PCB congener selective biodegradation by the white rot fungus Pleurotus ostreatus in contaminated soil

Six strains of white rot fungi were tested for their biodegradation ability of low chlorinated polychlorinated biphenyl (PCB) commercial mixture (Delor 103) in real soil system. Phanerochaete chrysosporium and Trametes versicolor did not show any ability to degrade PCBs in soil. On the contrary, four strains of Pleurotus ostreatus were able to remove about 40% of Delor 103 in two months. All P. ostreatus strains decomposed PCBs selectively with the preference for congeners with chlorine atoms in ortho > meta > para position. Degradation efficiency decreased with increasing number of chlorination.     

Differential accumulation of low-chlorinated (Delor 103) and high-chlorinated (Delor 106) biphenyls in human placental tissue and opposite effects on conversion of DHEA to E2

OBJECTIVE: Polychlorinated biphenyls (PCBs) and related compounds elicit a diverse spectrum of toxic responses. Additionally, they are able to pass through the human placenta. The aim of the presented data was to compare the action of low-chlorinated (Delor 103) and (Delor 106) high-chlorinated biphenyls on placental steroidogenesis. METHODS: Explants of human placental tissue were used to test differences in PCBs accumulation and influence on placental steroidogenesis. Delor 103 or 106, were added daily for six days at a dose of 200 pg from day 0 to day 6 of culture. The media in the control and experimental groups were changed every day, and collected and frozen for steroid analysis by RIA. Determinations of PCBs of tissue and medium were analysed by GC/MS/MS. RESULTS: Delor 103 was found at a higher level in the tissue than Delor 106. The first day of exposure to Delor 103 had no effect on the conversion of dehydroepiandrosterone (DHEA) to estradiol (E2) while there was a 2-fold decrease in E2 secretion from days 3 to 6. Conversely, Delor 106 caused an immediate increase in E2 secretion, which was maintained at higher levels throughout the exposure period. CONCLUSION: Differences between the accumulation of lower chlorinated and higher chlorinated biphenyls in human placental tissue and in the properties of the congeners can have multiple effects that may intensify or counteract the effects on uterine contraction by PCBs.     

Metabolic pathways of polychlorinated biphenyls degradation by Pseudomonas sp. 2

Polychlorinated biphenyls (PCBs) included with the commercial mixture Delor 103 were degraded by immobilized cells of aerobic bacterial strain Pseudomonas sp. 2. The ability of the strain to metabolise selected tri- and tetrachlorobiphenyls, and the site of primary attack of the biphenyl skeleton were investigated. It was observed that the amount of residual PCBs was 1-48% of the original PCBs after three weeks of incubation. Identified metabolites indicate that the used bacterial strain attacks the biphenyl skeleton at the 2,3- and 3,4-positions, and it is also able to dehalogenate PCBs. Metabolic pathways of degradation of individual congeners were proposed. Transformation of 2,4- and 2,5-dichlorobenzoic acids by Pseudomonas sp. 2 was also observed.     

Physical factors negatively affecting evaluation of long-term biodegradation experiments of polychlorinated biphenyls

Behaviour of PCB added in the form of a technical mixture (Delor 106) and [¹⁴C]PCB 77 into different aqueous model cultivation media in long-term experiments was studied. The work was focused on monitoring PCB recovery from liquid media in the absence of micro-organisms. GC-ECD and radioanalysis were utilised for determination of PCB in the examined systems. Strong relations between duration of experiments, composition of media, degree of chlorination of biphenyls, and recovery of PCB were found. The lowest yields of PCB were observed for the extracts from model solutions based on N-limited cultivation media without veratryl alcohol and Tween 80. The addition of these components, mainly of Tween 80, caused a significant increase of PCB recoveries.     

Study of the biodegradation process of polychlorinated biphenyls in liquid medium and soil by a new isolated aerobic bacterium (Janibacter sp.)

We have isolated and characterised a novel aerobic bacterial strain, designated MS3-02, belonging to the genus Janibacter sp. The capability of this new strain to degrade polychlorinated biphenyls (PCBs) in a commercial mixture (Aroclor 1242) in liquid medium and in soil (sterile and non sterile soil), under laboratory scale, has been evaluated. MS3-02 was isolated from the soil around of an incinerator, located in the east of Madrid (Spain). Gas-chromatographic analysis showed that MS3-02 was able to reduce most peaks observed in the chromatogram between 70% and 100% after seven days of incubation in a culture mineral medium containing yeast extract, but without the addition of biphenyl. The presence of biphenyl in the culture medium decreased the rate of PCB degradation by this bacterium. Comparing the performance of the MS3-02 in liquid culture medium and in soil, degradation was less efficient in sterile soil and still less efficient in non sterile soil. Under the best conditions (sterile soil and 20 weeks of incubation) MS3-02 was able to reduce, between 50% and 100%, nine of the main gas-chromatographic peaks in Aroclor 1242.     

