Extensive biodegradation of polychlorinated biphenyls in Aroclor 1242 and electrical transformer fluid (Askarel) by natural strains of microorganisms indigenous to contaminated African systems

Evidence for substantial aerobic degradation of Aroclor 1242 and Askarel fluid by newly characterized bacterial strains belonging to the Enterobacter, Ralstonia and Pseudomonas genera is presented. The organisms exhibited degradative activity in terms of total PCB/Askarel degradation, degradation of individual congeners and diversity of congeners attacked. Maximal degradation by the various isolates of Askarel ranged from 69% to 86% whereas, Aroclor 1242, with the exception of Ralstonia sp. SA-4 (9.7%), was degraded by 37% to 91%. PCB analysis showed that at least 45 of the representative congeners in Aroclor 1242 were extensively transformed by benzoate-grown cells without the need for biphenyl as an inducer of the upper degradation pathway. In incubations with Aroclor 1242, no clear correlation was observed between percentage of congener transformed and the degree of chlorination, regardless of the presence or absence of biphenyl. Recovery of significant but nonstoichiometric amounts of chloride from the culture media showed partial dechlorination of congeners and suggested production of partial degradation products. Addition of biphenyl evidently enhanced dechlorination of the mixture by some isolates. With the exception of Ralstonia sp. SA-5, chloride released ranged from 24% to 60% in the presence of biphenyl versus 0.35% to 15% without biphenyl.     

Fungal degradation of metsulfuron-methyl in pure cultures and soil

A fungal strain capable of utilizing metsulfuron-methyl as sole carbon and energy sources was isolated from a metsulfuron-methyl treated soil. The degradation characteristics of metsulfuron-methyl by this fungal strain were investigated in liquid culture and soil. More than 79% of metsulfuron-methyl at concentrations of 0.10 mgl(-1), 1.0 mgl(-1) and 10.0 mgl(-1) in pure culture was degraded by strain MD after incubation for 7 days, whereas only 5.6%, 8.6% and 13.1% of metsulfuron-methyl were degraded at levels of 0.10 mgl(-1), 1.0mgl(-1) and 10.0 mgl(-1) in the controls, respectively. The incorporation of strain MD into soil was found to substantially increase the degradation of metsulfuron-methyl. Degradation was 7.5 and 3.8 times faster in strain MD amended soils than in sterilized and fresh soils. The results show that addition of the isolated strain MD enhances degradation of metsulfuron-methyl in water and soil.     

Anaerobic biodegradation of biphenyl in various paddy soils and river sediment

The anaerobic degradation of biphenyl was investigated in four uncontaminated Japanese paddy soils and one river sediment sample contaminated with benzene and chlorinated aliphatics. Two of the paddy soils and the sediment were capable of degrading biphenyl anaerobically without any additional medium or electron acceptors. The half-lives of biphenyl biodegradation in the three samples were 212 d in the Kuridashi soil, 327 d in the Kamajima soil, and 429 d in the river sediment. The Kuridashi soil metabolized 1+/-0.3% of [U-14C]-biphenyl into CO2 and 5+/-2% into water-soluble metabolites after 45 d of incubation. Submerged conditions, which result in lower nitrate and iron oxide contents, and neutral pH, appeared to be the common properties among the samples that influenced their degradation capacities. The addition of 10mM sulfate and 20mM Fe(III) as electron acceptors did not enhance the biphenyl degradation rate, whereas 10mM nitrate completely inhibited biphenyl degradation. The addition of different electron donors (lactate, acetate, or pyruvate) slightly slowed the degradation. Molybdate (an inhibitor of sulfate-reducing bacteria) had an inhibitory effect on biphenyl biodegradation, but bromoethanesulfonic acid (an inhibitor of methanogens) did not. Most biphenyl degradation was observed when only water was added, with no other electron acceptors or donors. These results suggest that sulfate-reducing bacteria and fermentative microbial populations play important roles in anaerobic biphenyl biodegradation in paddy soil.     

Isolation and characterization of 1,2,4-trichlorobenzene mineralizing Bordetella sp. and its bioremediation potential in soil

A soil which has been polluted with chlorinated benzenes for more than 25 years was used for isolation of adapted microorganisms able to mineralize 1,2,4-trichlorobenzene (1,2,4-TCB). A microbial community was enriched from this soil and acclimated in liquid culture under aerobic conditions using 1,2,4-TCB as a sole available carbon source. From this community, two strains were isolated and identified by comparative sequence analysis of their 16S-rRNA coding genes as members of the genus Bordetella with Bordetella sp. QJ2-5 as the highest homological strain and with Bordetella petrii as the closest related described species. The 16S-rDNA of the two isolated strains showed a similarity of 100%. These strains were able to mineralize 1,2,4-TCB within two weeks to approximately 50% in liquid culture experiments. One of these strains was reinoculated to an agricultural soil with low native 1,2,4-TCB degradation capacity to investigate its bioremediation potential. The reinoculated strain kept its biodegradation capability: (14)C-labeled 1,2,4-TCB applied to this inoculated soil was mineralized to about 40% within one month of incubation. This indicates a possible application of the isolated Bordetella sp. for bioremediation of 1,2,4-TCB contaminated sites.     

