Biodiversity in wetland+ system: a passive solution for HCH dump effluents.

The hexachlorocyclohexane isomers (HCH) are long-banned pesticides. Even though their use has been prohibited for decades, their presence in the environment is still reported worldwide. Wetland + is a registered trademark of the remedial treatment technology consisting of an aerobic sedimentary tank, a permeable reactive barrier, a biosorption system, and an aerobic wetland. This proven method combines a reductive treatment known from PRBs with the natural wetland self-cleaning processes. The average efficiency of the system is 96.8% for chlorobenzenes (ClB) and 81.7% for HCH, during the first 12 months of the system operation. The presence of the genes encoding enzymes involved in the degradation of the HCH compounds indicates that the removal of HCH and ClB occurs not only by chemical removal but also through aerobic and anaerobic combining biodegradation. Changes in abundance and the composition of the diatom community were found to be suitable indicators of the water quality and of the impact of the Wetland + operation on the water ecosystem. The system's annual operation exhibited a markedly higher number of diatom species in the closing profiles of the Ostrovský Creek, the Wetland + effluent recipient.

Revelation of bioremediation approaches for hexachlorocyclohexane degradation in soil.

This review elucidates different bioremediation approaches used for degradation of HCH from contaminated sites. It highlights the significance of degradative pathways, microbial diversity and impact of different environmental factors for developing viable bioremediation strategies. The application of innovative biotechnological approaches and a thorough understanding of HCH biodegradation pathways show great promise for the creation of long-term solutions to HCH pollution and the restoration of polluted soil ecosystems. Bioremediation technologies viz. biostimulation, bioaugmentation, phytoremediation have been considered till date for treating HCH-contaminated sites. Different bacterial and fungal strains have been reported for degradation of HCH residues. However, these methods are limited to γ-HCH degradation, at laboratory scale and achieving lower success rate for large scale demonstration trials. This review presents a theoretical background for degradation of different HCH isomers in soil through plants, microbes and through their cooperative interactions. This work briefly overviews the substantial contamination of the environment by HCH residues, along with spontaneous evolution of degradation pathways through various HCH degrading microbes. Bioremediation mechanism and pathways of HCH degradation through plants and microbes have been discussed thoroughly. Through molecular and genetic investigations, the complex metabolic pathways used by these microbes, including reductive dechlorination, hydrolysis, and ring cleavage, has been clarified. This study seeks to give a thorough summary of recent discoveries and developments in bioremediation methods for soil HCH degradation. Numerous microbial consortia, including fungi, plants, and bacteria have been recognised as important participants in the transformation of HCH.

Characterization of Hexachlorocyclohexane Isomer Dehydrochlorination by LinA1 and LinA2 Using Multi-element Compound-Specific Stable Isotope Analysis.

Dehydrochlorination is one of the main (thus far discovered) processes for aerobic microbial transformation of hexachlorocyclohexane (HCH) which is mainly catalyzed by LinA enzymes. In order to gain a better understanding of the reaction mechanisms, multi-element compound-specific stable isotope analysis was applied for evaluating α- and γ-HCH transformations catalyzed by LinA1 and LinA2 enzymes. The isotopic fractionation (εE) values for particular elements of (+)α-HCH (εC = -10.8 ± 1.0‰, εCl = -4.2 ± 0.5‰, εH = -154 ± 16‰) were distinct from the values for (-)α-HCH (εC = -4.1 ± 0.7‰, εCl = -1.6 ± 0.2‰, εH = -68 ± 10‰), whereas the dual-isotope fractionation patterns were almost identical for both enantiomers (ΛC-Cl = 2.4 ± 0.4 and 2.5 ± 0.2, ΛH-C = 12.9 ± 2.4 and 14.9 ± 1.1). The εE of γ-HCH transformation by LinA1 and LinA2 were -7.8 ± 1.0‰ and -7.5 ± 0.8‰ (εC), -2.7 ± 0.3‰ and -2.5 ± 0.4‰ (εCl), -170 ± 25‰ and -150 ± 13‰ (εH), respectively. Similar ΛC-Cl values (2.7 ± 0.2 and 2.9 ± 0.2) were observed as well as similar ΛH-C values (20.1 ± 2.0 and 18.4 ± 1.9), indicating a similar reaction mechanism by both enzymes during γ-HCH transformation. This is the first data set on 3D isotope fractionation of α- and γ-HCH enzymatic dehydrochlorination, which gave a more precise characterization of the bond cleavages, highlighting the potential of multi-element compound-specific stable isotope analysis to characterize different transformation processes (e.g., dehydrochlorination and reductive dehalogenation).