Isomer-specific analysis of chlorinated biphenyls,naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.     

Novel metabolic pathways of organochlorine pesticides dieldrin and aldrin by the white rot fungi of the genus Phlebia

White rot fungi can degrade a wide spectrum of recalcitrant organic pollutants, including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated biphenyls (PCBs). In this experiment, 20 white rot fungi, belonging to genus Phlebia, were investigated for their ability to degrade dieldrin. Based on the screening results, we further investigated Phlebia acanthocystis, Phlebia brevispora, and Phlebia aurea to determine their degradation capacity and metabolic products towards dieldrin and aldrin. The three fungi were able to remove over 50% of dieldrin in a low nitrogen medium, after 42 d of incubation. Three hydroxylated products were detected as metabolites of dieldrin, suggesting that in Phlebia strains, hydroxylation reactions might play an important role in the metabolism of dieldrin. In contrast to dieldrin, aldrin exhibited higher levels of degradation activity. Over 90% of aldrin was removed after 28 d of incubation, and several new metabolites of aldrin in microorganisms, including 9-hydroxyaldrin and two carboxylic acid products, were detected in fungal cultures. These results indicate that the methylene moiety of aldrin and dieldrin molecules might be prone to enzymatic attack by white rot fungi. In this study, we describe for the first time a new metabolic pathway of both compounds by fungi of genus Phlebia.     

Fungal laccase-catalyzed degradation of hydroxy polychlorinated biphenyls

Hydroxy polychlorinated biphenyls (hydroxy PCBs) are toxic metabolites of PCBs. Their toxicity such as strong endocrine disruption demands effective remediation methods. Laccases from Trametes versicolor and Pleurotus ostreatus were tested to degrade hydroxy PCBs. Optimum pHs for both enzymes were around 4.0. Laccase from T. versicolor degrades hydroxy PCBs more rapidly than that from P. ostreatus. The enzymatic activities remained little changes in up to 10% organic solvents, but decreased rapidly in more than 10% acetone, acetonitrile or DMSO. Degradation rate constants decreased with increase of chlorination and no degradation was observed with tetra-, penta- and hexa-chloro hydroxy PCBs in non-mediated reactions. However, the tetra- to hexa-chloro hydroxy PCBs were degraded by laccase from T. versicolor in the presence of the mediator 2,2,6,6-tetramethylpiperidine-N-oxy radical. The other mediators, 4-ethyl-2-methoxyphenol, 2,2'-azino-bis(3-ethylbenzthiazoline sulfonic acid) diammonium salt and 1-hydroxybenzotriazole and humic acid, also enhanced degradation of all the hydroxy PCBs except 4-hydroxy-2',3,3',4',5,5'-hexachlorobiphenyl. The results showed that 3-hydroxy biphenyl was more resistant to laccase degradation than 2- or 4-hydroxy analogues. Significant linear-correlations (coefficient of determination, r2 = 0.9097 and 0.8186 for laccases from P. ostreatus and T. versicolor, respectively) were found between the ionization potentials and the removal rate constants of hydroxy PCBs.     

Bioremediation trial on aged PCB-polluted soils—a bench study in Iceland

Polychlorinated biphenyls (PCBs) pose a threat to the environment due to their high adsorption capacity to soil organic matter, stability and low reactivity, low water solubility, toxicity and ability to bioaccumulate. With Icelandic soils, research on contamination issues has been very limited and no data has been reported either on PCB degradation potential or rate. The goals of this research were to assess the bioavailability of aged PCBs in the soils of the old North Atlantic Treaty Organization facility in Keflavík, Iceland and to find the best biostimulation method to decrease the pollution. The effectiveness of different biostimulation additives (N fertiliser, white clover and pine needles) at different temperatures (10 and 30 °C) and oxygen levels (aerobic and anaerobic) were tested. PCB bioavailability to soil fauna was assessed with earthworms (Eisenia foetida). PCBs were bioavailable to earthworms (bioaccumulation factor 0.89 and 0.82 for earthworms in 12.5 ppm PCB soil and in 25 ppm PCB soil, respectively), with less chlorinated congeners showing higher bioaccumulation factors than highly chlorinated congeners. Biostimulation with pine needles at 10 °C under aerobic conditions resulted in nearly 38 % degradation of total PCBs after 2 months of incubation. Detection of the aerobic PCB degrading bphA gene supports the indigenous capability of the soils to aerobically degrade PCBs. Further research on field scale biostimulation trials with pine needles in cold environments is recommended in order to optimise the method for onsite remediation.     

Dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans on fly ash

Dechlorination of commercial mixtures of polychlorinated biphenyls (PCB) as well as polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) on extracted and non-extracted fly ash obtained from municipal waste incinerator (MWI) was studied in closed systems under nitrogen atmosphere at temperatures of 260°C and 340°C. Decomposition results (given as the difference between PCB or PCDD/F molar amounts before and after the experiment (in %) due predominantly to dechlorination reactions) and detoxification data (expressed similarly but related to toxic PCB and PCDD/F congeners only and given in I-TEQ units) are reported. Detoxification of Delor 105/80T at 260°C and 340°C at a loading of 0.65 wt% was 99.48% and 100%, respectively. The decomposition of Delor 103 at 340°C and for the loading of 0.75 wt% corresponded to 99.99%. The detoxification capability of PCDD/Fs on extracted and non-extracted fly ash for loading of 130 and 264 ng/0.4 g of fly ash at 340°C made 96 and 98%, respectively.     

The effect of terpenes on the biodegradation of polychlorinated biphenyls by Pseudomonas stutzeri.

The effect of two terpenes, carvone and limonene, on the biodegradation of DELOR 103, a commercial mixture of polychlorinated biphenyls (PCBs), by Pseudomonas stutzeri, an isolate from long-term PCB-contaminated soil, was studied in detail. The addition of both carvone and limonene as potential inducers of the dioxygenase metabolic pathway exerted an enhancing effect on PCB biodegradation when glycerol and xylose were used as carbon sources, whereas no such effect could be determined with biphenyl and glucose as substrates. Promising biodegradation values were determined with xylose as carbon source and carvone as terpene inducer. In this system, 30-70% of the congeners were degraded in the presence of 10 mg l(-1) and 20 mg l(-1) carvone, respectively, irrespective of the used concentration, whereas only 7-37% of individual PCB congeners were eliminated from the system without terpene addition.     

Study of transportation and distribution of PCBs using an ecologically simulated growth chamber

This study was designed to investigate the transportation, distribution, and bioaccumulation of PCBs in various environmental media and compartments using an ecologically simulated growth chamber. Spatial and temporal trends of PCBs in the growth chamber were discussed. The release of PCB congeners in soil was affected by the amount of rainfall with the transporting direction moving away from PCBs contaminated point. Two pathways of PCBs accumulation in plants were the uptake of roots and the deposition on shoots/leaves. There were 29 PCB congeners been found in the lalang grass. Higher concentrations of lower chlorinated PCBs were identified than higher chlorinated PCBs because of relatively higher vapor pressure for lower chlorinated congeners. After 10months of monitoring, PCBs were detected in water samples which were contributed by the release of PCBs from leached soil. Analysis of sediment showed that the percentages of low- and mid-chlorinated biphenyls were decreased 1% and 13%, respectively compared to the increase (14%) of high-chlorinated biphenyls. The increase of high-chlorinated PCBs was possibly caused by their low hydrophilicity which had resulted higher adsorption rate in sediment. All of five species of fish had been found significant amount of PCBs accumulation ( summation operatorPCBs: 21.7-102.1 microg/g-lipid). The concentrations of PCBs in fish were varied significantly among species. The range of bioaccumulation factors (BAFs) among different species of fish could be as much as 5 times depending on the consumption habits of fish. The mass balance of PCBs distribution in the growth chamber was also discussed.     

