Iron-mediated reactions of polychlorinated biphenyls in electrochemical peroxidation process (ECP)

A study was conducted to explore some of the basic processes of polychlorinated biphenyl (PCB) destruction by a new technology termed electrochemical peroxidation process (ECP). ECP represents an enhancement of the classic Fenton reaction (H2O2 + Fe2+) in which iron is electrochemically generated by steel electrodes. Focus was on the extent of adsorption of a mixture of Aroclor 1248 on steel electrodes in comparison to iron filings. Commercially available zero-valent iron filings rapidly adsorbed PCBs from an aqueous solution of Aroclor 1248. Within 4 h, all the PCBs were adsorbed at 1%, 5%, and 10% Fe0 (w/v) concentrations. Little difference in adsorption was found between acidic (2.3) and unamended solutions (pH 5.5), even though significant differences in iron oxidation state and Fe2+ concentrations were measured in solution. PCB adsorption also occurs on steel electrodes regardless of the pH or electric current applied (AC or DC), suggesting the combination of oxidizing (free radical-mediated reactions) and reducing (dechlorination reactions) iron-mediated degradation pathways may be possible. Extraction of the iron powder after 48 h of contact time yielded the progressive recovery of biphenyl with increasing Fe mass(from 0.4% to 3.5%) and changes of the PCB congener-specific pattern as a consequence of dechlorination. A variety of daughter congeners similar to those accumulated during anaerobic microbial dechlorination of Aroclor 1248 in contaminated sediments indicate preferential removal of meta- and para-chlorines.     

Microbial reductive dechlorination of polychlorinated biphenyls in heat treated and bromoethanesulfonate treated anaerobic sediment slurries

Anaerobic reductive dechlorination of polychlorinated biphenyls (PCBs) in heat treated, bromoethanesulfonate (BES) treated, and untreated slurries of PCB-contaminated upper Hudson River sediment was investigated to better understand the microorganisms that mediate this process. Extensive meta-and para-dechlorination of Aroclor 1242 and 2,3,4-trichlorobiphenyl (2,3,4-CB) occurred in both the untreated and heat treated slurries. Heat treatment of the slurries eliminated methanogenesis, enhanced 2,3,4-CB dechlorination, and caused extensive meta- and para-dechlorination of Aroclor 1242 earlier than in untreated slurries. BES treatment (1 mM) of the slurries caused a 90% reduction in methanogenesis and inhibited metadechlorination of PCB congeners containing 2,3- and 2,5-dichlorophenyl groups. The results suggest that there are at least two distinct microbial PCB reductive dechlorination activities in PCB-contaminated upper Hudson River sediment, a meta-dechlorination activity and a para-dechlorination activity on Aroclor 1242. Both of these microbial activities are apparently not methanogenic and are resistant to or activated by heat treatment. In addition, the meta- but not the para-dechlorinating activity is inhibited by BES treatment.     

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.     

Polychlorinated biphenyls in Narragansett Bay surface sediments

Polychlorinated biphenyls (PCBs) were evaluated in 41 surface sediments collected from Narragansett Bay, RI in 1997-1998. Highest concentrations of total PCBs (1760 ng/g) were in rivers at the head of the bay and the values decreased southward toward the mouth of the bay, with elevated concentrations in some of the coves. The PCB levels in approximately 43% of the samples exceeded the effects range median (ERM) guideline [Environ. Manage. 19 (1995) 81] indicating possible adverse biological effects at these stations. Principal component analysis (PCA) of the surface sediment PCBs separated the Taunton River samples from the rest of the samples. This result suggests that this river has a different PCB composition and sources than the other areas investigated. It also showed that this river has a limited influence on other bay stations as the adjacent samples downstream did not have the same chemical signature. Congener ratios derived from the PCA were useful in distinguishing stations that had different sources of PCBs than the bulk of the bay sediments. Although Aroclor 1268 and 1270 accounted for <1% of all PCB production, their major components, CB206 and CB209, account for 3-6% of the CBs in most bay samples. This may reflect more local use of these Aroclor mixtures and/or be indicative of their relative stability, compared to less chlorinated mixtures. Using linear alkyl benzenes (LABs) as a marker for sewage derived PCBs suggested that up to 95% of the PCBs at the most contaminated sites in the Seekonk, Providence, and Taunton Rivers were sewage derived. This analysis also showed that there is a high background level (167 ng/g) of PCBs in the Seekonk and Providence River, while the Taunton River had a relatively low background level (23.7 ng/g). At the furthest stations south in the Providence River, the sewage derived PCBs only accounted for 23% of the total which suggests that PCB associated with sewage particles are rapidly deposited and are therefore not the most significant source of these compounds to the lower reaches of Narragansett Bay.     

