Molecular insight into endosulfan degradation by Ese protein from Arthrobacter: Evidence-based structural bioinformatics and quantum mechanical calculations.

Endosulfan is an organochlorine insecticide widely used for agricultural pest control. Many nations worldwide have restricted or completely banned it due to its extreme toxicity to fish and aquatic invertebrates. Arthrobacter sp. strain KW has the ability to degrade α, ß endosulfan and its intermediate metabolite endosulfate; this degradation is associated with Ese protein, a two-component flavin-dependent monooxygenase (TC-FDM). Employing in silico tools, we obtained the 3D model of Ese protein, and our results suggest that it belongs to the Luciferase Like Monooxygenase family (LLM). Docking studies showed that the residues V59, V315, D316, and T335 interact with α-endosulfan. The residues: V59, T60, V315, D316, and T335 are implicated in the interacting site with ß-endosulfan, and the residues: H17, V315, D316, T335, N364, and Q363 participate in the interaction with endosulfate. Topological analysis of the electron density by means of the Quantum Theory of Atoms in Molecules (QTAIM) and the Non-Covalent Interaction (NCI) index reveals that the Ese-ligands complexes are formed mainly by dispersive forces, where Cl atoms have a predominant role. As Ese is a monooxygenase member, we predict the homodimer formation. However, enzymatic studies must be developed to investigate the Ese protein's enzymatic and catalytic activity.

Biodegradation of Endosulfan-a Chlorinated Cyclodiene Pesticide by Indigenous Pseudomonas sp. MSCAS BT01.

Endosulfan remains as a lipophilic insecticide that causes serious medical problems because of biological stability and toxicity also found in air, water, soil sediments, and foodstuffs. Henceforward, the present study reveals a novel bacterial species isolated from pesticide-contaminated soil for enhanced endosulfan degradation. Next, isolated bacterial species was characterized with biochemical assays and 16S rRNA sequencing technique. Subsequently, the optimal conditions for endosulfan biodegradation such as pH, concentration of endosulfan, and bacterial growth were estimated with non-sulfur medium (NSM). Sequentially, the amount of endosulfan and compound degradation were analyzed through thin-layer chromatography and gas chromatography/mass spectrometry. Overall, the obtained results revealed the endosulfan acting as primary carbon source for bacterial growth. From the GC-MS analysis, the metabolic products released during endosulfan degradation by Pseudomonas sp. MSCAS BT01 were compared with standard GC-MS spectra. The highest (98%) endosulfan degradation was obtained at pH 7.0. The complete endosulfan degradation was achieved at 14th day of incubation and the less toxic endosulfan diol produced was observed via GC-MS. To conclude, the pesticide-contaminated isolate Pseudomonas sp. MSCAS BT01 emerged as a promising bioremediation tool and effectively employed to degrade endosulfan from contaminated soils, sediments, and wastewaters in the days yet to come.

System biology analysis of endosulfan biodegradation in bacteria and its effect in other living systems: modeling and simulation studies.

Endosulfan is a broadly applied cyclodiene insecticide which has been in use across 80 countries since last 5 decades. Owing to its recalcitrant nature, endosulfan residues have been reported from air, water and soil causing toxicity to various non-target organisms. Microbial decontamination of endosulfan has been reported previously by several authors. In the current study, we have evaluated the pathways of endosulfan degradation and its hazardous impact on other living beings including insects, humans, plants, aquatic life and environment by in-silico methods. For establishment of the endosulfan metabolism in different ecosystems, cell designer was employed. The established model was thereafter assessed and simulated to understand the biochemical and physiological metabolism of the endosulfan in various systems of the network. Topological investigation analysis of the endosulfan metabolism validated the presence of 207 nodes and 274 edges in the network. We have concluded that biomagnification of the endosulfan generally occurs in the various elements of the ecosystem. Dynamics study of endosulfan degrading enzymes suggested the important role of monooxygenase I, II and hydrolase in endosulfan bioremediation. Endosulfan shows toxicity in human beings, fishes and plants, however it is biodegraded by the microbes. To date, there are no reports of in- silico analysis of bioremediation of endosulfan and its hazardous effects on the environment. Thus, this report can be important in terms of modelling and simulation of biodegradation network of endosulfan and similar compounds and their impact on several other systems.Communicated by Ramaswamy H. Sarma.