Stable Carbon Isotope Analysis of Hexachlorocyclohexanes by Liquid-Liquid Extraction Gas Chromatography Isotope Ratio Mass Spectrometry: Method Evaluation and Applications.

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid-liquid extraction method of HCHs in water. The results showed that there were negligible changes in the δ13C of HCHs after extraction, indicating that liquid-liquid extraction can be used as a pre-concentration method for the determination of δ13C of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the α-HCH oxidation by CaO2/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched δ13C in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (εC) of -1.90 ± 0.10‱ were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.

Association between toxic organochlorine levels in human serum and systemic lupus erythematosus.

Organochlorines (OCs) are groups of highly toxic pesticides with known immunotoxicity. The present work aimed to study the potential association between serum residues of OCs and the risk of developing systemic lupus erythematosus (SLE) as well as correlating to the clinical-laboratory manifestations in a sample of Egyptian SLE patients. A cross-sectional study was conducted on 132 patients environmentally exposed to OCs. Patients were diagnosed as SLE based on the American College of Rheumatology (ACR) revised criteria. Systemic Lupus Erythematosus Disease Activity Index-2000 (SLEDAI-2K) score was calculated to stratify the disease severity. Blood and urine samples were collected to measure the levels of OCs, serological markers, and urinary protein. The most frequently detected OCs were p,p'-DDE; lindane; and hexachlorobenzene (HCB). The risk of developing SLE was significantly associated with detected p,p'-DDE and HCB (B value 7.704 and 14.33, respectively). Hexachlorobenzene, in addition, was significantly associated with increased SLEDAI-2K score and polycythemia. Lindane was significantly associated with hypocomplementemia, cardiac manifestations of SLE, anemia, and leucopenia. In conclusion, the detected OCs p,p'-DDE and HCB are associated with increased risk of SLE in Egyptian patients and correlates to the manifestations of disease severity.

Accelerated remediation of organochlorine pesticide-contaminated soils with phyto-Fenton approach: a field study.

Phytoremediation and advanced oxidation processes are among the most promising techniques for removing organic pollutants from soils. A field trial was performed for six months to evaluate the effect of nano-Fe3O4 on the degradation of organochlorine pesticide residues including Lindane, p,p'-dichlorodiphenyltrichloroethane (DDT), p,p'-dichlorodiphenyldichloroethylene (DDE), and p,p'-dichlorodiphenyldichloroethane (DDD) in pesticide-contaminated soils in the presence of vetiver in Bac Giang province, Vietnam. Vetiver was planted in three zones with different nano-Fe3O4 concentrations. Soil samples from each zone were periodically collected to determine the remaining concentrations of selected organochlorine pesticides via gas chromatography-electron capture detector. Results indicated that the total DDT concentrations in the examined soil were 1.9-13 times higher than the permissible threshold level (10 µg g-1) established by the national technical regulation on pesticide residues in soil. The (p,p'-DDE + p,p'-DDD)/p,p'-DDT ratios ranged from 13.5 to 114, indicating the absence of recent inputs of technical DDTs at the study area. DDT dechlorination mainly occurred under aerobic pathways to form DDE. Furthermore, DDE degradation in soil was adequately described by the pseudo-first-order kinetics model (R2 > 0.892). In the presence of vetiver, the rate constants of DDE degradation were 0.264, 0.350, and 0.434 month-1 with 0, 25, and 100 mg kg-1 of added nano-Fe3O4, respectively, indicating that the degradation of DDE correlated positively with Fe3O4 concentration in the soil. Additionally, the presence of vetiver and nano-Fe3O4 in the soil increased DDT removal rates, which might be linked to the involvement of Fenton/Fenton-like reactions.

