Determination of polychlorinated biphenyls in tea using gas chromatography-tandem mass spectrometry combined with dispersive solid phase extraction.

A gas chromatography-tandem mass spectrometry method was developed for simultaneous determination of 38 polychlorinated biphenyls (PCBs) in tea. Sample preparation was based on a dispersive solid phase extraction procedure through an extraction of target compounds. An appropriate amount of polyvinylpolypyrrolidone was directly added in tea extractions to effectively remove polyphenols, and then tea extracts were cleaned up with primary secondary amine, florisil and graphitised carbon black. The method was validated, and linearity with correlation coefficients higher than 0.99 was obtained. Satisfactory recoveries at 2, 10, 50, and 100 µg kg-1 ranged from 71% to 117% with a maximum relative standard deviation of 23%, except for PCB 81, 77, 126 and 169, of which recoveries were in the range of 32%-63%. Limits of quantitation for PCBs were 2 or 10 µg kg-1, which was set as the lowest validated and spiked level meeting the acceptable accuracy and precision.

The relationship of maternal PCB, toxic, and essential trace element exposure levels with birth weight and head circumference in Chiba, Japan.

Maternal exposure to high levels of persistent organic pollutants (POPs) and trace elements is an important concern for fetal growth. In our previous study, we showed the polychlorinated biphenyl (PCB) levels in maternal serum from the Chiba Study of Mother and Child Health (C-MACH) cohort and their relationships between PCB levels in cord serum with birth weight of newborn. Various reports on the relationship between chemical exposure and birth status have been published; however, studies that analyze the effects of both PCB and metal exposure together in one cohort are still limited. In this study, we aimed to determine the relationship of maternal serum levels of PCBs and toxic and essential trace elements [mercury (Hg), manganese (Mn), selenium (Se), and cadmium (Cd)], with birth weight and head circumference, in the C-MACH cohort. The median concentration of total PCBs in maternal serum around 32 gestational weeks (n = 62) was 360 pg g-1 wet wt (41 ng g-1 lipid wt). The levels of Hg, Mn, Se, and Cd in maternal serum were 0.89, 0.84, 100, and 0.024 ng g-1, respectively. In this study, the Bayesian linear model determined the relationships of the birth weight and head circumference with combinations of PCB levels, toxic and essential trace elements, and questionnaire data. We found that PCB concentrations in maternal serum were weakly and negatively related to birth weight, whereas trace elements were not associated with birth weight. Serum PCB and Mn levels were negatively associated with head circumference, whereas other trace elements were not associated with head circumference. These results showed that maternal exposure to PCBs may be related to birth weight and head circumference, while maternal exposure to Mn is related to head circumference, even when adjusted based on the exposure levels of other contaminants, and maternal and fetal characteristics. Therefore, our findings indicate that maternal exposure to PCBs and Mn might be negatively related with birth weight and head circumference.

Intervention to reduce PCBs: learnings from a controlled study of Anniston residents.

Nonabsorbable dietary lipid reduces the absorption of dietary PCBs and increases the excretion of previously absorbed stored PCBs. Absorption of all PCB congeners will presumably be interrupted by nonabsorbable lipid; however excretion will be enhanced only for PCBs that have not been metabolized and also for their lipophilic metabolites. Our study with the nonabsorbable lipid, olestra, in a controlled trial in Anniston residents with elevated PCB levels demonstrated that it is possible to enhance removal of PCBs from the body in the clinically meaningful time frame of 1 year. The rate of disappearance of PCBs in participants who ate 15 g/day of olestra was significantly faster than the rate determined during the 5 years prior to intervention. The rate of disappearance was not changed from the pretrial rate in participants who ingested vegetable oil. Consideration of the role of body weight and fat is an important factor in the design of intervention trials of this kind, and the results of this trial suggest that the level of body fat in individuals will influence the rate of removal from the body. Previously reported data from animals and from a case report indicate that weight loss combined with nonabsorbable dietary lipid will maximize removal of PCBs and presumably other stored organochlorine compounds. The design of future intervention trials should include a focus on body fat levels and changes. Future trials should also include the testing of dietary compounds other than olestra that have affinity for PCBs, such as plant-derived polyphenols.

