Soil contamination at abandoned sawmill areas

Contamination of soil by technical chlorophenol formulation at wood preserving sites was studied. The examined soils contained 50 to 1000 mg of polychlorinated phenols (CPs), 1 to 50 mg of polychlorinated phenoxyphenols (“pre-dioxins”, PCPPs) and 0.1 to 5 mg of polychlorinated dibenzofurans (PCDFs) per kg of dry soil. CPs were found to be mobile, leaching deep into the soil, while PCPPs and PCDFs accumulated in the top soil. All three classes of contaminants were stable in soil.     

Examination of dioxin fluxes recorded in dated aquatic-sediment cores in the Kanto region of Japan using multivariate data analysis

Past dioxin (coplanar polychlorinated biphenyl (Co-PCB), 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin (PCDD) and 2,3,7,8-substituted polychlorinated dibenzofuran (PCDF)) fluxes recorded in dated aquatic-sediment cores were analyzed using principal component analysis (PCA). The data set consisted of samples from four cores collected from the Kanto region of Japan. Time trends and spatial differences in the dioxin flux were examined, and the potential relationship to emission sources was investigated. Twenty-five compounds and 58 core slices, corresponding to the later half of the 20th century, were subjected to the analysis. The PCA of both log-transformed and maximum-value-standardized data successfully divided the dioxin compounds into a small number of groups, and three similar clusters of Co-PCBs, PCDDs and penta- to hepta-CDFs were identified. PCB formulations used in the past are judged to have been responsible for the major part of the Co-PCB flux recorded in the sediment cores. However, the relationship to emission sources needs further investigation. It is suggested that most 2,3,7,8-substituted PCDDs and PCDFs are different from Co-PCBs in their emission sources or movements in the environment. The subcore clusters obtained from the PCA of log-transformed data show that the cores from different sampling areas exhibited distinct dioxin fluxes and compositions. Common time trends among the cores were more effectively summarized by the PCA of maximum-value-standardized data focusing on relative time trends. PC scores show that recently the flux of each dioxin compound in the four cores has been generally declining after having reached a peak.     

Decreased blood level of β2-microglobulin in the employees of a factory which produced polychlorinated biphenyls

Under the project of evaluating the health status of the employees of CHEMKO factory (East Slovakia) which produced PCBs between 1955 and 1985, the level of β₂-microglobulin (β₂-m) was measured in the serum of 242 subjects from CHEMKO (Group A) and two control groups from much less polluted areas: 1. 277 females from a small mountainous village (Group B), 2. 179 adults from the area of a large city of Ko ice (Group C). The level of thymidine kinase (TK) was measured in the groups A and B only. In addition, age-matched groups of 155 women each from all areas were evaluated. In both the whole group and the age-matched group from CHEMKO the level of β₂-m was significantly lower (P<0.001) than that in the respective control groups, while no difference was found in the level of TK. In conclusion, it is suggested that the decrease of β₂-m in CHEMKO employees might be related to the immunotoxic effects of organochlorines.     

Detection of polychlorinated biphenyls employing chemical dechlorination followed by biphenyl whole cell sensing system

Polychlorinated biphenyls (PCBs) are a mixture of 209 individual chlorinated compounds commonly known as PCB congeners. These compounds are hydrophobic and are persistent in the environment. Their use was banned in the US a few decades ago because of harmful health effects. Therefore, detection of PCBs in environmental samples is increasingly important. To that end, we have developed a two-step simple and sensitive method for the detection of total PCBs. Specifically, our method involves dechlorination of PCBs to biphenyl followed by detection of biphenyl using a whole cell sensing system as the detection system. The whole cell sensing system consists of cells of the strain Pseudomonas pseudoalcaligenes KF707 harboring plasmid pSD7000. Plasmid pSD7000 contains the gene of lacZ, a reporter protein under the control of the bph operon. The detection is achieved through the emission of light afforded by the expression of reporter protein triggered by the presence of biphenyl. Due to the fact that this operon is activated only by few PCB congeners, a chemical dechlorination method was employed to convert all PCBs to biphenyl, and thus all the PCBs present in a given sample are able to be detected. The results showed that PCB congeners were rapidly (30?min) and efficiently (>98.5%) dechlorinated to biphenyl using a Mg/K₂PdCl₆ catalyst, and the biphenyl could be subsequently quantified using the whole cell sensing system. This hybrid analytical method that combines classical dechlorination with novel biosensing methods may find applications in the on-site monitoring of PCBs contamination levels.     

Effects of two different intercropping systems on arbuscular mycorrhizal fungal colonization and polychlorinated biphenyl (PCB) dissipation北大核心CSCD

