Anaerobic biodegradation of DDT residues (DDT, DDD, and DDE) in estuarine sediment.

The potential for anaerobic biodegradation of 1,1,1-trichloro-2,2-bischlorophenylethane (DDT), 1,1-dichloro-2,2,-bischlorophenylethane (DDD), and dichlorodiphenylchloroethylene (DDE) in anoxic sediment slurries collected from the Keelung River was investigated in this study. o,p'- and p,p'-DDT were dechlorinated to o,p'- and p,p'-DDD, respectively, and then transformed to other compound(s). 1-Chloro-2,2-bis (p-chlorophenyl) ethylene (DDMU) and trace amount of dichlorobenzophenone (DBP) were detected in sediment slurries amended with p,p'-DDT or p,p'-DDD. DDMU was also detected in sediment slurries amended with p,p'-DDE. The relative transformation rates for both o,p'- and p,p'-isomers of DDT, DDD, and DDE were DDT>DDD>DDE. Re-addition of DDT, DDD, or DDE to the sediment slurries after initial removal enhanced the respective dechlorination rates. The transformation rates of the p,p'-isomers of both DDT and DDD were faster than those of the respective o,p'-isomers. p,p'-DDT dechlorination in the p,p'-DDT-adapted sediment slurries were inhibited by the addition of molybdate, or molybdate plus sulfate, but not inhibited by the addition of sulfate. Addition of bromoethane-sulfonic acid (BESA) slightly inhibited p,p'-DDT dechlorination. Non-adapted sediment slurries lost the ability to dechlorinate pentachlorophenol during adaptation to p,p'-DDT. p,p'-DDD was the major transformation product of p, p'-DDT in 3,4,4',5-tetrachlorobiphenyl-adapted sediment slurries, which suggested that the microbial community in the 3,4,4',5-CB-adapted sediment was unable to remove chlorine from the aromatic rings of p,p'-DDT.     

Organochlorine pesticides in soil under irrigated cotton farming systems in Vertisols of the Namoi Valley, north-western New South Wales, Australia

Organochlorine pesticides (OCPs) such as DDT and DDE have been detected in the surface 0.2 m of Vertisols in the lower Namoi Valley of north western New South Wales, Australia even though they have not been applied to crops since 1982. However, their presence in the deeper soil horizons has not been investigated. The objective of this study was to determine if OCPs were present to a depth of 1.2 m in Vertisols under irrigated cotton farming systems in the lower Namoi Valley of New South Wales. Soil was sampled from the 0-1.2 m depths in three sites, viz. the Australian Cotton Research Institute, ACRI, near Narrabri (149°36′E, 30°12′S), and two cotton farms near Wee Waa (149°27′E, 30°13′S) and Merah North (149°18′E, 30°12′S) in northern New South Wales, Australia. The OCPs detected and their metabolites were α-endosulfan, β-endosulfan, endosulfan sulphate, DDD, DDE, DDT and endrin. The metabolite DDE, a breakdown product of DDT, was the most persistent OCP in all depths analysed. Endosulfan sulphate was the second most persistent followed by endrin > α-endosulfan > β-endosulfan > DDT and DDD. DDT was sprayed extensively in the lower Namoi Valley up to the early 1980s and may explain the persistence of DDE in the majority of soil samples. Dicofol and Dieldrin, two OCPs previously undocumented in Vertisols were also detected. The movement of OCPs into the subsoil of Vertisols may occur when irrigation or rain transports soil colloids and organic matter via preferential flow systems into the deeper layers of a soil profile. Persistence of OCPs was closely correlated to soil organic carbon concentrations. The persistence in soil of OCP’s applied to cotton crops grown more than two decades ago suggests that they could enter the food chain. Their presence at depths of 1.2 m suggests that they could move into groundwater that may eventually be used for domestic and stock consumption.     