Anniston community health survey: Follow-up and dioxin analyses (ACHS-II)--methods.

High serum concentrations of polychlorinated biphenyls (PCBs) have been reported previously among residents of Anniston, Alabama, where a PCB production facility was located in the past. As the second of two cross-sectional studies of these Anniston residents, the Anniston Community Health Survey: Follow-Up and Dioxin Analyses (ACHS-II) will yield repeated measurements to be used to evaluate changes over time in ortho-PCB concentrations and selected health indicators in study participants. Dioxins, non-ortho PCBs, other chemicals, heavy metals, and a variety of additional clinical tests not previously measured in the original ACHS cohort will be examined in ACHS-II. The follow-up study also incorporates a questionnaire with extended sections on diet and occupational history for a more comprehensive assessment of possible exposure sources. Data collection for ACHS-II from 359 eligible participants took place in 2014, 7 to 9 years after ACHS.

Treatment of a suspension of PCB contaminated soil using iron nanoparticles and electric current.

Contaminated soils and sediments with polychlorinated biphenyls (PCB) are an important environmental problem due to the persistence of these synthetic aromatic compounds and to the lack of a cost-effective and sustainable remediation technology. Recently, a new experimental setup has been proposed using electrodialytic remediation and iron nanoparticles. The current work compares the performance of this new setup (A) with conventional electrokinetics (setup B). An historically contaminated soil with an initial PCB concentration of 258 µg kg(-1) was treated during 5, 10, 20 and 45 d using different amounts of iron nanoparticles in both setups A and B. A PCB removal of 83% was obtained in setup A compared with 58% of setup B. Setup A also showed additional advantages, such as a higher PCB dechlorination, in a shorter time, with lower nZVI consumption, and with the use of half of the voltage gradient when compared with the traditional setup (B). Energy and nZVI costs for a full-scale reactor are estimated at 72 € for each cubic meter of PCB contaminated soil treated on-site, making this technology competitive when compared with average off-site incineration (885 € m(-3)) or landfilling (231 € m(-3)) cost in Europe and in the USA (327 USD m(-3)).

Electrokinetic delivery of persulfate to remediate PCBs polluted soils: effect of injection spot.

Persulfate-based in situ chemical oxidation (ISCO) is a promising technique for the remediation of organic compounds contaminated soils. Electrokinetics (EK) provides an alternative method to deliver oxidants into the target zones especially in low permeable-soil. In this study, the flexibility of delivering persulfate by EK to remediate polychlorinated biphenyls (PCBs) polluted soil was investigated. 20% (w/w) of persulfate was injected at the anode, cathode and both electrodes to examine its transport behaviors under electrical field, and the effect of field inversion process was also evaluated. The results showed that high dosage of persulfate could be delivered into S4 section (near cathode) by electroosmosis when persulfate was injected from anode, 30.8% of PCBs was removed from the soil, and the formed hydroxyl precipitation near the cathode during EK process impeded the transportation of persulfate. In contrast, only 18.9% of PCBs was removed with the injection of persulfate from cathode, although the breakthrough of persulfate into the anode reservoir was observed. These results indicated that the electroosmotic flow is more effective for the transportation of persulfate into soil. The addition of persulfate from both electrodes did not significantly facilitate the PCBs oxidation as well as the treatment of electrical field reversion, the reinforced negative depolarization function occurring in the cathode at high current consumed most of the oxidant. Furthermore, it was found that strong acid condition near the anode favored the oxidation of PCBs by persulfate and the degradation of PCBs was in consistent with the oxidation of Soil TOC in EK/persulfate system.

In situ sequestration of hydrophobic organic contaminants in sediments under stagnant contact with activated carbon. 2. Mass transfer modeling.