Protective effect of Catharanthus roseus plant extracts against endosulfan and its isomers induced impacts on non-targeted insect model, Drosophila melanogaster and live brain cell imaging.

Endosulfan has been recognized as a highly controversial pesticide due to its acute toxicity, potential bioaccumulation, persistency, and long-range atmospheric transport. Several plant extracts act as antioxidant agents against wide-range of pesticide toxicity hazards through the free radicals scavenging properties. Plants' secondary metabolites are considered as efficient protective agents against various cellular toxic injuries. Understanding these properties of botanicals, several researchers currently focused on the detoxification and ameliorative potency of plant extracts against highly toxic chemicals. In our studies, we focused on the endosulfan total and its isomers (alpha and beta) induced changes on Drosophila melanogaster and their ameliorative effects by co-administrated with methanolic and aqueous extracts of Catharanthus roseus whole plant. We selected the 1/5th EC50 concentration of alpha-endosulfan, beta-endosulfan, and endosulfan (total) and co-administrated with 1/50th EC50 concentration of aqueous and methanolic extracts and evaluated their ameliorative effects, in terms of verifying the life stage activities, protein profiling and also by using live brain cells imaging. We finally concluded that, the methanolic and aqueous extracts inhibit the toxic impacts caused by endosulfan and its isomers and also increasing the survival rate of the test organism.

Degradation of endosulfan by high-energy ball milling with CaO: process and mechanism.

Mechanochemical degradation (MCD) technology has shown its remarkable potential in the disposal of persistent organochlorines in a non-combustion manner. In the present study, endosulfan, as the newly listed persistent organic pollutants (POPs) in the Stockholm Convention, was investigated for its feasibility of mechanochemical destruction using high-energy ball milling. Using calcium oxide (CaO) as a co-milling reagent, the degradation efficiency of endosulfan was nearly 100% after ball milling for 60 min, while the dechlorination efficiency and the sulfate formation efficiency were delayed for endosulfan degradation. After ball milling for 120 min, the dechlorination efficiency and sulfate formation efficiency reached 87.55% and 26.28%, respectively. Based on the measurement results from various material characterization approaches, the main degradation pathway of endosulfan was proposed as sequential dechlorination followed by the destruction of hydrocarbon skeleton. The GC-MS analysis confirmed that complete desulfurization and dechlorination had been realized finally. This study provides an option for the way toward the efficient and rapid destruction of endosulfan as a new POPs using mechanochemical technology.

Carbonyl reductase sniffer from the model organism daphnia: Cloning, substrate determination and inhibitory sensitivity.