Enhanced transformation and dechlorination of p-chloronitrobenzene in the combined ZVI–anaerobic sludge system

The combination of zero-valent iron (ZVI) with anaerobic sludge for enhancing reductive transformation and dechlorination of p-chloronitrobenzene (p-ClNB) was investigated in this study. p-ClNB was quickly reduced into p-chloroaniline (p-ClAn) and subsequently dechlorinated into aniline in the complex system, and the strengthening factor for pseudo-first-order transformation rate constant of p-ClNB (Q, k _ZVI?+?sludge/(k _sludge?+?k _ZVI)) was above 3. The Q values for the different ZVI types with anaerobic sludge were as following: Reduced ZVI (RZVI)?>?Industrial ZVI?>?Nanoscale ZVI (NZVI). Thereinto, the aggregation of NZVI occurred, and its reaction activity declined. Furthermore, the increase of ZVI dosage promoted the p-ClNB transformation, but the p-ClAn dechlorination rate and Q value were not improved. With the anaerobic biomass increasing, the dechlorination rate of p-ClAn was significantly enhanced, and the Q value had positive relation with the mass ratio of anaerobic sludge to RZVI.     

pH值对“Fe^0．厌氧微生物”体系去除2，4，6-三氯酚过程的影响

考察了pH值对“Fe^0一厌氧微生物”体系降解2，4，6，一三氯酚（2，4，6．TCP）效果的影响，结果表明：pH值是影响“Fe^0-厌氧微生物”体系降解2，4，6-TCP效果的重要参数，初始pH值直接影响微生物活性和铁腐蚀，进而影响过程pH值变化，反过来又影响铁腐蚀和微生物活性，pH7．0～9．0的中性偏碱范围较适于厌氧微生物生长。Fe^0与微生物对目标污染物的降解具有协同促进作用，其协同促进机制表现在3方面：Fe^0与微生物对体系过程pH值具有互补调节作用，可将体系的pH值调节值适于微生物生长的中性范围；Fe^0腐蚀产生的Fe2＋和H2可为微生物代谢提供电子对和营养物质，从而促进生物还原脱氯的进行；Fe^0的腐蚀过程直接对氯代有机物还原脱氯，而微生物又可促进Fe^0腐蚀。     

Production and use of DDT containing antifouling paint resulted in high DDTs residue in three paint factory sites and two shipyard sites, China

This study provides the first intensive investigation of Dichlorodiphenyltrichloroethanes (DDT) distribution in typical paint factories and shipyards in China where DDT containing antifouling paint were mass produced and used respectively. DDTs were analyzed in soil, sludge and sediment samples collected from three major paint factories and two shipyards. The results showed that the total DDTs concentrations detected in paint factory and shipyard sites ranged from 0.06 to 8387.24 mg kg⁻¹. In comparison with paint factory sites, the shipyard sites were much more seriously contaminated. However, for both kinds of sites, the DDTs level was found to be largely affected by history and capacity of production and use of DDT containing antifouling paint. (DDE + DDD)/DDT ratios indicated that DDT containing antifouling paint could serve as important fresh input sources for DDTs. It can be seen that most samples in shipyards were in ranges where heavy contamination and potential ecological risk were identified.     

pH值对"Fe0-厌氧微生物"体系去除2,4,6-三氯酚过程的影响

考察了pH值对"Fe0-厌氧微生物"体系降解2,4,6,-三氯酚(2,4,6-TCP)效果的影响,结果表明:pH值是影响"Fe0-厌氧微生物"体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH 7.0～9.0的中性偏碱范围较适于厌氧微生物生长。Fe0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面:Fe0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe0腐蚀产生的Fe2+和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe0腐蚀。     

Effect of coplanar PCB concentration on dechlorinating microbial communities and dechlorination in estuarine sediments