Pathways and products of the degradation of PCBs by the sodium dispersion method

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SD) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and m,p-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (MS) methods.     

Source determination of highly chlorinated biphenyl isomers in pine needles - comparison to several PCB preparations

The isomer specific composition of 13 technical PCB formulations of different origin and of pine needles was analyzed using GC/MS and HRGC/HRMS. Nonachlorinated biphenyls were identified in 11 among 13 formulations analyzed, with the highest abundance found for highly chlorinated ones (Aroclors 1268 and 1260, Chlorofen, Sovol, Kanechlors 600 and 500, Delor 106, Clophen A60). Decachlorobiphenyl was identified only in Aroclor 1268, Clophen A60, Aroclor 1260 and Chlorofen, comprising, respectively, 8.9, 2.8, 1.3 and 0.82% of the total bulk of nona- and decaCBs detected. Nona- and decaCB were detected in pine needles in Poland with the highest concentrations found at the sites neighboring to a former production sites of the Polish PCB formulations, while in pine needles collected around the Tokyo Bay nona- and decacCB were detected only in four of 10 sites and the concentrations corresponded to those found at the rural areas of Poland.     

Microbial dechlorination of three PCB congeners in river sediment.

We investigated the potential for the anaerobic degradation of three PCB congeners (2,3,5,6-CB, 2,3,4,5-CB, and 2,3,4,5,6-CB) in sediments collected from five monitoring sites along the Keelung River in northern Taiwan. Optimal conditions for congener dechlorination were 30 degrees C and pH 7.0. Intermediate 2,3,4,5-CB products were identified as 2,3,5-CB, 2,4,5-CB, and 2,5-CB. Intermediate 2,3,4,5,6-CB products were identified as 2,3,5,6-CB, 2,3,6-CB, and 2,5-CB. For 2,3,5,6-CB, intermediate products were identified as 2,3,6-CB and 2,5-CB. Dechlorination rates for PCB congeners were observed as (fastest to slowest): 2, 3, 4-CB > 2, 3, 4, 5-CB > 2, 3, 4, 5, 6-CB > 2, 3, 5, 6-CB > 2, 2', 3, 3', 4, 4'-CB > 2, 2', 4, 4' 6, 6'-CB > 2, 2', 3, 4, 4', 5, 5'-CB > 2, 2', 3, 3', 4, 4', 5, 5'-CB. Rates decreased for mixtures of the eight congeners. Dechlorination rates for the three primary congeners under different reducing conditions occurred in the order of (fastest to slowest): methanogenic condition > sulfate-reducing condition > nitrate-reducing condition. Under methanogenic and sulfate-reducing conditions, dechlorination rates were enhanced by the addition of lactate, pyruvate, or acetate, but delayed by the addition of manganese oxide, or ferric chloride. Under nitrate-reducing condition, dechlorination rates were delayed by the addition of lactate, pyruvate, acetate, manganese oxide or ferric chloride. Treatment with such microbial inhibitors as bromoethanesulfonic acid (BESA) or molybdate revealed that methanogen and sulfate-reducing bacteria were involved in the dechlorination of these three PCB congeners.     

Polychlorinated biphenyl (PCB) anaerobic degradation in marine sediments: microcosm study and role of autochthonous microbial communities

Polychlorobiphenyl (PCB) biodegradation was followed for 1 year in microcosms containing marine sediments collected from Mar Piccolo (Taranto, Italy) chronically contaminated by this class of hazardous compounds. The microcosms were performed under strictly anaerobic conditions with or without the addition of Dehalococcoides mccartyi, the main microorganism known to degrade PCBs through the anaerobic reductive dechlorination process. Thirty PCB congeners were monitored during the experiments revealing that the biodegradation occurred in all microcosms with a decrease in hepta-, hexa-, and penta-chlorobiphenyls (CBs) and a parallel increase in low chlorinated PCBs (tri-CBs and tetra-CBs). The concentrations of the most representative congeners detected in the original sediment, such as 245-245-CB and 2345-245-CB, and of the mixture 2356-34-CB+234-245-CB, decreased by 32.5, 23.8, and 46.7 %, respectively, after only 70 days of anaerobic incubation without any bioaugmentation treatment. Additionally, the structure and population dynamics of the microbial key players involved in the biodegradative process and of the entire mixed microbial community were accurately defined by Catalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD-FISH) in both the original sediment and during the operation of the microcosm. The reductive dehalogenase genes of D. mccartyi, specifically involved in PCB dechlorination, were also quantified using real-time PCR (qPCR). Our results demonstrated that the autochthonous microbial community living in the marine sediment, including D. mccartyi (6.32E+06 16S rRNA gene copy numbers g^?1 sediment), was able to efficiently sustain the biodegradation of PCBs when controlled anaerobic conditions were imposed.     