The validity of a hydrophobic organic contaminant mass transfer model to predict the effectiveness of in situ activated carbon (AC) treatment under stagnant sediment-AC contact is studied for different contaminants and sediments. The modeling results and data from a previous 24-month column experiment of uptake in polyethylene samplers are within a factor of 2 for parent- and alkylated-polycyclic aromatic hydrocarbons in petroleum-impacted sediment and factors of 3-10 for polychlorinated biphenyls. The model successfully reproduces the relative effects of AC-sediment contact time, contaminant properties, AC particle size, AC mixing regime, AC distribution, and hydraulic conditions observed in the sediment column experiments. The model tracks contaminant concentrations in different sediment compartments over time, which provides useful information on the contaminant sequestration by the added AC. Long-term projection of the effectiveness of AC amendment using the model shows that the effects of AC particle size and particle-scale heterogeneity in AC distribution are pronounced within a year or so. However, the effect of those factors becomes less significant after a much longer contact period (on the order of a decade or two), resulting in substantial reduction in pore-water concentrations, for example, greater than 99% for benz[a]anthracene, under various scenarios.

In situ sequestration of hydrophobic organic contaminants in sediments under stagnant contact with activated carbon. 1. Column studies.

The effectiveness of activated carbon (AC) treatment to sequester hydrophobic organic contaminants in sediments under stagnant contact was comprehensively studied for the first time. Two years of column experiments were conducted to simulate field conditions with two study sediments contaminated with petroleum and polychlorinated biphenyls, respectively, and variations in AC-sediment contact times, initial AC mixing regimes and distribution, AC particle sizes, and pore-water flow. The benefit of AC treatment was gradually enhanced with time toward the end point of the treatment, where sorption equilibrium is established between sediment and AC. After two years of stagnant contact, the contaminant uptake in polyethylene passive samplers embedded in the columns was reduced by 95-99% for polycyclic aromatic hydrocarbons and 93-97% for polychlorinated biphenyls with 5 and 4 wt % AC dose, respectively, when AC was initially applied by mechanical mixing. These results verify that AC treatment can effectively control the availability of hydrophobic organic contaminants under stagnant conditions within a reasonable time frame following an initial distribution of AC into the sediment. The effectiveness of AC treatment was strongly dependent on AC particle size and AC distribution, while the effect of AC initial mixing regimes and pore-water flow was not pronounced.

Does dietary copper supplementation enhance or diminish PCB126 toxicity in the rodent liver?

Copper is essential for the function of the mitochondrial electron transport chain and several antioxidant proteins. However, in its free form copper can participate in Fenton-like reactions that produce reactive hydroxyl radicals. Aryl-hydrocarbon receptor (AhR) agonists, including the most potent polychlorinated biphenyl (PCB) congener, 3,3',4,4',5-pentachlorobiphenyl (PCB126), increase copper levels in rodent livers. This is accompanied by biochemical and toxic changes. To assess the involvement of copper in PCB toxicity, male Sprague-Dawley rats were fed an AIN-93G diet with differing dietary copper levels: low (2 ppm), adequate (6 ppm), and high (10 ppm). After three weeks, rats from each group were given a single ip injection of corn oil (control), 1, or 5 µmol/kg body weight PCB126. Two weeks following injections, biochemical and morphological markers of hepatic toxicity, trace metal status, and hepatic gene expression of metalloproteins were evaluated. Increasing dietary copper was associated with elevated tissue levels of copper and ceruloplasmin. In the livers of PCB126-treated rats, the hallmark signs of AhR activation were present, including increased cytochrome P450 and lipid levels and decreased glutathione. In addition, a doubling of hepatic copper levels was seen, and overall metal homeostasis was disturbed, resulting in decreased hepatic selenium, manganese, zinc, and iron. Expression of key metalloproteins was either decreased (cytochrome c oxidase), unchanged (ceruloplasmin and CuZnSOD), or increased (tyrosinase and metallothioneins 1 and 2) with exposure to PCB126. Increases in metallothionein may contribute/reflect the increased copper seen. Alterations in dietary copper did not amplify or abrogate the hepatic toxicity of PCB126. PCB126 toxicity, i.e., oxidative stress and steatosis, is clearly associated with disturbed metal homeostasis. Understanding the mechanisms of this disturbance may provide tools to prevent liver toxicity by other AhR agonists.