Evidence for enhanced dissipation of chlorpyrifos in an agricultural soil inoculated with Serratia rubidaea strain ABS 10

The insecticide ¹⁴C-chlorpyrifos was found mineralized in a Tunisian soil with repeated exposure to it. From this soil, a bacterial strain was isolated that was able to grow in a minimal salt medium (MSM) supplemented with 25 mg L^?1 of chlorpyrifos. It was characterized as Serratia rubidaea strain ABS 10 using morphological and biochemical analyses, as well as 16S rRNA sequencing. In a liquid culture, the S. rubidaea strain ABS 10 was able to dissipate chlorpyrifos almost entirely within 48 h of incubation. Although the S. rubidaea strain ABS 10 was able to grow in an MSM supplemented with chlorpyrifos and dissipate it in a liquid culture, it was not able to mineralize ¹⁴C-chlorpyrifos. Therefore, it can be concluded that the dissipation capability of this bacteria might be attributed to its capacity to adsorb CHL. It can also be ascribed to other reasons such as the formation of biogenic non-extractable residues. In both non-sterile and sterile soil inoculated with S. rubidaea strain ABS 10, chlorpyrifos was more rapidly dissipated than in controls with DT₅₀ of 1.38 and 1.05 days, respectively.

     

Degradation of atrazine by an acclimatized soil fungal isolate

A fungal strain able to use atrazine (2-chloro-4-ethylamino-5-isopropylamino-1,3,5-triazine) as a source of nitrogen was isolated from a corn field soil that has been previously treated with the herbicide. This strain was purified and acclimatized to atrazine at a higher level in the laboratory. A supplemented N was required to trigger the reaction. Atrazine was degraded at a faster rate in inoculated mineral salt medium (MSM) than non-inoculated MSM. Within 20 days, nearly 34% of the atrazine was degraded in inoculated medium while only 2% of the herbicide was degraded in non-inoculated medium. Degradation of atrazine by the isolated fungal strain was also studied in sterile and non-sterile soil to determine the compatibility of the isolated strain with native microorganisms in soil. The degradation of atrazine was found to be more in inoculated sterile soil than in inoculated non-sterile soil. Cell free extract (CFE) of fungal mycelium degraded about 50% of the atrazine in buffer in 96 hours compared to the control. Four atrazine metabolites were isolated and characterized by LCMS. On the basis of morphological parameters the isolate was identified as Penicillium species. Results indicated that the microorganism may be useful for remediation of atrazine-contaminated soil.     

Biodegradation of polychlorinated biphenyls using biofilm grown with biphenyl as carbon source in fluidized bed reactor

This study investigated the use of biofilms in the biodegradation of polychlorinated biphenyls. The biofilm used was developed on modified cement particles using mixed microbial culture isolated from PCB-contaminated soil. The biofilm formed was first acclimatized to PCBs by feeding the reactor alternately with biphenyl and PCBs. The acclimatized biofilm was tested on simulated PCB-contaminated water containing Aroclor 1260 by using a three-phase fluidized-bed reactor operated in batch mode. The initial batch run yielded 80+/-2.38% PCB removal from medium in one day and 91+/-1.34% in 5 days. The percent PCB removal gradually increased in the succeeding runs reaching 92+/-2.48% in one day and a steady state value of 95+/-2.01% in 5 days from batch eight onwards. PCB removal from the medium was highest during the first day reaching 80-92%. The sudden decrease in PCB concentration was attributed to an initial adsorption of the PCB on the biofilm and then the compound was degraded gradually. Yellow intermediates were observed as the pH of the medium decreased. These intermediate products were further metabolized as indicated by the disappearance of the yellow substance.     