Carbonyl reductases (CRs) represent a fundamental enzymatic defense mechanism against oxidative stress. While commonly two carbonyl reductases (CBR1 and CBR3) are found in mammalian genomes, invertebrate model organisms like Drosophila melanogaster express no CR but a functional homolog to human CBR1, termed sniffer. The importance of sniffer could be demonstrated in D. melanogaster where it protected against age-dependent neurodegeneration. Interestingly, the microcrustacean Daphnia harbors four copies of the CR gene (CR1, CR2, CR3, CR4) in addition to one sniffer gene. Due to this unique equipment Daphnia is an ideal model organism to investigate the function of sniffer. Recombinant sniffer from D. magna und D. pules were produced in E. coli, purified by Ni-affinity chromatography and tested with a variety of aliphatic and aromatic diketones, reactive aldehydes and precursors of advanced glycation end products (AGE). The highest catalytic activities were determined for sniffer from D. pulex with the aromatic dicarbonyls 9,10-phenanthrenequinone (kcat/Km = 2.6 s-1 x µM-1) and isatin (kcat/Km = 1.5 s-1 x µM-1). While sniffer from D. magna displayed preference for the same two substances, the respective catalytic activities were noticeably lower. Kinetic constants with aliphatic diketones were generally lower than those with aromatic dicarbonyls for both sniffer enzymes. The best aliphatic diketone as substrate for sniffer from D. magna and D. pulex was hexane-3,4-dione with kcat/Km = 0.23 s-1 µM-1 and kcat/Km = 0.35 s-1 µM-1, respectively. Poor or no detectable activity of the two sniffer enzymes was seen with the aliphatic diketones 2,5-hexanedione and 3,5-heptanedione, the aldehydes butanal, hexanal, decanal, crotonaldehyde, acrolein, trans-2-hexenal, and the AGE precursors glyoxal, methylglyoxal, furfural and glyceraldehyde, indicating no physiological function in the metabolism of short-chain aldehydes. Substrate inhibition for both sniffer enzymes was observed with the quinone substrates 1,4-naphthoquinone and 2-methyl-1,4-benzoquinone. From a variety of pesticides endosulfan turned out as an effective inhibitor of the sniffer enzymes (Ki = 9.2 µM for sniffer from D. magna, Ki = 12.0 µM for sniffer from D. pulex). In conclusion, the present results on sniffer from the protein superfamily of the short-chain dehydrogenases/reductases (SDR) in Daphnia ssp. complement earlier studies on carbonyl reductases in the same species and indicate that Daphnia is an interesting model to study the overall response to carbonyl stress.

Kinetic field dissipation and fate of endosulfan after application on Theobroma cacao farm in tropical Southwestern Nigeria.

Endosulfan, 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano,2,4,3-benzodioxathiepin-3-oxide, is still a pesticide of choice for most cocoa farmers in Southwestern Nigeria, in spite of its persistence, bioaccumulative, toxicological properties, and restriction. A single treatment of 1.4 kg ai/ha (0.5% ai) of technical grade endosulfan (Thiodan, 35EC) was applied to 0.0227 ha of cultivated Theobroma cacao L. (Cocoa) farm at the Cocoa Research Institute of Nigeria (CRIN). Levels of parent endosulfan (α-, ß-endosulfan) and major metabolite (endosulfan sulfate) were determined in vegetation and surrounding matrices at days 0, 7, 14, 21, 28, 42, and 60 using GC-MS. Their kinetic variables were determined. Order of ∑endosulfan distribution at day 0 was dry foliage > fresh foliage > bark > pods > soil (0-15 cm). No residual endosulfan was found in cocoa seeds and subsurface soil (15-30 cm). Low residual levels in pods on day 0 may be due to endogenous enzymatic breakdown, with α-isomer more susceptible and α/ß-endosulfan ratio being 0.90. Fell dry foliage as mulch was predominantly the receiving matrix for non-target endosulfan sprayed. Volatilization was key in endosulfan dissipation between days 0 and 7 from foliage surfaces (> 60% loss), while dissipation trend was bi-phasic and tri-phasic for vegetation and soil, respectively. ∑endosulfan loss at terminal day ranged between 40.60% (topsoil) and 99.47% (fresh foliage). Iteratively computed half-lives (DT'50) ranged from 6.48 to 30.13 days for ∑endosulfan in vegetation. Endosulfan was moderately persistent in pods-a potential source for cross contamination of seeds during harvest. Iteratively determined DT'50 and initial-final day DT50 are highly correlated (R = 0.9525; n = 28) and no significant difference (P = 0.05) for both methods.

Determination of Endosulfan Concentrations in Biological Samples by GC-MS/MS.