The effect of concentration of coplanar PCB on the dechlorinating microbial community and dechlorination were investigated in anoxic estuarine sediment collected from Er-Jen River and enriched with 10 and 50 mg L⁻¹ of 3,4,4′,5-tetrachlorobiphenyl, 3,3′,4,4′,5-pentachlorobiphenyl, and 3,3′,4,4′,5,5′-hexachlorobipheny. Dechlorination rates were similar in the cultures enriched with 10 and 50 mg L⁻¹ of 3,4,4′,5-tetrachlorobiphenyl, whereas significantly higher dechlorination rates were observed in cultures enriched with 10 mg L⁻¹ of 3,3′,4,4′,5-pentachlorobiphenyl. No dechlorination was observed in sediment slurries enriched with 3,3′,4,4′,5,5′-hexachlorobipheny. Para dechlorination occurred prior to meta dechlorination during reductive dechlorination of 3,4,4′,5-tetrachlorobiphenyl and 3,3′,4,4′,5-pentachlorobiphenyl. GC-MS and denaturing gradient gel electrophoresis (DGGE) were used to detect dechlorination products and dechlorinating microorganisms in the enriched sediment cultures during the process of degradation. Two Chloroflexi phylotypes observed in DGGE were responsible for para and meta dechlorination respectively. Phylotype Cp-1 has 98% similarity to uncultured bacterium N5-12. Phylotype Cm-1 has 99% similarity to uncultured dechlorinating bacterium m1 or SF1 belonging to the ο-17/DF-1 group of PCB-dechlorinating bacteria.     

Evidence of non-DDD pathway in the anaerobic degradation of DDT in tropical soil

Environmental Science and Pollution Research - DDT transformation to DDD in soil is the most commonly reported pathway under anaerobic conditions. A few instances of DDT conversion to products...     

Enhanced reductive dechlorination of polychlorinated biphenyl-contaminated soil by in-vessel anaerobic composting with zero-valent iron

Anaerobic dechlorination is an effective degradation pathway for higher chlorinated polychlorinated biphenyls (PCBs). The enhanced reductive dechlorination of PCB-contaminated soil by anaerobic composting with zero-valent iron (ZVI) was studied, and preliminary reasons for the enhanced reductive dechlorination with ZVI were investigated. The results show that the addition of nanoscale ZVI can enhance dechlorination during in-vessel anaerobic composting. After 140 days, the average number of removed Cl per biphenyl with 10 mg g^?1 of added nanoscale ZVI was 0.63, enhancing the dechlorination by 34 % and improving the initial dechlorination speed. The ZVI enhances dechlorination by providing a suitable acid base environment, reducing volatile fatty acid inhibition and stimulating the microorganisms. The C/N ratios for treatments with the highest rate of ZVI addition were smaller than for the control, indicating that ZVI addition can promote compost maturity.     

Cytogenetic status of human lymphocytes after exposure to low concentrations of p,p'-DDT, and its metabolites (p,p'-DDE, and p,p'-DDD) in vitro

Despite that the use of DDT has been restricted for more than 40 years to malaria affected areas, low doses of this pesticide and its metabolites DDE and DDD can be found in the environment around the world. Although it has been shown that these pollutants induce cell and DNA damage, the mechanisms of their cytogenotoxic activity remains largely unknown. This study looks into their possible genotoxic effects, at doses that can be found in body fluids, on human lymphocytes using the cytokinesis-block micronucleus assay and the comet assay. After exposure for 1, 6, and 24 h compounds p,p′-DDT (0.1 μg mL⁻¹), p,p′-DDE (4.1 μg mL⁻¹), and p,p′-DDD (3.9 μg mL⁻¹) showed increase in DNA damage. The most significant results were observed at exposure period of 24 h where number of micronucleated cells increased from control 2.5 ± 0.71 to 23.5 ± 3.54, 13.5 ± 0.71, and 16.5 ± 6.36 for DDT, DDE, and DDD, respectively. Similar effect was observed using comet test where the percentage of DNA in comets tail increased from control 1.81 ± 0.16 to 17.24 ± 0.55, 11.21 ± 0.56 and 9.28 ± 0.50 for each compound, respectively. At the same time Fpg-comet assay failed to report induction of oxidative DNA damage of these pollutants. Additionally, the type of cell death was determined using diffusion assay and necrosis dominated. Our findings suggest that even at low concentrations, these pesticides could induce cytogenetic damage to human peripheral blood lymphocytes and in that manner have the impact on human health as well.     