Polychlorinated biphenyls (PCBs) are typical organic contaminants in the environment. It is indicated that plants and soil microorganisms have a positive synergistic effect on the remediation of PCB-contaminated soil. To investigate the effect of intercropping on arbuscular mycorrhizal (AM) fungal colonization and PCB remediation, a pot-cultivation experiment with two intercropping treatments, corn (Zea mays L.) / ryegrass (Lolium perenne L.) and corn/alfalfa (Medicago sativa L.), and a corn monoculture was conducted in a greenhouse. All treatments were inoculated with Funneliformis mosseae M47V. Plant biomass, root mycorrhizal colonization rate, concentration of PCBs and their homologs in soil, 16S rDNA gene abundance, and community composition measured by Terminal Restriction Fragment Length Polymorphism (T-RFLP) were determined after harvesting the plants. Intercropping significantly increased the root mycorrhizal colonization rate and plant biomass of corn (P < 0.05), as well as the available N content of the soil. A significant difference of the bacterial community composition was found among different treatments (P < 0.05). Compared with corn monoculture, corn/alfalfa intercropping significantly increased soil bacteria abundance (P < 0.05). The dissipation rates of total PCBs, as well as that of penta-chloro biphenyls were significantly increased in the intercropping treatments, when compared to the corn monoculture treatment. Moreover, corn/ryegrass intercropping has a significantly positive effect on the dissipation of tri-chloro biphenyls. Non-metric multidimensional scaling (NMDS) analysis indicated that the PCBs homologues composition were significantly correlated with the relative abundance of 128 bp and 148 bp T-RFs. Corn intercropping with ryegrass or alfalfa has a positive effect on root mycorrhizal colonization rate and plant biomass of corn. Inoculation of AM fungi in intercropping treatments significantly improved the efficiency of PCB remediation by promoting bacterial abundance and shifting the bacterial community composition. In conclusion, intercropping combined with AM fungi have positive synergistic effects on the remediation of PCB-contaminated soils. © 2018 Science Press. All rights reserved.     

Tissue distribution of polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) in harbour porpoises (Phocoena phocoena) from Swedish waters

Polychlorinated naphthalenes (PCNs) and non-ortho chlorinated biphenyls (non-ortho CBs) were analysed in blubber, nuchal fat, liver, muscle, kidney and brain of three male harbour porpoises (Phocoena phocoena) from the west coast of Sweden. To estimate spatial variation, PCNs and non-ortho CBs were analysed in six blubber samples collected at different anatomical sites of each animal. Highest wet weight concentrations of ΣPCNs were detected in the lipid rich tissues (blubber and nuchal fat) and liver (520–730 and 520 pg/g, respectively) and lowest in brain (22 pg/g). TetraCNs were most abundant in muscle, kidney and brain, while the hexaCNs were most abundant in the lipid rich tissues and liver. The highest lipid weight concentration recorded (11 ng/g) was for the hexaCN congeners no. 66/67 in liver. These coeluting hexaCN congeners accounted for 80–100% of total hexaCNs in all tissues examined.Concentrations of Σnon-ortho CBs were highest in lipid rich tissues (220–280 pg/g wet weight). Non-ortho CB no. 77 and 169 constituted between 62–86% and 4.9–9.3%, respectively, of total Σnon-ortho CBs. No major variation of Σnon-ortho CB concentrations was found between the six different blubber sites but higher ΣPCN concentrations (wet weight) were found dorsally at the peduncle. Toxic equivalent concentrations (TEQs) showed that non-ortho CB no. 126 was the main contributor to total TEQs in all tissues, except liver in which hexaCN congener nos. 66/67 contributed to about 50% of total TEQs.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

Results from the first year of the Swedish dioxin survey

PCDD/F levels are presented for food baskets, raw and fried herring, wolf muscle and moose tallow collected from the same area, three burbot liver samples, a sediment core from the Baltic Sea and leach water from three garbage dumps. Levels in food baskets were at or below detection limits making the estimation of intake via the diet difficult. Frying herring produces no net change in PCDD/F levels. Moose have lower PCDD/F levels than wolf from the same area. Levels in burbot liver samples are much higher near industrial discharges than in a more undisturbed area. The top 4 cm of the sediment core contain the highest levels of PCDD/F. Thereafter the levels drop and reach a low level. This low level is probably caused by contamination during sampling and is not evidence of PCDD/F presence far back in time. Leach water from city dumps contains low levels of PCDD/F but that from a dump that takes industrial wastes had higher levels and a different congener pattern.     

Coating effects on the glass adsorption of polychlorinated biphenyl (PCB) congeners

The effects of coating materials on polychlorinated biphenyl (PCB) adsorption in aqueous solution were assessed in an attempt to minimize PCB sorption loss during sampling processes. A coating material, which enhances PCB adsorption and allows adsorbed PCBs to be readily extracted by solvents, can act as a sampling concentrator to reduce PCB losses from both adsorption and evaporation. Several coating materials were evaluated, including paraffin oil, silicone oil, dimethyldichlorosilane (Sylon-CT), Prosil 28^® and polydimethylsiloxane (PDS) with viscosity 0.65, 50 (PDS 50), and 500 (PDS 500) cSt. PDS and silicone oil enhanced adsorption for all five congeners examined (IUPAC No. 28, 52, 101, 138, and 180). Sylon-CT, paraffin oil and Prosil 28^® had inconsistent effects on adsorption of different congeners. Desorption of adsorbed PCBs onto all coating types was assessed. The recovery efficiency of extracting PCBs with solvents was enhanced greatly with all coatings as opposed to non-coated surfaces, with the exception of paraffin oil. Coating with silicon oil, PDS 50, and 500 resulted in virtually 100% recovery of adsorbed PCBs. It was also found that Teflon containers were poor substitutes for glass containers and failed to minimize PCB losses. Among the materials studied, the best coating that could be used as a sampling concentrator was PDS 500.     

Theoretical study on the formation mechanism of polychlorinated dibenzothiophenes/thianthrenes from 2-chlorothiophenol molecules

Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes(PCDT/TAs),sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans(PCDD/Fs), has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol(2-CTP) as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene(1-MCTA), 1,6-dichlorothianthrene(1,6-DCTA), 4,6-dichlorodibenzothiophene(4,6-DCDT)and 1,6-dichlorodibenzothiophene(1,6-DCDT). The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.