Congener-specific approach to human PCB concentrations by serum analysis

The objective of this study was to evaluate all congeners of polychlorinated biphenyls (PCBs) in human serum samples. Concentrations of all PCB congeners in the serum of 87 volunteers were determined by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The participants consisted of 47 males and 40 females, including 25 men working at municipal solid waste incinerators (MSWIs). The mean concentrations of total PCBs and dioxin-like PCBs were 242.77ng/g lipid (median: 180.17ng/g lipid) and 18.57ng/g lipid (median: 15.34ng/g lipid), respectively. Penta-, hexa-, and heptachlorinated biphenyls contributed more than 80% of the total PCBs detected in human serum. Congener-specific analysis indicated that PCB153, PCB138, PCB180, PCB187, and PCB118 contributed 57.3% of the total PCBs detected in human serum samples. A statistical analysis was performed to determine whether there were significant correlations between PCB concentrations and specific variables such as age, gender, smoking habits, occupation, and body mass index (BMI). However, serum PCB concentrations correlated only with age. In addition, we found that total PCBs and dioxin-like PCBs highly correlated with PCB153 (correlation coefficient r=0.93, p<0.01) and PCB118 (correlation coefficient r=0.98, p<0.01), respectively. Thus these two congeners could be satisfactory indicators for total PCBs and dioxin-like PCBs in human serum.     

Microbial dechlorination of polychlorinated biphenyls in anaerobic sewage sludge.

The potential of a chlorophenol (CP)-adapted consortium to dechlorinate polychlorinated biphenyls (PCBs) in sewage sludge was investigated. Results show that dechlorination rates differed significantly depending on sludge source and PCB congener. Higher total solid concentrations in sewage sludge and higher concentrations of chlorine in PCB resulted in slower dechlorination rates. No significant difference was found for 2,3,4,5-CB dechlorination from pH 6.0 to pH 8.0; however, dechlorination did not occur at pH 9.0 during a 41-day incubation period. Results show that at concentrations of 1 to 10 mg/L, the higher the PCB concentration, the faster the dechlorination rate. In addition, dechlorination rates were in the following order: methanogenic conditions > sulfate-reducing conditions > denitrifying conditions. The addition of acetate, lactate, pyruvate, and ferric chloride decreased lag times and enhanced dechlorination; however, the addition of manganese dioxide had an inhibitory effect. Dechlorination rates were also enhanced by the addition of PCB congeners, including 2,3,4-CB, 2,3,4,5-CB and 2,3,4,5,6-CB in mixture. Overall results show that the CP-adapted consortium has the potential to enhance PCB dechlorination. The optimal dechlorination conditions presented in this paper may be used as a reference for feasibility studies of PCB removal from sludge.     

A kinetic distribution model of evaporation, biosorption and biodegradation of polychlorinated biphenyls (PCBs) in the suspension of Pseudomonas stutzeri

Kinetics of distribution of PCBs in an active bacterial suspension of Pseudomonas stutzeri was studied by monitoring the evaporated amounts and the concentration remaining in the liquid medium with the biomass. To determine the biodegradation rate constants of the individual congeners of the PCB formulation Delor 103, a model considering biosorption, evaporation, and primary biodegradation constructed previously was used. Rate constants of biodegradation imply that biodegradation of individual congeners is structure-dependent process. Biodegradability decreases with increasing number of chlorine substituents in the molecule, especially if they are in the ortho and para positions. On the other hand, the increasing number of free ortho and meta positions in the biphenyl molecule leads to better biodegradability. For a simple empirical determination of the influence of the chlorine substitution pattern on biodegradability, the di- and trichlorobiphenyl rate constants of biodegradation were analysed.     

Evidence for bioamplification of nine polychlorinated biphenyl (PCB) congeners in yellow perch (Perca flavascens) eggs during incubation

This study investigated bioamplification of polychlorinated biphenyls (PCBs) in yellow perch (Perca flavescens) eggs resulting from nutrient utilization by developing embryos during incubation. Newly fertilized eggs containing trace levels of PCBs via maternal deposition were collected from an aquaculture pond in which adult broodstock had been reared over their natural lives. The eggs were incubated using a flow through system that received the same pond water at in-situ temperatures from which they were spawned. Replicate samples of eggs were collected at six time points throughout incubation, ranging from day 0 (newly fertilized eggs) to post-hatch larvae (2-d old). Congener specific PCB fugacities in pooled egg samples showed increases over the incubation period. Just prior to hatching, incubated eggs averaged 2.7-fold higher PCB fugacities compared to fresh eggs. The increase in PCB fugacity with egg incubation time was independent of chemical K_OW. After hatching, PCB residues were lost from the larvae, attenuating the maximum chemical fugacity achieved in late-incubated eggs. However, the rate of PCB elimination in the early larvae stages was K_OW dependent such that a significant larvae/egg fugacity ratio was still evident for intermediate and highly hydrophobic compounds 2 d post-hatching. This study provides the first evidence of in-ovo PCB bioamplification in eggs of an aquatic species and suggests that incubating fish embryos are exposed to higher chemical fugacities in-ovo than would be predicted by maternal deposition alone.     