Anaerobic biodegradation of weathered polychlorinated biphenyls (PCBs) in contaminated sediments of Porto Marghera (Venice Lagoon,Italy)

The biodegradation of weathered polychlorinated biphenyls (PCBs) (mono and di-chlorinated biphenyls along with PCBs partially ascribed to Aroclor 1242 and 1254) occurring at 1.5-2.5 mg/kg in three different sediments collected from the Porto Marghera contaminated area of Venice Lagoon (Italy) was reported in this study. Strictly anaerobic, slurry microcosms consisting of sediments suspended (at 25% v/v) in a marine salt medium, lagoon water or lagoon water supplemented with NaHCO3 and Na2S were developed and monitored for PCB transformation, sulfate consumption and methane (CH4) production for 6 months. A marked depletion of highly chlorinated biphenyls along with the accumulation of low-chlorinated, often ortho-substituted biphenyls was observed in the biologically active microcosms, where a remarkable consumption of sulfate and/or a significant production of CH4 were also detected. Notably, a more extensive PCB transformation was observed in the microcosms developed with site water (both without or with NaHCO3 plus Na2S), where both the initial concentration of sulfate and sulfate consumption were five fold-higher than in the corresponding microcosms with salt medium. These data indicate that weathered PCBs of the three contaminated sediments of Porto Marghera utilized in this study can undergo reductive dechlorination, probably mediated by indigenous sulfate-reducing and/or methanogenic bacteria.     

Bioleaching of heavy metals from sediment: significance of pH

Bioleaching process, which causes acidification and solubilization of heavy metals, is one of the promising methods for removing heavy metals from contaminated sediments. The solubilization of heavy metals from contaminated sediments is governed by the sediment pH. In the present study, the significance of pH in bioleaching of heavy metals from contaminated sediment was evaluated at different solid contents of sediments in a bench-scale reactor. Results showed that a temporal change of pH in the bioleaching process was effected by the buffering capacity of the sediment particulates. The variations of pH in this bioleaching process were calculated by a modified logistic model. It was observed that solubilization of heavy metals from sediments is highly pH-dependent. In addition, a non-linear equation for metal solubilization relating pH value in the bioleaching process was established. This allows an easier and faster estimate of metal solubilization by measuring pH in the bioleaching process.     

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

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

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.     

Spatial distribution and source apportionment of PCBs in sediments around İzmit industrial complexes, Turkey

The spatial distribution, degree of pollution and major sources of PCBs were evaluated in surficial sediments within the heavily urbanized and industrialized ?zmit Bay and its main freshwater inputs. ΣPCB concentrations range from 2.90 to 85.4ngg(-1) in marine sediments and from ND to 47.7ngg(-1) in freshwater sediments. Results suggest that high concentrations of ΣPCBs were localized around a chlor-alkali plant and an industry that handles bulk liquid, dry and drummed chemicals, and petroleum products in the Bay. Using a chemical mass balance receptor model (CMB), major sources of PCBs in the region were investigated. The CMB model identified Aroclor 1254 and 1260 to be the major PCB sources in marine sediments and the less chlorinated Aroclor 1248 and 1242 as the major PCB sources in freshwater sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.     

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.     

Occurrence of polychlorinated biphenyls (PCBs) in the Soulou stream in the power generation area of Eordea, northwestern Greece

The occurrence of polychlorinated biphenyls (PCBs) was investigated in the Soulou stream in the area of Eordea, northwestern Greece, receiving the effluents of two lignite burning power plants. The study was carried out after an accidental fire in one of the power plants during which losses of an amount of Aroclor 1232 were recorded. PCBs were determined in water and sediment samples collected from the wastewater treatment unit of the power plant and various points across the stream. Concentrations of PCBs were in the same order of magnitude as in other surface waters and sediments previously found in the Greek territory. The sum concentrations of seven PCBs (#28, #52, #101, #118, #138, #153, #180) varied between 94 and 206 ngl(-1) in waters, and between 67 and 500 ngg(-1) in sediments. Profile analysis of PCB congeners revealed large differences between waters and sediments, showing also significant dissimilarity with the profile of Aroclor 1232.     