OBJECTIVES: To establish an analytical method of the endosulfan concentrations （α-endosulfan and ß-endosulfan） in biological samples by GC-MS/MS. To observe the distribution of endosulfan in aquatic animals and provide experimental evidence for forensic identification of relevant cases. METHODS: Acetonitrile was added to the blood and muscle samples for precipitating the protein. The endosulfan concentrations were determined by GC-MS/MS in multiple reaction monitoring mode. Qualitative analysis was performed according to the retention time and ion rate, and quantitative analysis was performed by external standard working curve method. RESULTS: In blood samples, the calibration curves of α-endosulfan and ß-endosulfan ranging from 0.062 5 to 10 µg/mL had good linear relationship, the correlation coefficients （r） of which were >0.99. The limits of detection （LOD） were 1 ng/mL and 2 ng/mL and the limits of quantification （LOQ） were 4 ng/mL and 8 ng/mL, respectively. In muscle samples, the calibration curves of α-endosulfan and ß-endosulfan ranging from 0.062 5 to 10 µg/g, the r of which were >0.98. The LOD were 1 ng/g and 4 ng/g and the LOQ were 4 ng/g and 16 ng/g, respectively. The accuracy of α-endosulfan and ß-endosulfan was 90.76%-108.91% both in blood and muscle samples, the interday and intraday precision were 2.35%-8.71% and 5.44%-10.29%, respectively. In poisoning cases, endosulfan were detected in all parts of fish and crab and the content difference was statistically significant. CONCLUSIONS: The endosulfan detection method based on GC-MS/MS established in the present study is rapid, sensitive and accurate, which can be applied to the endosulfan detection in traces biological samples. The distribution of endosulfan in fish and crab was different, which can provide evidence to the sample collection and analysis for toxicological analysis in relevant forensic identification.

Solvent effect on endosulfan adsorption onto polymeric arginine-methacrylate cryogels.

Endosulfan is a persistent insecticide that is still used in some countries even though it is life-threatening and banned in the agricultural struggle. The solubility of pesticides in water is negligible. It is known that pesticides with better solubility in organic solvents have different solubility when the dielectric constants of these solvents are taken into account. The polymeric structure of arginine was modified with methacrylate to be a functional monomer, and it was immobilized on a solid support, poly(HEMA), and finally, poly(2-hydroxyethyl methacrylate-arginine methacrylate) was obtained and used as an effective adsorbent. The effect of organic solvents on endosulfan adsorption was investigated for the first time in the literature. Endosulfan was removed from alcohol media by using this polymeric structure synthesized by exploiting alcoho-phobic interaction in this work. Nuclear magnetic resonance (NMR), elemental analysis, and Fourier transform infrared spectroscopy (FTIR) methods were used for the structural characterization and therefore to prove successful synthesis of cryogels. Morphological characteristics were also investigated by scanning electron microscopy (SEM), an N2 adsorption method, and swelling test. Adsorption experiments were carried out against varying interaction time and concentration parameters in the batch system. Since the alcohol used as a solvent has a pH value close to the ionic strength of drinking water, no change was made in the pH of the solution. Endosulfan molecules dissolved in solvents such as toluene, dichloromethane, acetone, and chloroform were removed using poly(HEMA-ArMA) cryogels to determine the solvent effect on the adsorption of endosulfan. As expected, the removal of endosulfan from the solvent toluene provided the best result. Although the adsorption in toluene is almost 9.5 times higher than that in ethanol, the use of toluene in the adsorption process due to its chemical structure is not feasible. Thus, experiments were carried out in ethanol.

Selecting of a cytochrome P450cam SeSaM library with 3-chloroindole and endosulfan - Identification of mutants that dehalogenate 3-chloroindole.

Cytochrome P450cam (a camphor hydroxylase) from the soil bacterium Pseudomonas putida shows potential importance in environmental applications such as the degradation of chlorinated organic pollutants. Seven P450cam mutants generated from Sequence Saturation Mutagenesis (SeSaM) and isolated by selection on minimal media with either 3-chloroindole or the insecticide endosulfan were studied for their ability to oxidize of 3-chloroindole to isatin. The wild-type enzyme did not accept 3-chloroindole as a substrate. Mutant (E156G/V247F/V253G/F256S) had the highest maximal velocity in the conversion of 3-chloroindole to isatin, whereas mutants (T56A/N116H/D297N) and (G60S/Y75H) had highest kcat/KM values. Six of the mutants had more than one mutation, and within this set, mutation of residues 297 and 179 was observed twice. Docking simulations were performed on models of the mutant enzymes; the wild-type did not accommodate 3-chloroindole in the active site, whereas all the mutants did. We propose two potential reaction pathways for dechlorination of 3-chloroindole. This article is part of a Special Issue entitled: Cytochrome P450 biodiversity and biotechnology, edited by Erika Plettner, Gianfranco Gilardi, Luet Wong, Vlada Urlacher, Jared Goldstone.

