Chemical reaction of polychlorinated biphenyls on soils with poly(ethylene glycol)/KOH

Polychlorinated biphenyls (PCB's) with higher chlorination levels have been found to be highly reactive toward poly(ethylene glycol)/KOH under ambient conditions. Artificially contaminated and real world samples of PCB on soils have been reacted with PEG/KOH, affording aryl polyglycols as products. Complete reaction of Aroclor 1260 occurs in less than two weeks in open jars under ambient conditions.     

Reaction of polychlorinated biphenyls with mercaptans in non-polar media: Formation of polychlorobiphenyl sulfides

Polychlorinated biphenyls (PCB's) react readily with alkyl mercaptans in non-polar solvents such as toluene or transformer oil. Reactions occur readily with KOH as the base in the presence of a variety of phase transfer catalysts, including phosphonium salts, crown ethers, and poly (ethylene glycols).     

Effect of metal and glycol on mechanochemical dechlorination of polychlorinated biphenyls (PCBs)

This paper assesses the potential of mechanochemical method with fine metal powder, glycol and alkali for polychlorinated biphenyls (PCBs) removal from waste insulating oil. The effects of relevant parameters, such as kinds of chemicals, rate and time of milling were examined. After each run, the total PCBs content in waste insulating oil was measured. Polyethylene glycol 200, long chain-glycol was more effective than triethylene glycol and ethylene glycol, short chain-glycol as hydrogen donor in mechanochemical dechlorination of PCBs. A maximum of 99.9% PCBs removal (below 2ppm) and 94% total chlorine removal were achieved with the mechanochemical process for 2h.     

Levels of polychlorinated biphenyls (PCB) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in fillets of farmed Southern Bluefin Tuna (Thunnus maccoyii)

Southern Bluefin Tuna (SBT) (Thunnus maccoyii) is the only farmed tuna species in the southern hemisphere, with production centred offshore of Port Lincoln, South Australia. SBT farming is a quota-based fishery where farmers fatten wild-caught stock for subsequent sale as fresh-chilled or frozen product, mainly to Japanese markets. Fillets from wild-caught and farmed SBT were analysed and the concentration of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are reported for the first time. Time of farming was separated into two periods: a typical farming period of approximately five months and an experimental scenario that involved holding (farming) these fish for an additional 12 months. WHO-PCB and WHO-PCDD/F TEQ concentrations in fillets on a fresh weight basis at the same times and over the same periods were, 0.67-1.18pg-TEQg(-1) and 0.16-0.29pg-TEQg(-1), respectively. All WHO-PCB congeners, and only three WHO-PCDD/F congeners, were found to biomagnify during farming, after blank correction. Caution should be exercised when extrapolating these results to SBT farming as a whole because of the use of varying husbandry and feeding practices employed by different companies.     

Changes in serum concentrations of polychlorinated biphenyls (PCBs), hydroxylated PCB metabolites and pentachlorophenol during pregnancy

We studied pregnancy-related changes in serum concentrations of five polychlorinated biphenyls (PCBs, CB 118, CB 138, CB 153, CB 156, CB 180), three hydroxylated PCB metabolites (4-OH-CB107, 4-OH-CB146, 4-OH-CB187), and pentachlorophenol (PCP). Median serum lipid content increased 2-fold between early (weeks 9-13) and late pregnancy (weeks 35-36) (N = 10), whereas median PCB levels in serum lipids decreased 20-46%, suggesting a dilution of PCB concentrations in serum lipids. Nevertheless, strong positive intra-individual correlations (Spearman’s r = 0.61-0.99) were seen for PCBs during the whole study period. Thus, if samples have been collected within the same relative narrow time window during pregnancy, PCB results from one single sampling occasion can be used in assessment of relative differences in body burdens during the whole pregnancy period. Concentrations of OH-PCBs in blood serum tended to decline as pregnancy progressed, although among some women the concentrations increased at the end of pregnancy. Positive intra-individual correlations (r = 0.66-0.99) between OH-PCB concentrations were observed during the first and second trimester, whereas correlations with third trimester concentrations were more diverging (r = −0.70-0.85). No decline in PCP concentrations was observed during pregnancy and no significant correlations were found between concentrations at different sampling periods. Our results suggest that for both OH-PCBs and PCP, sampling has to be more specifically timed depending on the time period during pregnancy that is of interest. The differences in patterns of intra- and inter-individual variability of the studied compounds may be due to a combination of factors, including lipid solubility, persistence of the compounds, distribution in blood, metabolic formation, and pregnancy-related changes in body composition and physiological processes.     