Seasonal variation of organochlorine contaminants in bonito (Sarda sarda L. 1758) and anchovy (Engraulis encrasicolus L. 1758) in Black Sea region, Turkey

The concentrations of indicator polychlorinated biphenyls (PCBs) and organochlorine insecticides were determined in bonito (Sardasarda L. 1758) and anchovy (Engraulisencrasicolus L. 1758) from the Black Sea, Turkey. Concentrations of total indicator PCBs ranged between <1-17.0 in bonito, and <1-17.5 ng/g fresh weight in anchovy, and total of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane and its metabolites’ (DDTs) concentrations ranged between 13.4-26.3, and 2.96-19.0 ng/g fresh weight in bonito and anchovy respectively. PCB 52, p,p′-DDE and endosulfan (α + β) were found dominant in both of the fish species. Except endosulfan, and some DDT metabolites, none of the studied organochlorine pesticides was detected in the fish samples. Concentrations of PCBs in anchovy were found higher than those in bonito, whereas DDT and endosulfan concentrations were found similar in both of the fish species. All of the fish samples had residue concentrations below the maximum residue limits (MRL) recommended by FAO/WHO Codex Alimentarius Commission.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

Hydrodechlorination of dichlorobenzenes and their derivatives over Ni-Mo/C catalyst: kinetic analysis and effect of molecular structure of reactant

The kinetics of the catalytic hydrodechlorination (HDC) process of selected dichlorobenzenes (DCBs), dichlorotoluenes (DCTs) and dichlorodiphenyls (DCDs) was studied in the presence of a sulphided carbon-supported Ni-Mo catalyst. The HDC runs were performed in a magnetic stirred batch reactor in the range of 210-230 °C under the hydrogen pressure of 3 MPa. The kinetic constants were evaluated and the reaction network was proposed assuming the pseudo-first order kinetics of dechlorination process. The HDC of aromatic dichloroderivatives proceeded via a network of sequential-parallel reactions. At 210 °C DCBs, DCTs and DCDs followed mainly the pathway of direct transformation to respective aromatic hydrocarbon. At 230 °C, the contribution of sequential dechlorination to monochloroderivative became more predominant.     

Occurrence and levels of organochlorine compounds in human breast milk in Bangladesh

In low-income countries, the use of some organochlorine pesticides is still common in order to increase food production. Monitoring the chemical exposure is an important step in risk-reducing strategies. This is the first study to report concentrations of organochlorines in breast milk of women from Bangladesh where farming is the main income source.Organochlorines such as p,p′-DDT, o,p′-DDT, p,p′-DDE, p,p′-DDD (i.e., ∑DDT), HCB, α-, β- and γ-HCH, trans-chlordane, cis-chlordane, oxy-chlordane, trans-nonachlor, cis-nonachlor, mirex and polychlorinated biphenyls (CB 28, 52, 99, 101, 105, 114, 118, 123, 128, 138, 141, 149, 153, 156, 157, 163, 167, 170, 180, 183, 187, 189, 194) were analyzed in breast milk collected in 2002 from 72 first-time mothers (median age 20 years) living in the rural area Matlab, Bangladesh.While the concentrations of PCBs and many of the pesticides were low, the concentrations of p,p′-DDT and its metabolite p,p′-DDE were high (median 349 and 1645 ng g⁻¹ lipid, respectively) in comparison to other countries. The median value of ∑DDT was 2123 ng g⁻¹ lipid. The estimated daily exposure to p,p′-DDT, p,p′-DDE and ∑DDTs was 10, 30 and 42 μg kg⁻¹ body weight, respectively, in 3 months old infants. The p,p′-DDE/p,p′-DDT ratio ranged from 1 to 23, where 58% of the mothers had a ratio below 5 indicating recent or ongoing DDT exposure.This study reports infant exposure and maternal body burden of organochlorines through breast milk. Although the findings give no reason to limit breast-feeding, it is essential to identify the main exposure sources and find means to decrease the exposure.     