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 endosulfan by Mortieralla sp. strain W8 in soil: Influence of different substrates on biodegradation

To examine the bioremediation potential of Mortierella sp. strain W8 in endosulfan contaminated soil, the fungus was inoculated into sterilized and unsterilized soil spiked with endosulfan. Wheat bran and cane molasses were used as substrates to understand the influence of different organic materials on the degradation of endosulfan in soil. Strain W8 degraded α- and β-endosulfan in both sterilized and unsterilized soil. In unsterilized soil with wheat bran+W8, α- and β- endosulfan were degraded by approximately 80% and 50%, respectively after 28 d incubation against the initial endosulfan concentration (3 mg kg(-1) dw). The corresponding values for α- and β-endosulfan degradation with wheat bran only were 50% and 3%. Endosulfan diol metabolite was detected after 14 d incubation in wheat bran+W8 whereas it was not found with wheat bran only. Production of endosulfan sulfate, the main metabolite of endosulfan, was suppressed with wheat bran+W8 treatment compared with wheat bran only. It was demonstrated that wheat bran is a more suitable substrate for strain W8 than cane molasses. Wheat bran+W8 is a superior fungus and substrate mix for bioremediation in soil contaminated with endosulfan.     

Atmospheric PCB congeners across Chicago

We have measured PCBs in 184 air samples collected at 37 sites in the city of Chicago using an innovative system of high-volume air samplers mounted on two health clinic vans. Here we describe results of sampling conducted from November 2006 to November 2007. The samples were analyzed for all 209 PCB congeners using a gas chromatograph with tandem mass spectrometry (GC-MS/MS). The ΣPCBs (sum of 169 peaks) in Chicago ranged from 75 pg m(-3) to 5500 pg m(-3) and primarily varied as a function of temperature. The congener patterns are surprisingly similar throughout the city even though the temperature-corrected concentrations vary by more than an order of magnitude. The average profile resembles a mixture of Aroclor 1242 and Aroclor 1254, and includes many congeners that have been identified as being aryl hydrocarbon receptor (AhR) agonists (dioxin-like) and/or neurotoxins. The toxic equivalence (TEQ) and neurotoxic equivalence (NEQ) in air were calculated and investigated for their spatial distribution throughout the urban-industrial complex of Chicago. The NEQ concentrations are linearly correlated with ΣPCBs while the TEQ concentrations are not predictable. The findings of this study suggest that airborne PCBs in Chicago are widely present and elevated in residential communities; there are multiple sources rather than one or a few locations of very high emissions; the emission includes congeners associated with dioxin-like and neurotoxic effects and congeners associated with unidentified sources.     

Acetone-induced photodechlorination of Aroclor 1254 in alkaline 2-propanol: Probing the mechanism by thermolysis in the presence of di-t- butyl peroxide

Aroclor 1254 (1860 mg/l) in alkaline 2-propanol and in the presence of acetone (4% v/v) was photodechlorinated to biphenyl at λ >300 nm with exceptionally high quantum yield (Φ= 18). Under similar conditions photodechlorination of extracts of Aroclor 1254 contaminated soil (730 mg/kg) proceeded with lower quantum yield Φ= 0.4. While oxygen severely quenched photolysis, dechlorination was accomplished under thermal conditions using di-t-butyl peroxide, t-BuOOBu-t, as free radical initiator. A free radical chain reaction is suggested in which acetone triplet, T₁(n,π*), or t-BuO^· radical abstracts H-atom from 2-propanol to give the ketyl radical, (CH₃)₂ OH, which after losing a proton to the alkaline medium gives the ketyl radical anion, (CH₃)₂CHO^·−. The Aroclor in turn reacts with the latter species through an electron-transfer process giving unstable aryl radical anion, , which cleaves releasing the chloride anion, Cl⁻ and the aryl radical, A^·     

Evaluation of cumulative PCB exposure estimated by a job exposure matrix versus PCB serum concentrations

Although polychlorinated biphenyls (PCBs) have been banned in many countries for more than three decades, exposures to PCBs continue to be of concern due to their long half-lives and carcinogenic effects. In National Institute for Occupational Safety and Health studies, we are using semiquantitative plant-specific job exposure matrices (JEMs) to estimate historical PCB exposures for workers (n?=?24,865) exposed to PCBs from 1938 to 1978 at three capacitor manufacturing plants. A subcohort of these workers (n?=?410) employed in two of these plants had serum PCB concentrations measured at up to four times between 1976 and 1989. Our objectives were to evaluate the strength of association between an individual worker’s measured serum PCB levels and the same worker’s cumulative exposure estimated through 1977 with the (1) JEM and (2) duration of employment, and to calculate the explained variance the JEM provides for serum PCB levels using (3) simple linear regression. Consistent strong and statistically significant associations were observed between the cumulative exposures estimated with the JEM and serum PCB concentrations for all years. The strength of association between duration of employment and serum PCBs was good for highly chlorinated (Aroclor 1254/HPCB) but not less chlorinated (Aroclor 1242/LPCB) PCBs. In the simple regression models, cumulative occupational exposure estimated using the JEMs explained 14–24 % of the variance of the Aroclor 1242/LPCB and 22–39 % for Aroclor 1254/HPCB serum concentrations. We regard the cumulative exposure estimated with the JEM as a better estimate of PCB body burdens than serum concentrations quantified as Aroclor 1242/LPCB and Aroclor 1254/HPCB.     