Application of microwave irradiation in the removal of polychlorinated biphenyls from soil contaminated by capacitor oil

The applicability of microwave irradiation in the removal of polychlorinated biphenyls (PCBs) from the soil heavily contaminated by capacitor oil was studied. Granular activated carbon (GAC) was added into the soil as a microwave-absorbing material to rapidly increase the temperature of the reaction system. Effects of sodium hypophosphite (SHP) and iron powder (IP) as reductants on PCB removal, as well as the effects of water content in soil, microwave power and the amount of GAC added were investigated. The results indicated that in the presence of SHP and GAC, about 80% of PCBs in soil were effectively removed by 10 min microwave irradiation, and the further addition of IP could raise the average removal efficiency to a higher level, more than 95%. In the removal of PCBs with the microwave/GAC/IP/SHP system, an appropriate amount of water proved to be helpful in promoting the removal of PCBs from soil by steam distillation and in acting as a co-solvent of SHP and H-donor of IP.     

Congener-specific accumulation of polychlorinated biphenyls in ovarian follicular wall follows repeated exposure to PCB 126 and PCB 153. Comparison of tissue levels of PCB and biological changes

OBJECTIVE: Small (SF), medium (MF) and large (LF) preovulatory porcine follicles were isolated and incubated in an Erlenmeyer flask containing 5 ml of medium with addition of PCB 126 or PCB 153 to test differences in their accumulation in the follicular wall. METHODS; The follicles were incubated in M199 medium at 37 degrees C with constant shaking at 70 rpm, for 6 days. The media were changed every day and repeated dose 25 pg/ml of PCB 126 or 25 ng/ml of PCB 153 was added each day till 6 days of culture. Media were collected every day and frozen for steroid analysis by RIA. 24 h after the last treatment follicles were frozen for further polychlorinated biphenyls (PCB) content analysis. PCB concentrations in the follicular wall were analysed by mass spectrometry. RESULTS: 3.3%; 3.6% and 5.6% of total PCB 126 dose, and 71%; 71.4% and 30.4% of total PCB 153 dose accumulated in SF, MF and LF follicles, respectively. The accumulative effect of PCB was manifested by the disruption of estradiol (E2) secretion. In SF antiestrogenic action of PCB 126 was observed during the whole time of exposure while PCB 153 decreased E2 till 4 days of culture and then estrogenic action was observed. In MF, both these congeners decreased E2 till 5 days of exposure and then estrogenic actions were noted with the highest magnification in the case of PCB 126. In LF both PCB studied increased E2 till 3 days of exposure with the highest magnification of PCB 126, then antiestrogenic action was noted. Testosterone secretion was generally affected in a pattern oposite to that of E2 suggesting action on P450arom activity. CONCLUSION: The results of these studies demonstrated that disruption of aromatization process in the follicles following repeated exposure to both congeners is not directly correlated with the bioaccumulation or amount of PCB within the follicular wall.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC-MS/MS) and gas chromatography-mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001-0.003 ng g(-1) dry weight (dw) for PCNs, 1.8 ng g(-1) for SCCPs and 0.006-0.014 ng g(-1)dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g(-1)dw for PCNs, between 0.21 and 1.17 microg g(-1)dw for SCCPs, and from 2.33 to 44.00 ng g(-1) (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g(-1)dw for PCNs, between 1.25 and 2.09 microg g(-1)dw for SCCPs and from 22.34 to 37.74 ng g(-1)dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.     

Occurrence of co-planar polybrominated/chlorinated biphenyls (PXBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk of women from Spain

In this study, for the first time, levels and accumulation profiles of eight currently available polybrominated/chlorinated biphenyl congeners (PXBs; XB-77, -105, -118, -126A, -126B, -126C, -156 and -169, named according to IUPAC nomenclature) in human breast milk collected form Spanish women in 2005 were reported. Concentrations and congener specific profiles of polychlorinated biphenyls (PCBs), including co-planar PCBs, (co-PCBs) and polybrominated diphenyl ethers (PBDEs) were also reported.A concentration of 0.45 pg g⁻¹ lipid weight was found for total PXBs, and arithmetic mean concentrations of 125, 25 and 5.5 ng g⁻¹ lipid weight were determined for total PCBs, co-PCBs and total PBDEs respectively. Detectable levels of all congeners investigated, except CB-123 and XB-169 were found. Levels of PCBs were similar to those found in Spanish samples collected after 2000, and lower than those obtained before 2000. CB-138, -153 and -180 were the predominant PCB congeners. PBDE levels, dominated by BDE-47, -99, -100 and -209, were lower than PCB levels. PXB concentrations were the lowest, with XB-156 being the most abundant. The concentration levels of PCBs and PBDEs found in this study were in the same range as those from other European countries. Levels of PXBs were much lower than published values determined in Japan which were the only data found in the literature.     