Effect of mixing on reductive dechlorination of persistent organic pollutants by Fe/Pd nanoparticles.

Herein, we report the comparison of two different mixing methods for reductive dechlorination of gamma-hexachlorocyclohexane (γ-HCH), aldrin, and p, p'-dichlorodiphenyl-trichloroethane (p, p'-DDT), using iron/palladium (Fe/Pd) bimetallic nanoparticles. A noticeable enhancement of the reaction rate was found when the reductive dechlorination reaction was carried out in an ultrasound bath as compared with a platform shaker. These enhancements could be attributed to (a) the continuous cleaning and chemical activation of the surfaces of nanoscale Fe/Pd bimetallic nanoparticles by the combined chemical and physical effects of acoustic cavitation; and (b) the accelerated mass transport rates of target POPs to the surfaces of the Fe/Pd nanoparticles. Finally, the degradation intermediates and final products were determined by gas chromatography/mass spectrometry (GC/MS) analysis and the plausible degradation pathways for γ-HCH, aldrin, and p, p'-DDT by Fe/Pd bimetallic nanoparticles were proposed. PRACTITIONER POINTS: Exposure to POPs is a resilient global environmental and health issue. Fe/Pd bimetallic nanoparticles demonstrated > 90 % removal of POPs in the first 30 minutes of the reaction via ultrasonic mixing. GC-MS analyses provided verification of POPs degradation intermediates and final products.

Can Alkaline Hydrolysis of γ-HCH Serve as a Model Reaction to Study Its Aerobic Enzymatic Dehydrochlorination by LinA?

Hexachlorocyclohexane (HCH) isomers constitute a group of persistent organic pollutants. Their mass production and treatment have led to a global environmental problem that continues to this day. The characterization of modes of degradation of HCH by isotope fractionation is a current challenge. Multi isotope fractionation analysis provides a concept to characterize the nature of enzymatic and chemical transformation reactions. The understanding of the kinetic isotope effects (KIE) on bond cleavage reaction contributes to analyses of the mechanism of chemical and enzymatic reactions. Herein, carbon, chlorine, and hydrogen kinetic isotope effects are measured and predicted for the dehydrochlorination reaction of γ-HCH promoted by the hydroxyl ion in aqueous solution. Quantum mechanical (QM) microsolvation with an implicit solvation model and path integral formalism in combination with free-energy perturbation and umbrella sampling (PI-FEP/UM) and quantum mechanical/molecular mechanical QM/MM potentials for including solvent effects as well as calculating isotope effects are used and analyzed with respect to their performance in reproducing measured values. Reaction characterization is discussed based on the magnitudes of obtained isotope effects. The comparative analysis between the chemical dehydrochlorination of γ-HCH in aqueous media and catalyzed reaction by dehydrochlorinase, LinA is presented and discussed. Based on the values of isotope effects, these two processes seem to occur via the same net mechanism.

Streptomyces sp. is a powerful biotechnological tool for the biodegradation of HCH isomers: biochemical and molecular basis.