Maternal and cord serum exposure to PCB and DDE methyl sulfone metabolites in eastern Slovakia

Polychlorinated biphenyls (PCBs) were commercially produced between 1959 and 1984 in eastern Slovakia. Improper handling led to a highly contaminated local environment and high levels of PCBs in humans and wildlife in the Michalovce area. The aim of this study was to analyse serum for methylsulfonyl metabolites of PCB (MeSO(2)-PCBs) and DDE (3-MeSO(2)-DDE) in serum samples from pregnant women and in a selected number of paired cord blood samples to assess maternal sulfone levels and patterns, and transplacental transfer of these metabolites. The donating women were from two districts in eastern Slovakia. A liquid-liquid extraction method together with separation of substance groups and further clean-up on silica gel columns were applied prior to analysis by gas chromatography/mass spectrometry. 3-MeSO(2)-DDE was the major methyl sulfone in most of the samples followed by a yet not identified MeSO(2)-hexaCB, 4'-MeSO(2)-CB101, 4'-MeSO(2)-CB87 and 4-MeSO(2)-CB149. The women from the contaminated area had three times higher concentrations of the MeSO(2)-PCBs than women from the reference area. This is the first report on methyl sulfone metabolites of PCB and DDE in human cord serum. It is shown that these metabolites are transported through the placenta. The levels of MeSO(2)-PCBs in the maternal serum were about 1.5 times higher than in the corresponding cord serum on a lipid weight basis. For 3-MeSO(2)-DDE, the levels were about the same in maternal and cord serum. The difference in the maternal:cord ratio, comparing MeSO(2)-PCBs with 3-MeSO(2)-DDE might be due to differences in transport through the placenta caused by their different affinities for lipoproteins and plasma proteins.     

Tidal salt marsh sediment in California, USA. Part 1: occurrence and sources of organic contaminants

Surface sediment samples (0-5 cm) from five tidal marshes along the coast of California, USA were analyzed for organic pollutants to investigate their relationship to land use, current distribution within marshes, and possible sources. Among the study areas, Stege Marsh, located in San Francisco Bay, was the most contaminated. Compared to San Francisco Bay, Stege Marsh had much higher levels of organic contaminants such as PCBs (polychlorinated biphenyls), DDTs, and chlordanes. At reference marshes (Tom's Point and Walker Creek in Tomales Bay), organic contaminants in sediments were very low. While PAHs (polycyclic aromatic hydrocarbons) were found at all of the study areas (22-13,600 ng g(-1)), measurable concentrations of PCBs were found only in the sediments from Stege Marsh (80-9,940 ng g(-1)). Combustion related (pyrogenic) high molecular weight PAHs were dominant in sediments from Stege and Carpinteria Marshes, while in sediments from Tom's Point and Walker Creek petroleum related (petrogenic) low molecular weight PAHs and alkyl-substituted PAHs were much more abundant than pyrogenic PAHs. PCB congener patterns in all of the Stege Marsh samples were the same and revealed that Aroclor 1248 was a predominant source. In all marshes, the sum of DDE and DDD accounted for more than 90% of total DDTs, indicating that DDT has degraded significantly. The ratios of p,p'-DDE to p,p'-DDD in sediments from Stege Marsh provide evidence of possible previous use of technical DDD. Chlordane ratios indicated that chlordanes have degraded slightly. Bis(2-ethylhexyl)phthalate (280-32,000 ng g(-1)) was the most abundant phthalate. The data indicates that Stege Marsh may be a source of contaminants that continue to be discharged into San Francisco Bay.     

Negative effects of humic acid addition on phytoremediation of pyrene-contaminated sediments by mangrove seedlings

Vegetated (with Kandelia candel seedlings) and non-vegetated mangrove microcosms were employed to remove pyrene from contaminated sediments, and the effects of adding 6.7% humic acid (HA) on such removal were investigated. At the end of 6-month treatment, residual pyrene concentrations in surface sediments (0-2 cm) of the contaminated microcosms reduced from an initial 5.82 to 0.63 microg g(-1) dw, and the reduction was less in HA amended microcosms with the residual pyrene concentration remained at 3.12 microg g(-1) dw. The pyrene removal percentages in microcosms with HA amendment were 29% for surface aerobic sediments and 41% for bottom (anaerobic) sediments, while the respective removal percentages in microcosms without HA amendment were 89% (surface sediments) and 53% (bottom sediments). Microcosms planted with K. candel seedlings had a significantly higher pyrene removal when compared to the non-vegetated ones, and the average removal percentages were 70.9% and 61.4%, respectively. However, when humic acid was added, no significant difference was found between vegetated and non-vegetated microcosms in pyrene removal, both had less than 40% removal, probably because plant growth in humic acid amended contaminated microcosms, in terms of total biomass, was reduced by 50%. Roots of K. candel could accumulate pyrene from contaminated microcosms, and pyrene concentrations in roots harvested from microcosms with and without humic acid addition were 6.01 and 3.46 microg g(-1) dw, respectively. These results suggest that the addition of HA to contaminated sediments decreased the mangrove microcosm's ability to remove pyrene as pyrene was more tightly bound to the organic matter and plant growth was reduced.