Caged Gammarus fossarum (Crustacea) as a robust tool for the characterization of bioavailable contamination levels in continental waters: towards the determination of threshold values.

We investigated the suitability of an active biomonitoring approach, using the ecologically relevant species Gammarus fossarum, to assess trends of bioavailable contamination in continental waters. Gammarids were translocated into cages at 27 sites, in the Rhône-Alpes region (France) during early autumn 2009. Study sites were chosen to represent different physico-chemical characteristics and various anthropic pressures. Biotic factors such as sex, weight and food availability were controlled in order to provide robust and comparable results. After one week of exposure, concentrations of 11 metals/metalloids (Cd, Pb, Hg, Ni, Zn, Cr, Co, Cu, As, Se and Ag) and 38 hydrophobic organic substances including polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyles (PCBs), pentabromodiphenylethers (PBDEs) and organochlorine pesticides, were measured in gammarids. All metals except Ag, and 33 organic substances among 38 were quantified in G. fossarum, showing that this species is relevant for chemical biomonitoring. The control of biotic factors allowed a robust and direct inter-site comparison of the bioavailable contamination levels. Overall, our results show the interest and robustness of the proposed methodological approach for assessing trends of bioavailable contamination, notably for metals and hydrophobic organic contaminants, in continental waters. Furthermore, we built threshold values of bioavailable contamination in gammarids, above which measured concentrations are expected to reveal a bioavailable contamination at the sampling site. Two ways to define such values were investigated, a statistical approach and a model fit. Threshold values were determined for almost all the substances investigated in this study and similar values were generally derived from the two approaches. Then, levels of contaminants measured in G. fossarum at the 27 study sites were compared to the threshold values obtained using the model fit. These threshold values could serve as a basis for further implementation of quality grids to rank sites according to the extent of the bioavailable contamination, with regard to the applied methodology.

Bioaugmentation of a historically contaminated soil by polychlorinated biphenyls with Lentinus tigrinus.

BACKGROUND: Several species belonging to the ecological group of white-rot basidiomycetes are able to bring about the remediation of matrices contaminated by a large variety of anthropic organic pollutants. Among them, polychlorobiphenyls (PCBs) are characterized by a high recalcitrance due to both their low bioavailability and the inability of natural microbial communities to degrade them at significant rates and extents. Objective of this study was to assess the impact of a maize stalk-immobilized Lentinus tigrinus CBS 577.79 inoculant combined with soybean oil (SO), as a possible PCB-mobilizing agent, on the bioremediation and resident microbiota of an actual Aroclor 1260 historically contaminated soil under unsaturated solid-phase conditions. RESULTS: Best overall PCB depletions (33.6 ± 0.3%) and dechlorination (23.2 ± 1.3%) were found after 60 d incubation in the absence of SO where, however, the fungus appeared to exert adverse effects on both the growth of biphenyl- and chlorobenzoate-degrading bacteria and the abundance of genes coding for both biphenyl dioxygenase (bph) and catechol-2,3-dioxygenase. A significant (P < 0.001) linear inverse relationship between depletion yields and degree of chlorination was observed in both augmented and control microcosms in the absence of SO; conversely, this negative correlation was not evident in SO-amended microcosms where the additive inhibited the biodegradation of low chlorinated congeners. The presence of SO, in fact, resulted in lower abundances of both biphenyl-degrading bacteria and bph. CONCLUSIONS: The PCB depletion extents obtained in the presence of L. tigrinus are by far higher than those reported in other remediation studies conducted under unsaturated solid phase conditions on actual site soils historically contaminated by Aroclor 1260. These results suggest that the bioaugmentation strategy with the maize stalk-immobilized mycelium of this species might be promising in the reclamation of PCB-contaminated soils. The addition of SO to matrices contaminated by technical PCB mixtures, such as Aroclor 1242 and Delor 103 and characterized by a large preponderance of low chlorinated congeners, might not be advisable.