Actinobacteria are well-known degraders of toxic materials that have the ability to tolerate and remove organochloride pesticides; thus, they are used for bioremediation. The biodegradation of organochlorines by actinobacteria has been demonstrated in pure and mixed cultures with the concomitant production of metabolic intermediates including γ-pentachlorocyclohexene (γ-PCCH); 1,3,4,6-tetrachloro-1,4-cyclohexadiene (1,4-TCDN); 1,2-dichlorobenzene (1,2-DCB), 1,3-dichlorobenzene (1,3-DCB), or 1,4-dichlorobenzene (1,4-DCB); 1,2,3-trichlorobenzene (1,2,3-TCB), 1,2,4-trichlorobenzene (1,2,4-TCB), or 1,3,5-trichlorobenzene (1,3,5-TCB); 1,3-DCB; and 1,2-DCB. Chromatography coupled to mass spectrometric detection, especially GC-MS, is typically used to determine HCH-isomer metabolites. The important enzymes involved in HCH isomer degradation metabolic pathways include hexachlorocyclohexane dehydrochlorinase (LinA), haloalkane dehalogenase (LinB), and alcohol dehydrogenase (LinC). The metabolic versatility of these enzymes is known. Advances have been made in the identification of actinobacterial haloalkane dehydrogenase, which is encoded by linB. This knowledge will permit future improvements in biodegradation processes using Actinobacteria. The enzymatic and genetic characterizations of the molecular mechanisms involved in these processes have not been fully elucidated, necessitating further studies. New advances in this area suggest promising results. The scope of this paper encompasses the following: (i) the aerobic degradation pathways of hexachlorocyclohexane (HCH) isomers; (ii) the important genes and enzymes involved in the metabolic pathways of HCH isomer degradation; and (iii) the identification and quantification of intermediate metabolites through gas chromatography coupled to mass spectrometry (GC-MS).

Anaerobic biotransformation of hexachlorocyclohexane isomers by Dehalococcoides species and an enrichment culture.

The biotransformation of hexachlorocyclohexane isomers (HCH) by two Dehalococcoides mccartyi strains (195 and BTF08) and an enrichment culture was investigated and compared to conversion by the obligate anaerobic strain Clostridium pasteurianum strain DSMZ 525. The D. mccartyi strains preferentially transformed γ-HCH over α-HCH and δ-HCH isomers while ß-HCH biotransformation was not significant. In case of the enrichment culture, γ-HCH was preferentially transformed over the δ-HCH, ß-HCH and α-HCH isomers. Major observed metabolites in both cases were tetrachlorocyclohexene and as end products monochlorobenzene (MCB) and benzene. Dechlorination of the γ-HCH isomer was linked to an increase in cell numbers for strain 195. γ-HCH transformation was linked to considerable carbon stable isotope fractionation with the enrichment factor εc = - 5.5 ± 0.8‰ for D. mccartyi strain 195, εc = - 3.1 ± 0.4‰ for the enrichment culture and εc = - 4.1 ± 0.6‰ for co-metabolic transformation by C. pasteurianum.

Lindane dissipation in a biomixture: Effect of soil properties and bioaugmentation.

The biomixture is the major constituent of a biopurification system and one of the most important factors in its efficiency; hence the selection of the components is crucial to ensure the efficient pesticides removal. Besides, bioaugmentation is an interesting approach for the optimization of these systems. A mixed culture of the fungus Trametes versicolor SGNG1 and the actinobacteria Streptomyces sp. A2, A5, A11, and M7, was designed to inoculate the biomixtures, based on previously demonstrated ligninolytic and pesticide-degrading activities and the absence of antagonism among the strains. The presence of lindane and/or the inoculum in the biomixtures had no significant effect on the development of culturable microorganisms regardless the soil type. The consortium improved lindane dissipation achieving 81-87% of removal at 66 d of incubation in the different biomixtures, decreasing lindane half-life to an average of 24 d, i.e. 6-fold less than t1/2 of lindane in soils. However, after recontamination, only the bioaugmented biomixture of silty loam soil enhanced lindane dissipation and decreased the t1/2 compared to non-bioaugmented. The biomixture formulated with silty loam soil, sugarcane bagasse, and peat, inoculated with a fungal-actinobacterial consortium, could be appropriate for the treatment of agroindustrial effluents contaminated with organochlorine pesticides in biopurification systems.

