coupling with three different chlorophenols are described, and the cyclization of an octachlorodiphenyl ether to octachlorodibenzofuran is shown.     

Polychlorinated organic compounds (PCOCs) in waters, suspended solids and sediments of the Yangtse River

The contamination levels of polychlorinated organic compounds (PCOCs) in waters, suspended solids and sediments of the Yangtse River (Nanjing part) were analyzed in this paper. Their concentrations determined by GC/MS were very low in comparison with those in European River. The average concentration of total HCH (alpha-HCH, beta-HCH, gamma-HCH) was much higher than that of other PCOCs in all waters, which made up 65% of total amount of PCOCs. Due to the complete dilution and mixture of pollutants in the mighty Yangtse River, the content of PCOCs at each sampling station demonstrated very similar spatial pattern for waters and suspended solids. Since the small suspended solid (<0.7 microm) passed through the filter was also considered as dissolved part, the dominant parts of HCHs, PCA and PCBs were found in dissolved phase with percentage proportion of 85-94%, 72-85% and 61-78%, respectively. For DDTs, HCB and PeCB, their contents in dissolved phase were slightly higher than in particulate phase. The contents of PCOCs in sediments were also very low and varied with high fluctuation at different sampling points, indicating the heterogeneous deposition. HCB and its metabolite (PeCB) presented the highest contamination levels among PCOCs in sediments.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in soils and sediments from Daliao River Basin, China

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) were analyzed in surface sediments and top soils collected from 30 sites in Daliao River Basin. The concentrations of PCDD/F ranged from 0.28 to 29.01 ng TEQ kg(-1) dw (mean value, 7.45 ng TEQ kg(-1)dw) in sediments, and from 0.31 to 53.05 ng TEQ kg(-1)dw (mean value, 7.00 ng TEQ kg(-1)dw) in soils. PCDD/F pollution in sediments from the mid- and downstream sections of Hun River was found to be relatively heavy, and the levels of PCDD/F contamination in paddy soils were generally higher than those of upland soils. Using multivariate statistical analysis, the PCDD/F homologue and congener profiles of all soil and sediment samples were compared with those of suspected PCDD/F sources. The results showed that, PCDD/F contamination in most sediments of Hun River should mainly originated from the production of organochlorine chemicals, while metal smelting was the important potential source of PCDD/F in the drainage area of Taizi River. PCDD/F contamination in paddy soils should be simultaneously attributed to the polluted water irrigation and the organochlorine pesticide application.