Role of oil vehicle on hepatic cell proliferation in PCB-treated rats.

We report the role of dietary glycine and the type of oil used as a vehicle in the hepatotoxicity of control rats and rats treated with 2,2',4,4',5,5'-hexachlorobiphenyl (PCB-153). In our first experiment, glycine or valine (as control) was fed in an unrefined diet at 5% for the entire study duration (5 days) to inhibit Kupffer cell activity. PCB-153 (100 or 300 µmol/kg) dissolved in medium chain triglyceride (MCT) oil, was injected intraperitoneally 2 days before euthanasia; the peroxisome proliferator Wy-14,643 was included as a positive control. MCT oil decreased cell proliferation by approximately 50%. PCB-153 slightly increased hepatic cell proliferation, but dietary glycine did not reduce cell proliferation. Because of the inhibition of cell proliferation in rats receiving MCT oil compared with rats receiving no injection, we hypothesized that MCT oil may have been inhibiting the hepatocyte proliferation in PCB-153-treated rats. We therefore performed another experiment using 3 types of oil as a vehicle for PCB-153: MCT oil, corn oil, and olive oil. Rats were injected with PCB-153 (300 µmol/kg) or one of the vehicles, again 2 days before euthanasia. MCT oil again decreased the hepatocyte proliferation by approximately 50%. In rats receiving PCB-153, hepatocyte proliferation was slightly higher than their respective vehicle controls for corn oil and olive oil but not for MCT oil. These studies show that the oil vehicle is important in cell proliferation after PCB exposure, with MCT oil appearing to be protective.

Phytoextraction and uptake patterns of weathered polychlorinated biphenyl-contaminated soils using three perennial weed species.

Three promising phytoextracting perennial weed species [ L. (ox-eye daisy), L. (curly dock), and L. (Canada goldenrod)] were planted in monoculture plots at two polychlorinated biphenyl (PCB)-contaminated sites in southern Ontario and followed over 2 yr to investigate the effects of plant age, contaminant characteristics, and species-specific properties on PCB uptake and accumulation patterns in plant tissues. Results from this study indicate that, for each of these weed species, shoot contaminant concentrations and total biomass are dependent on plant age and life cycle (vegetative and reproductive stages), which affects the total amount of PCBs phytoextracted on a per-plant basis. Even at suboptimal planting densities of 3 to 5 plants m, all three weed species extracted a greater quantity of PCBs per unit area (4800-10,000 µg m) than the known PCB-accumulator L. ssp (cv Howden pumpkins) (1500-2100 µg m) at one of the two sites. Calculated PCB extractions based on theoretical optimal planting densities were significantly higher at both sites and illustrate the potential of these weeds for site remediation. This study also demonstrates that plants may accumulate PCBs along the stem length in a similar manner as plants.

Treatment of polychlorinated biphenyls in two surface soils using catalyzed H2O2 propagations.

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H(2)O(2) propagations (CHP-modified Fenton's reagent). The two soils were first evaluated for the potential for in situ treatment based on two criteria: (1) temperature (< 40 °C after CHP reagent addition), and (2) hydrogen peroxide longevity (> 24h). In situ CHP remediation was more applicable to the Fletcher soil, while the Merrimack soil was better suited to ex situ treatment based on temperature increases and hydrogen peroxide lifetimes. Using the highest hydrogen peroxide concentrations appropriate for in situ treatment in each soil, PCB destruction was 94 % in the Fletcher soil but only 48% in the Merrimack soil. However, 98% PCB destruction was achieved in the Merrimack soil using conditions more applicable to ex situ treatment (higher hydrogen peroxide concentrations with temperatures > 40 °C). Analysis of degradation products by gas chromatography/mass spectroscopy showed no detectable chlorinated degradation products, suggesting that the products of PCB oxidation were rapidly dechlorinated and degraded. The results of this research document that the two PCB-contaminated soils studied can be effectively treated using aggressive CHP conditions, and that such a detailed bench study provides important information before implementing field treatment.