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation.

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants - chlordecone (CLD) and beta-hexachlorocyclohexane (ß-HCH) in 1 mg L-1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of ß-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for ß-HCH the major product peak exhibited C3H3Cl2 as most abundant fragment.

Enhanced photocatalytic degradation of lindane using metal-semiconductor Zn@ZnO and ZnO/Ag nanostructures.

To achieve enhanced photocatalytic activity for the degradation of lindane, we prepared metal-semiconductor composite nanoparticles (NPs). Zn@ZnO core-shell (CS) nanocomposites, calcined ZnO, and Ag-doped ZnO (ZnO/Ag) nanostructures were prepared using pulsed laser ablation in liquid, calcination, and photodeposition methods, respectively, without using surfactants or catalysts. The as-prepared catalysts were characterized by using X-ray diffraction (XRD), field-emission scanning electron microscopy, high-resolution transmission electron microscopy, ultraviolet-visible (UV-vis) spectroscopy, and photoluminescence spectroscopy. In addition, elemental analysis was performed by energy dispersive X-ray spectroscopy. The obtained XRD and morphology results indicated good dispersion of Zn and Ag NPs on the surface of the ZnO nanostructures. Investigation of the photocatalytic degradation of lindane under UV-vis irradiation showed that Zn@ZnO CS nanocomposites exhibit higher photocatalytic activity than the other prepared samples. The maximum degradation rate of lindane was 99.5% in 40min using Zn@ZnO CS nanocomposites. The radical trapping experiments verified that the hydroxyl radical (·OH) was the main reactive species for the degradation of lindane.

Important amino acid residues of hexachlorocyclohexane dehydrochlorinases (LinA) for enantioselective transformation of hexachlorocyclohexane isomers.

LinA-type1 and LinA-type2 are two well-characterized variants of the enzyme 'hexachlorocyclohexane (HCH)-dehydrochlorinase'. They differ from each other at ten amino acid positions and exhibit differing enantioselectivity for the transformation of the (-) and (+) enantiomers of α-HCH. Amino acids responsible for this enantioselectivity, however, are not known. An in silico docking analysis identified four amino acids (K20, L96, A131, and T133) in LinA-type1 that could be involved in selective binding of the substrates. Experimental studies with constructed mutant enzymes revealed that a combined presence of three amino acid changes in LinA-type1, i.e. K20Q, L96C, and A131G, caused a reversal in its preference from the (-) to the (+) enantiomer of α-HCH. This preference was enhanced by the additional amino acid change T133 M. Presence of these four changes also caused the reversal of enantioselectivity of LinA-type1 for δ-HCH, and ß-, γ-, and δ-pentachlorocyclohexens. Thus, the residues K20, L96, A131, and T133 in LinA-type1 and the residues Q20, C96, G131, and M133 in LinA-type 2 appear to be important determinants for the enantioselectivity of LinA enzymes.

Ecotoxicological assessment of soils polluted with chemical waste from lindane production: Use of bacterial communities and earthworms as bioremediation tools.

An ecotoxicological survey of soils that were polluted with wastes from lindane (γ-HCH) production assessed the effects of organochlorine compounds on the metabolism of microbial communities and the toxicity of these compounds to a native earthworm (Allolobophora chlorotica). Furthermore, the bioremediation role of earthworms as facilitators of soil washing and the microbial degradation of these organic pollutants were also studied. Soil samples that presented the highest concentrations of ε-HCH, 2,4,6-trichlorophenol, pentachlorobenzene and γ-HCH were extremely toxic to earthworms in the short term, causing the death of almost half of the population. In addition, these soils inhibited the heterotrophic metabolic activity of the microbial community. These highly polluted samples also presented substances that were able to activate cellular detoxification mechanisms (measured as EROD and BFCOD activities), as well as compounds that were able to cause endocrine disruption. A few days of earthworm activity increased the extractability of HCH isomers (e.g., γ-HCH), facilitating the biodegradation of organochlorine compounds and reducing the intensity of endocrine disruption in soils that had low or medium contamination levels.