Development of controlled release formulations of azadirachtin-A employing poly(ethylene glycol) based amphiphilic copolymers

Controlled release (CR) formulations of azadirachtin-A, a bioactive constituent derived from the seed of Azadirachta indica A. Juss (Meliaceae), have been prepared using commercially available polyvinyl chloride, polyethylene glycol (PEG) and laboratory synthesized poly ethylene glycol–based amphiphilic copolymers. Copolymers of polyethylene glycol and various dimethyl esters, which self assemble into nano micellar aggregates in aqueous media, have been synthesized. The kinetics of azadirachtin-A, release in water from the different formulations was studied. Release from the commercial polyethylene glycol (PEG) formulation was faster than the other CR formulations. The rate of release of encapsulated azadirachtin-A from nano micellar aggregates is reduced by increasing the molecular weight of PEG. The diffusion exponent (n value) of azadirachtin-A, in water ranged from 0.47 to 1.18 in the tested formulations. The release was diffusion controlled with a half release time (t_1/2) of 3.05 to 42.80 days in water from different matrices. The results suggest that depending upon the polymer matrix used, the application rate of azadirachtin-A can be optimized to achieve insect control at the desired level and period.     

Assessment of polychlorinated biphenyls (PCBs) in cheese from Rio Grande do Sul, Brazil

Polychlorinated biphenyls (PCBs) are among the most toxic environmental pollutants. Food, especially animal based, has been described as the major source for human exposure to PCBs. We investigated PCB levels (congeners 10, 28, 52, 153, 138, and 180) in cheese from 14 cities of Rio Grande do Sul, Brazil. The fat was extracted using sodium sulfate and petroleum ether, and PCBs purification was conducted using florisil and hexane. The identification and quantification were made in a gas chromatograph with microelectron capture detector (GC-microECD). PCB congeners were found (lower bound data as ngg(-1) fat) in the following rank: 52 (15.75)>180 (4.91)>28 (3.43)>153 (3.00)>10 (2.38)>138 (1.37). Summation operatorPCB contamination ranged from 0 to 78.32 ngg(-1) fat. Differences in PCB levels between industrialized (33.32 ngg(-1) fat) and homemade (26.58 ngg(-1) fat) cheese and between two different regions (36.19 vs. 26.95 ngg(-1) fat) were not statistically significant. For university students, the estimated daily intake (EDI) of PCBs from cheese ranged from 0 to 3.13 pgkg(-1) b.w. EDI was significantly higher for industrialized than homemade cheese, and for cheese from Mountain/Porto Alegre region than from Santa Maria/South/Western region. No sample exceeded maximum level of PCBs allowed in dairy products in the European Community.     

Emissions of polychlorinated biphenyls (PCBs) from sludge drying beds to the atmosphere in Chicago

Ambient air PCB concentrations in the Lake Calumet region in Southeast Chicago have been found to be significantly higher than in nearby non-urban areas. This area is highly industrialized and also contains municipal sludge drying facilities and landfills. In an effort to quantify the importance of the sludge drying facilities to the elevated concentrations, upwind/downwind air samples from the Calumet East sludge drying bed were obtained between April and October 2002. For these samples, the downwind minus upwind (downwind-upwind) concentration varied from 0.33 to 1.27ngm(-3) for non-northeast (NE) direction winds suggesting sludge drying is a source of PCBs to the atmosphere. However, the upwind concentrations were higher than the downwind for winds from the NE of the sampling site suggesting more significant source(s), possibly Lake Calumet or the so called "Cluster site" NE of the sludge drying beds. Flux chamber experiments carried out during the sampling period measured average PCB fluxes of 210ngm(-2)h(-1) (range 43-910ngm(-2)h(-1)) which resulted in an overall flux of 0.005kgday (d)(-1) ( approximately 2kgyr(-1)). A developed regression equation between moisture content and sludge concentration estimated higher PCB losses of 0.26kgd(-1) ( approximately 95kgyr(-1)). Although these two approaches yielded different values, they both indicate that the emission from the Calumet East sludge drying beds were of minimal importance when compared to the total estimated amount of 2-70kgd(-1) (700-2100kgyr(-1)) of PCBs entering the Chicago atmosphere.     

Concentration-dependent enantioselective accumulation of chiral polychlorinated biphenyls in Nelumbo nucifera Gaertn. root from contaminative sediment

Environmental Science and Pollution Research - Nelumbo nucifera Gaertn. (lotus) roots were collected from contaminated sediments which were artificially adding different concentrations of chiral...     