Polychlorinated biphenyls-containing electrical insulating oil contaminated soil treatment with calcium and magnesium peroxides.

Calcium and magnesium peroxides were applied for the treatment of soil contaminated by polychlorinated biphenyls-containing electrical insulating oil (Aroclor 1016). The removal of PCB-containing electrical insulating oil was achieved with the addition of either calcium peroxide or magnesium peroxide alone and dependent on dosages of the chemical. A 21-d treatment of 60% watered soil with the moderate addition (chemical/oil weight ratio of 0.005/1) of either calcium peroxide or magnesium peroxide resulted in nearly complete (96 ± 2%) oil removal, unsubstantial increase in soil pH and almost no changes in oxygen consumption and dehydrogenase activity, making it suitable for the soil decontamination.

Evaluating daily exposure to polychlorinated biphenyls and polybrominated diphenyl ethers in fish oil supplements.

Fish oil supplements have become a popular means of increasing one's dietary intake of essential polyunsaturated fatty acids. However, there is growing concern that the levels and potential health effects of lipophilic organic contaminants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) may diminish some of the health benefits associated with the daily consumption of fish oil supplements. In this study, ten over-the-counter fish oil supplements available in the United States were analysed for PCBs and PBDEs and daily exposures calculated. Based on manufacturers' recommended dosages, daily intakes of PCBs and PBDEs ranged from 5 to 686 ng day(-1) and from 1 to 13 ng day(-1), respectively. Daily consumption of fish oil supplements expose consumers to PCBs and PBDEs. However, in comparison with fish ingestion, fish supplements may decrease daily PCB exposure and provide a safer pathway for individuals seeking to maintain daily recommended levels of polyunsaturated fatty acids.

Effects of decontaminated fish oil or a fish and vegetable oil blend on persistent organic pollutant and fatty acid compositions in diet and flesh of Atlantic salmon ( Salmo salar).

The health benefits of seafood are well documented and based on the unique supply of n-3 highly unsaturated fatty acids (HUFA). Aquaculture now contributes about 50 % of food-grade seafood globally and Atlantic salmon (Salmo salar) is a rich source of n-3 HUFA. However, salmon and other oily fish can accumulate lipophilic persistent organic pollutants (POP), including dioxins (PCDD/F), polychlorinated biphenyls (PCB) and polybrominated diphenyl ethers (PBDE), derived largely from feed. In the present study, triplicate groups of salmon, of initial weight 0.78 kg, were fed one of three experimental diets for 11 weeks. The diets were coated with either a northern fish oil (FO) with a high POP content (cNFO), the same oil that had been decontaminated (deNFO) or a blend of southern fish oil, rapeseed and soyabean oils (SFO/RO/SO). Dietary PCDD/F+dioxin-like PCB (DL-PCB) concentrations were 17.36, 0.45 and 0.53 ng toxic equivalents (TEQ)/kg, respectively. After 11 weeks, the flesh concentrations in fish fed the cNFO, deNFO and SFO/RO/SO diets were 6.42, 0.34 and 0.41 ng TEQ/kg, respectively. There were no differences in flesh EPA and DHA between fish fed the cNFO or deNFO diets although EPA and DHA were reduced by 50 and 30 %, respectively, in fish fed the SFO/RO/SO diet. Thus, decontaminated FO can be used to produce salmon high in n-3 HUFA and low in POP. Salmon produced using deNFO would be of high nutritional value and very low in POP and would utilise valuable fish oils that would otherwise be destroyed due to their high pollutant concentrations.