Polychlorinated biphenyl distribution and faecal excretion in rats fed wheat bran

Polychlorinated biphenyls (PCBs) are abundant and persistent environmental contaminants, which tend to accumulate through the food chain. Because of the toxic potential of these compounds, body burden should be kept as low as possible e.g. by taking dietary measures. In the present report, the effect of wheat bran consumption on absorption of dietary PCBs as well as on excretion of previously absorbed PCBs was investigated in rats. Moreover, the accumulation of 7 reference PCB congeners in liver and abdominal adipose tissue was studied. Faecal excretion of dietary PCBs was significantly higher in rats fed wheat bran compared to its placebo. As a result, apparent PCB digestibility was diminished, but not enough to significantly affect PCB accumulation in liver and abdominal adipose tissue. Furthermore, excretion of previously absorbed PCBs following switching of the rats to a control diet without added PCBs was enhanced by wheat bran fibre intake, although to a much lesser extent than excretion of PCBs originating directly from the diet. Consequently, stimulation of PCB clearance from liver and abdominal adipose tissue due to wheat bran consumption was not detectable. Although no preferential absorption of PCB congeners was observed, PCB patterns in tissues obviously differed from the dietary PCB pattern. This was mainly due to PCBs 52 and 101, which were metabolised in the body. Moreover, reduced levels of PCB 138 were found in liver, while PCB 28 and 138 were predominantly present in adipose tissue. The experiment also demonstrated that PCB redistribution from the liver to the adipose tissue occurs.     

Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry

Special polychlorinated biphenyls (PCBs) standards (native and isotope labeled) were analyzed by isotope dilution method using HRGC-HRMS. Multiple analysis of special PCBs standards by three different laboratories produced the relative response factors (RRFs) and relative standard deviations (RSDs %) was in the average of 0.979 and 3.86, respectively. Additionally, inter-laboratory analysis of various forms of transformer oil revealed the PCBs concentrations were in the following order; PCBs fortified transformer oil (940-1300 ng/g)>PCB polluted transformer oil (490-680 ng/g)>chemically degraded-transformer oil (480-490 ng/g) and PCBs free oil (ND-17 ng/g). Chemical degradation resulted in an order of magnitude decrease in the PCB concentrations. Specifically, higher chlorinated PCBs degraded into lower chlorinated PCBs. Also, composition of PCBs have been determined in PCB formulations from Japan (Kanechlor), Germany (Clophen), USA (Aroclor), Russia (Sovol) and Poland (Chlorofen). Major PCBs (24-PCB congeners) contributed 54-67%, 55-68%, 16-69%, 71% and 72% in Kanechlor, Clophen, Aroclor, Sovol and Chlorofen, respectively to total PCBs. The homologue pattern of Kanechlor, Aroclor and Clophen in technical fromulation was similar (e.g., Kanechlor-300 resembled to those of Clophen A-30 and Aroclor-1242). Furthermore, congener-specific distributions of major PCBs/dioxin-like PCBs and toxic equivalency quantities (TEQ) were calculated. Based on our tentative assumption calculations, cumulative production of five different technical PCB formulations, WHO-TEQ emission was estimated to be approximately 16.05 tons.     

PCB contamination in soils of the Pearl River Delta, South China: levels, sources, and potential risks

Polychlorinated biphenyls (PCBs) contamination in tropical and sub-tropical areas and the associated risks have attracted great concern. A total of 69 samples representing five distinct land types were collected to assess PCB concentrations in the Pearl River Delta (PRD), South China, including spatial distributions in soils of the area, the probable anthropogenic sources, and related potential risks. PCBs concentrations in soils of the PRD ranged from 0.3 to 202 ng?g^?1. More severe PCBs contamination was presented in the western part than in the eastern part of the PRD region. The PCBs were dominated by low-chlorinated biphenyls; however, the proportion of higher-chlorinated biphenyls was elevated with the influence of industrial activities. Principal component analysis indicated that PCBs contamination in soils of the PRD region was mainly associated with 1#PCBs, while 2#PCB and e-waste emission in South China also accounted for it partly, especially to the industrial activity severely impacted areas. Toxic equivalent (TEQ) of the dioxin-like PCBs in the soils indicated that higher risk of PCB contamination was presented in the Dongjiang River Valley (55 ng?TEQ?kg^?1, on average) than in the Xijiang River Valley, and were mostly contributed by the congener of PCB126.