Study of the genotoxic and cytotoxic effects of the α-, ß-, and γ- Hexachlorocyclohexane isomers in human lymphocyte cells using the cytokinesis-block micronucleus assay.

The genotoxic potential of hexachlorocyclohexane (HCH) isomers (α-, ß-, and γ-) which are organochlorine pesticides was tested in peripheral blood lymphocyte cultures from two donors by using the cytokinesis-block micronucleus assay. Micronucleus (MN) frequency, binucleated cells with micronucleus (BNMN), and cytokinesis-blocked proliferation index (CBPI) were determined as genotoxic and cytotoxic endpoints. At the concentration ranges tested (12.5-100 µg.L -1), all HCH isomers induced dose-dependent cytotoxic effects, γ-HCH being the most toxic. This isomer was also able to induce significant increase in MN frequency and BNMN cells indicating a genotoxic potential at 50 and 100 µg.L -1. The genotoxic test of ß-HCH showed a positive induction of MN and BNMN cells at the highest concentration of 100 µg.L -1 and a significant cytotoxicity at 50 µg.L -1. Under the experimental condition used, α-HCH was unable to induce any significant increase in MN frequency confirming that α-HCH is a non-genotoxic agent.

Occurrence, enantiomeric signature and ecotoxicological risk assessment of HCH isomers and DDT metabolites in the sediments of Kabul River, Pakistan.

Hexachlorocyclohexane (HCH) isomers and dichlorodiphenyltrichloroethane (DDT) metabolites were analyzed in sediments of three different depths (0-10, 10-20 and 20-30 cm) collected from Kabul River, Pakistan, in February 2014. The occurrence levels, enantiomer fractions and potential ecological risk of these organochlorine pesticides (OCPs) were evaluated. The total concentrations of ∑HCHs and ∑DDTs in surface sediments ranged from 4.9-23.9 ng g-1 and from 6.4-18.8 ng g-1 (dry weight basis), respectively. The vertical contamination profile of DDTs was found in order of 20-30 cm >10-20 cm >0-10 cm, indicated that the residue levels of DDTs gradually decreased after it was banned. The ratios of ß-HCH/HCHs ranged from 0.04 to 0.73 (69 % of samples below 0.5) suggesting the fresh input of HCHs, while isomeric ratios of α-HCH/γ-HCH (ranged from 0.02 to 7.94), with 76 % of samples less than 3, indicating the cocktail use of technical grade HCH and lindane in the study area. The ratio of (DDE + DDD)/DDTs (ranged from 0.42 to 0.90) indicated long-term biodegradation of parent DDT. The enantiomer of α-HCH was generally racemic or close to racemic for most of the samples, with enantiomeric fraction (EF) value <0.5 for some of the samples indicated the preferential biodegradation of (+)-α-HCH enantiomer, while for o,p'-DDT the EF values >0.5 indicated the depletion of (-)-o,p'-DDT enantiomer in most of the samples. According to sediment quality guidelines (SQGs), HCH contamination is the main concern for ecotoxicological risk in Kabul River.

The mode of bioturbation triggers pesticide remobilization from aquatic sediments.