Chronic treatment with polychlorinated biphenyls (PCB) during pregnancy and lactation in the rat: Part 1: Effects on somatic growth, growth hormone-axis activity and bone mass in the offspring.

Polychlorinated biphenyls (PCBs) are pollutants detected in animal tissues and breast milk. The experiments described in the present paper were aimed at evaluating whether the four PCB congeners most abundant in animal tissues (PCB-138, -153, -180 and -126), administered since fetal life till weaning, can induce long-term alterations of GH-axis activity and bone mass in the adult rat. We measured PCB accumulation in rat brain and liver, somatic growth, pituitary GH expression and plasma hormone concentrations at different ages. Finally, we studied hypothalamic somatostatin expression and bone structure in adulthood, following long-term PCB exposure. Dams were treated during pregnancy from GD15 to GD19 and during breast-feeding. A constant reduction of the growth rate in both male and female offspring from weaning to adulthood was observed in exposed animals. Long-lasting alterations on hypothalamic-pituitary GH axis were indeed observed in PCB-exposed rats in adulthood: increased somatostatin expression in hypothalamic periventricular nucleus (both males and females) and lateral arcuate nucleus (males, only) and decreased GH mRNA levels in the pituitary of male rats. Plasma IGF-1 levels were higher in PCB-exposed male and female animals as compared with controls at weaning and tended to be higher at PN60. Plasma testosterone and thyroid hormone concentrations were not significantly affected by exposure to PCBs. In adulthood, PCBs caused a significant reduction of bone mineral content and cortical bone thickness of tibiae in male rat joint to increased width of the epiphyseal cartilage disk. In conclusion, the developmental exposure to the four selected PCB compounds used in the present study induced far-reaching effects in the adult offspring, the male rats appearing more sensitive than females.

Removal of dioxins and dioxin-like PCBs from fish oil by countercurrent supercritical CO2 extraction and activated carbon treatment.

It has been known that fish oils are prone to contamination by polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs). In this study, the removal of contaminants from fish oil by countercurrent supercritical CO(2) extraction (CC-SCE) and activated carbon treatment was investigated. Fish oil was treated by CC-SCE at 70 degrees C and 30MPa and with a CO(2)/oil ratio of 72; this resulted in a 93% reduction in the sum of PCDDs, PCDFs and DL-PCBs concentration level by and 85% reduction in toxic equivalency (TEQ). CC-SCE uses 40% less CO(2) and yields 30% more refined oil than semi-batch-type processes. Subsequent treatment by activated carbon reduced the concentration level by 94% and TEQ by 93%. CC-SCE is effective for the removal of DL-PCBs, whereas activated carbon treatment is effective for the removal of PCDD/Fs. These results reveal that the combination of CC-SCE and activated carbon treatment is applicable to the removal of PCDD/Fs and DL-PCBs from fish oil.

Continuous catalytic hydrodechlorination of polychlorinated biphenyls (PCBs) in transformer oil.

Continuous catalytic hydrodechlorination of polychlorinated biphenyls (PCBs) in the presence of transformer oils was carried out in a fixed bed reactor using a 57.6 wt% Ni on silicon oxide-aluminum oxide (SiO(2)-Al(2)O(3)) catalyst. Reaction temperatures ranging 150-300 degrees C, PCBs concentrations ranging 50-200 ppm, and reaction times ranging 1-8 h were tested. At a higher reaction temperature or at a lower PCBs concentration, catalytic activity was higher and complete dechlorination of PCBs resulted even at long reaction time. Catalyst regeneration using hexane and 0.1 M sodium hydroxide (NaOH) was effective to restore the catalytic activity. Fresh, spent and regenerated catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. XRD analysis revealed growth of Ni crystallite size of the spent and the regenerated catalysts. XPS analysis showed that a considerable amount of chlorine and carbon species were deposited on the surface of the spent catalyst, which may play a role in the catalysts deactivation.