油污土中降解柴油细菌的分离鉴定及降解能力研究

从所采集柴油污染土壤样品中富集、分离得到柴油降解优势菌株,命名为B-3和B-4.根据其生理生化性质及16S rDNA序列比对分析,确定2株菌分别属于Tetrathiobacter kashmirensis、假单胞菌属(Pseudomonas sp.).由于实验中,B-3的生长曲线较特殊,故以B-3和典型石油烃降解菌假单...     

Biotic and abiotic degradation of illicit drugs, their precursor, and by-products in soil

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.     

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.     

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.     

Enrichment and isolation of endosulfan degrading and detoxifying bacteria

In the present study, degradation of endosulfan by a mixed culture isolated from a pesticide-contaminated soil was studied in batch experiments. After two weeks of incubation, the mixed culture was able to degrade 73% and 81% of alpha and beta endosulfan respectively. Endodiol was identified by GC/MS as degradation intermediate. The toxicity studies of endosulfan before and after degradation were carried out using micronucleus assay on human polymorphonuclear cells. The findings suggested that the metabolism of endosulfan isomers by the mixed culture was accompanied by significant reduction in the toxicity. Studies were also carried out to quantify the degradation potential of the individual species in the mixed bacterial culture. Two cultures identified by 16S rRNA as Stenotrophomonas maltophilia and Rhodococcus erythropolis were found to be responsible for majority of the degradation by the mixed culture. S. maltophilia showed better degradation efficiency compared to that by R. erythropolis. This is the first report of endosulfan degradation using the above-mentioned organisms.     

Enrichment and isolation of a mixed bacterial culture for complete mineralization of endosulfan

In the present study, we isolated three novel bacterial species, namely, Staphylococcus sp., Bacillus circulans-I, and Bacillus circulans-II, from contaminated soil collected from the premises of a pesticide manufacturing industry. Batch experiments were conducted using both mixed and pure cultures to assess their potential for the degradation of aqueous endosulfan in aerobic and facultative anaerobic condition. The influence of supplementary carbon (dextrose) source on endosulfan degradation was also examined. After four weeks of incubation, mixed bacterial culture was able to degrade 71.82 +/- 0.2% and 76.04 +/- 0.2% of endosulfan in aerobic and facultative anaerobic conditions, respectively, with an initial endosulfan concentration of 50 mg l(-1). Addition of dextrose to the system amplified the endosulfan degradation efficiency by 13.36 +/- 0.6% in aerobic system and 12.33 +/- 0.6% in facultative anaerobic system. Pure culture studies were carried out to quantify the degradation potential of these individual species. Among the three species, Staphylococcus sp. utilized more beta endosulfan compared to alpha endosulfan in facultative anaerobic system, whereas Bacillus circulans-I and Bacillus circulans-II utilized more alpha endosulfan compared to beta endosulfan in aerobic system. In any of these degradation studies no known intermediate metabolites of endosulfan were observed.     

Biodegradation of nicosulfuron by the bacterium Serratia marcescens N80

By enrichment culturing of the sludge collected from the industrial wastewater treatment pond, we isolated a highly efficient nicosulfuron degrading bacterium Serratia marcescens N80. In liquid medium, Serratia marcescens N80 grows using nicosulfuron as the sole nitrogen source, and the optimal temperature, pH values, and inoculation for degradation are 30-35°C, 6.0-7.0, and 3.0% (v/v), respectively. With the initial concentration of 10 mg L?1, the degradation rate is 93.6% in 96 hours; as the initial concentrations are higher than 10 mg L?1, the biodegradation rates decrease as the nicosulfuron concentrations increase; when the concentration is 400 mg L?1, the degradation rate is only 53.1%. Degradation follows the pesticide degradation kinetic equation at concentrations between 5 mg L?1 and 50 mg L?1. Identification of the metabolites by the liquid chromatography/mass spectrometry (LC/MS) indicates that the degradation of nicosulfuron is achieved by breaking the sulfonylurea bridge. The strain N80 also degraded some other sulfonylurea herbicides, including ethametsulfuron, tribenuron-methyl, metsulfuron-methyl, chlorimuron-ethyl,and rimsulfuron.