Organochlorine contaminants in the hair of Iranian pregnant women

In the present study, the hair of pregnant women was sampled between November 2007 and January 2008 in Ahvaz and Noushahr cities and the countryside of Noushahr, Iran. They were analyzed for organochlorine pesticides (OCPs), such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), α-, β-, and γ-hexachlorocyclohexane (HCH) isomers and seven polychlorinated (PCBs) congeners (IUPAC Nos. 28, 52, 101, 118, 138, 153 and 180). Significant differences between the concentrations of investigated pollutants were found between the locations (p < 0.05). For HCHs, the γ-HCH isomer was measured at higher mean concentrations (6 ng g⁻¹ hair) compared to the β-HCH isomer (0.03 ng g⁻¹), which generally is the most prevalent HCH in biological matrices. Very high mean concentrations of p,p′-DDT in countryside of Noushahr (24 ng g⁻¹) combined with lower values (0.6) of ratio p,p′-DDE/p,p′-DDT in the hair samples suggest recent exposure to “fresh” DDT in this region. Significant differences in OCPs and PCBs were found between primiparous and multiparous mothers (p < 0.05). There was no correlation between levels of OCPs and PCBs in the hair of Iranian pregnant women and their age. There was a significant difference (p < 0.05) in the organochlorine levels, including HCHs, between mothers who have eaten fish once a week and those who consumed fish more than once per week in Noushahr.     

Evaluation of TCDD biodegradability under different redox conditions

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.     

Complete dechlorination of DDE/DDD using magnesium/palladium system.

Kinetic studies on the dechlorination of 1,1-dichloro-2,2 bis (4,-chlorophenyl) ethane (DDD) and 1,1,dichloro-2,2 bis (4,-chlorophenyl) ethylene (DDE) in 0.05% biosurfactant revealed that the reaction follows second-order kinetics. The rate of reaction was dependent on the presence of acid, initial concentrations of the target compound, and zerovalent magnesium/tetravalent palladium. Gas chromatography-mass spectrometry analyses of DDE dechlorination revealed the formation of a completely dechlorinated hydrocarbon skeleton, with diphenylethane as the end product, thereby implying the removal of all four chlorine atoms of DDE. In the case of DDD, we identified two partially dechlorinated intermediates [namely, 1,1-dichloro-2, 2 bis (phenyl) ethane and 1, chloro-2, 2 bis (phenyl) ethane] and diphenylethane as the end product. On the basis of products formed from DDD dehalogenation, we propose the removal of aryl chlorine atoms as a first step. Our investigation reveals that biosurfactant may be an attractive solubilizing agent for DDT and its residues. The magnesium/palladium system is a promising option because of its high reactivity and ability to achieve complete dechlorination of DDE and DDD.     

Quantifying the effects of fumarate on in situ reductive dechlorination rates

In situ methods are needed to evaluate the effectiveness of chemical amendments at enhancing reductive dechlorination rates in groundwater that is contaminated with the priority pollutant, trichloroethene (TCE). In this communication, a method that utilizes single-well, “push–pull” tests to quantify the effects of chemical amendments on in situ reductive dechlorination rates is presented and demonstrated. Five push–pull tests were conducted in each of five monitoring wells located in a TCE-contaminated aquifer at the site of a former chemical manufacturing facility. Rates for the reductive dechlorination of the fluorinated TCE-surrogate, trichlorofluoroethene (TCFE), were measured before (test 1) and after (test 5) three successive additions (tests 2–4) of fumarate. Fumarate was selected to stimulate the growth and activity of indigenous microorganisms with the metabolic capability to reduce TCFE and TCE. In three wells, first-order rate constants for the reductive dechlorination of TCFE increased by 8.2–92 times following fumarate additions. In two wells, reductive dechlorination of TCFE was observed after fumarate additions but not before. The transformation behavior of fumarate was also monitored following each fumarate addition. Correlations between the reductive dechlorination of TCFE and the reduction of fumarate to succinate were observed, indicating that these reactions were supported by similar biogeochemical conditions at this site.