Distribution characteristics of polychlorinated biphenyls in crucian carp (Carassius auratus) from major rivers in Korea

Polychlorinated biphenyls (PCBs) levels in crucian carp were determined at 20 locations along four major river systems, several small-scale rivers and a wetland in Korea. Twenty-eight congeners, ranging from tri- to hepta-CBs were detected. A gas chromatograph with a mass selective detector was used to quantify the individual PCB congeners. The objectives of this study were to investigate the levels of contamination of PCBs in freshwater fish and to observe the pattern of their distribution. The sampling locations were chosen among 31 sampling sites that are currently used as environmental residue checkpoints by the Korean Ministry of Environment. Concentrations of individual congeners ranged from not detectable (n.d.) to 0.75 ng g(-1) on a wet weight basis. The total concentrations of PCBs at each site ranged from n.d. to 5.41 ng g(-1) of wet weight. The most heavily contaminated site was the Nakdong estuary located near the Shinpyung-Janglim factory district. The PCB 153 and 138 were the principal congeners and penta- and hexa-chlorinated biphenyls comprised the main congener groups.     

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.     

Uptake of polychlorinated biphenyls and organochlorine pesticides from soil and air into radishes (Raphanus sativus)

Uptake of organochlorine pesticides and polychlorinated biphenyls from soil and air into radishes was measured at a heavily contaminated field site. The highest contaminant concentrations were found for DDT and its metabolites, and for β-hexachlorocyclohexane. Bioconcentration factor (BCF, defined as a ratio between the contaminant concentration in the plant tissue and concentration in soil) was determined for roots, edible bulbs and shoots. Root BCF values were constant and not correlated to log K_OW. A negative correlation between BCF and log K_OW was found for edible bulbs. Shoot BCF values were rather constant and varied between 0.01 and 0.22. Resuspended soil particles may facilitate the transport of chemicals from soil to shoots. Elevated POP concentrations found in shoots of radishes grown in the control plot support the hypothesis that the uptake from air was more significant for shoots than the one from soil. The uptake of POPs from air was within the range of theoretical values predicted from log K_OA.     

Simultaneous mobilization of heavy metals and polychlorinated biphenyl (PCB) compounds from soil with cyclodextrin and EDTA in admixture

This study evaluated the efficacy of a washing process with cyclodextrin in combination with ethylenediaminetetraacetate (EDTA) for the simultaneous mobilization of heavy metals and PCBs from a field contaminated soil. Ultrasonically aided mixing of the field contaminated soil with a combination of cyclodextrin solution (10%, w/v) and a sparing quantity (2 mmol) of EDTA, simultaneously mobilized appreciable quantities of PCBs and much of the analyte metal (Cd, Cr, Cu, Mn, Ni, Pb, Zn) burdens. Relative to the action of individual reagents, a combination of randomly methylated (RAMEB) or hydroxypropyl beta-cyclodextrin (HPCD) with EDTA did not alter the PCB extraction efficiency nor did the presence of cyclodextrin change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb modestly. Three sonication-washes with the same charge of reagents mobilized appreciable quantities of PCBs (40-76%) and quantitatively extracted the labile fraction of Cd, Cu, Mn, and Pb. RAMEB proved to be more efficient than HPCD for PCB extractions. Three successive extractions with a single charge of cyclodextrin mobilized almost as much PCB (RAMEB, 76%; HPCD, 40%) as did the companion extractions that used fresh reagents each time (RAMEB, 78%; HPCD, 42%). Collectively, these studies demonstrated that PCB compounds and selected heavy metals can be co-extracted efficiently from soil with three successive washes with the same washing suspension containing EDTA and cyclodextrin.     

A mixture of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non-ortho polychlorinated biphenyls (PCBs) changed the lipid content of pregnant Long Evans rats

Pregnant Long Evans rats received 1.0 μg/kg of dioxin toxic equivalents (TEQ) by oral gavage on the 15th gestational day (GD 15), using a dosing mixture that contained two polychlorinated dioxins, four polychlorinated furans and three non-ortho polychlorinated biphenyls (PCBs). Rats were sacrificed on GD 16, GD 21 and postnatal day 4 (PND 4). The lipid content of fetus, pup, placenta and maternal liver, serum and adipose tissue were determined. Treated GD 16 and GD 21 fetuses had identical lipid content to the control group, yet the lipid content of treated pups on PND 4 was 32% higher than that of the control group. On the other hand, the lipid content of placenta, liver, and serum from the treated dams was 44–50%, 24%, and 38% lower than that of the control group, respectively. Thus, a low-dose mixture of dioxin-like compounds can cause changes in lipid content. The lipid content of offspring was not affected until they were exposed via lactation.