After their release into the aquatic environment, contaminants may - depending on the physicochemical properties - adsorb to sediments. From there these contaminants can either be buried or remobilised by abiotic factors (e.g., resuspension) as well as by the bioturbating activity of sediment dwelling invertebrates. Little is, however, know about the effects of bioturbation on the fate of pesticides. Therefore, the present study quantified the impact of the bioturbation mode of benthic invertebrate species (bio-diffusor vs. bio-irrigation), the invertebrate density (i.e. 0-8 individuals per replicate), and the substance-inherent properties (i.e. hydrophobicity, water solubility) on the remobilization of sediment-associated pesticides in a laboratory-based set-up over 13 days. We found that both the bioturbation mode (i.e., species identity) and species density, as well as pesticide properties (i.e., hydrophobicity) affected the direction and magnitude of remobilisation of sediment-bound pesticides. The oligochaeta Lumbriculus variegatus showed a density-dependent effect on the remobilization of lindane to the water phase, whereas those with the amphipod Monoporeia affinis and larvae of the midge Chironomus riparius did not. Although these findings show that sediments not per definition are a sink for pesticides, the rates of pesticide remobilization are limited. This observation, thus, suggests that the risk for aquatic communities posed by the remobilization of pesticides from the sediment due to bioturbation is low.

Evidence of α-, ß- and γ-HCH mixture aerobic degradation by the native actinobacteria Streptomyces sp. M7.

The organochlorine insecticide γ-hexachlorocyclohexane (γ-HCH, lindane) and its non-insecticidal α- and ß-isomers continue to pose serious environmental and health concerns, although their use has been restricted or completely banned for decades. In this study we report the first evidence of the growth ability of a Streptomyces strain in a mineral salt medium containing high doses of α- and ß-HCH (16.6 mg l(-1)) as a carbon source. Degradation of HCH isomers by Streptomyces sp. M7 was investigated after 1, 4, and 7 days of incubation, determining chloride ion release, and residues in the supernatants by GC with µECD detection. The results show that both the α- and ß-HCH isomers were effectively metabolized by Streptomyces sp. M7, with 80 and 78 % degradation respectively, after 7 days of incubation. Moreover, pentachlorocyclohexenes and tetrachlorocyclohexenes were detected as metabolites. In addition, the formation of possible persistent compounds such as chlorobenzenes and chlorophenols were studied by GC-MS, while no phenolic compounds were detected. In conclusion, we have demonstrated for the first time that Streptomyces sp. M7 can degrade α- and ß-isomers individually or combined with γ-HCH and could be considered as a potential agent for bioremediation of environments contaminated by organochlorine isomers.

Application of ligninolytic potentials of a white-rot fungus Ganoderma lucidum for degradation of lindane.

Lindane, a broad-spectrum organochlorine pesticide, has caused a widespread environmental contamination along with other pesticides due to wrong agricultural practices. The high efficiency, sustainability and eco-friendly nature of the bioremediation process provide an edge over traditional physico-chemical remediation for managing pesticide pollution. In the present study, lindane degradation was studied by using a white-rot fungus, Ganoderma lucidum GL-2 strain, grown on rice bran substrate for ligninolytic enzyme induction at 30 °C and pH 5.6 after incorporation of 4 and 40 ppm lindane in liquid as well as solid-state fermentation. The estimation of lindane residue was carried out by gas chromatography coupled to mass spectrometry (GC-MS) in the selected ion monitoring mode. In liquid-state fermentation, 100.13 U/ml laccase, 50.96 U/ml manganese peroxidase and 17.43 U/ml lignin peroxidase enzymes were obtained with a maximum of 75.50 % lindane degradation on the 28th day of incubation period, whereas under the solid-state fermentation system, 156.82 U/g laccase, 80.11 U/g manganese peroxidase and 18.61 U/g lignin peroxidase enzyme activities with 37.50 % lindane degradation were obtained. The lindane incorporation was inhibitory to the production of ligninolytic enzymes and its own degradation but was stimulatory for extracellular protein production. The dialysed crude enzyme extracts of ligninolytic enzymes were though efficient in lindane degradation during in vitro studies, but their efficiencies tend to decrease with an increase in the incubation period. Hence, lindane-degrading capabilities of G. lucidum GL-2 strain make it a potential candidate for managing lindane bioremediation at contaminated sites.