Impact of the composition of the bacterial population and additional carbon source on the pathway and kinetics of degradation of endosulfan isomers.

Abiotic and bacterial degradation is presented for the two isomers α- and ß- of the organochlorine pesticide endosulfan, denoted as ES-1 and ES-2, respectively. Biodegradation studies were conducted with two indigenous species Pseudomonas putida (P. putida) and Rhodococcus sp. Both ES isomers rapidly hydrolyzed in water at pH ≥ 7 but the hydrolysis was inhibited in the presence of biomass. The pesticide partitioned onto the biomass making it unavailable for abiotic hydrolytic reaction. Spontaneous temperature dependent abiotic conversion of ES-2 to ES-1 was reported in the presence of dual air-water phases but was not observed in the abiotic aqueous phase. Biodegradation experiments with pure isomers showed a small amount of interconversion (∼5%) in either direction and ruled out any preferential interconversion of the ES-2 isomer to ES-1 or vice versa. Both the species were shown to degrade ES-2 at a higher rate compared to ES-1 which may lead to enrichment of ES-1 in agricultural fields in short-term following application of the pesticide. P. putida degraded both the ES isomers through oxidative and hydrolytic pathways while the Rhodococcus sp. used only the hydrolytic pathway. Since ES-S (product of the oxidative pathway) is orders of magnitude more toxic than the parent isomers, the short term toxicity of a field following the application of the pesticide may increase if the composition of the indigenous bacterial population is such that the oxidative pathway is preferred over the hydrolytic one. The presence of an additional carbon source increased the rates of degradation of both the isomers but the enhancement was greater for the degradation rate of ES-2 than ES-1.

Adsorption and desorption characteristics of endosulfan in two typical agricultural soils in Southwest China.

Endosulfan is an organochlorine pesticide widely used in Southwest China. In this paper, the adsorption and desorption characteristics of endosulfan in two typical agricultural soils (latosol and lateritic red soil) in this area were studied. The results showed that Langmuir isothermal equation could well describe the adsorption thermodynamic characteristics of endosulfan in latosol and lateritic red soil, and the maximum adsorption capacities of α-endosulfan were 0.186 and 0.209 mg/g, while those of ß-endosulfan were 0.140 and 0.148 mg/g, respectively. Endosulfan adsorption in the two soils was an exothermic physicochemical process, but dominated by physical process. The adsorption kinetic characteristics of endosulfan in the two soils could be well described by second-order kinetic equation, and the initial rate constants were 0.228 and 0.325 mg/(g min) for α-endosulfan, while those were 0.119 and 0.125 mg/(g min) for ß-endosulfan, respectively. The adsorbed endosulfan in the two soils was difficult to be desorbed into the liquid phase, and showed weak desorption hysteresis. These results implied that endosulfan could be firmly adsorbed by the two soils, and their adsorption and desorption abilities may be related to the contents of soil clay and organic matter.

Distribution mode and environmental risk of POP pesticides such as endosulfan under the agricultural practice of straw incorporating.

The practice of incorporating post-harvest crop waste is widely used because it maintains soil fertility and avoids environmental pollution from straw burning. However, the practice of straw incorporation may also retain the pesticides that are applied to crop plants, which may pose a potential long term risk to local and regional environments if the applied pesticide is a Persistent, Bioaccumulative, and Toxic (PBT) substance or a Persistent Organic Pollutant (POP). Here we investigate the influence of the "receiving-retention-release" route on the distribution of a POP pesticide (endosulfan) and the associated environmental risk among different environmental compartments. Our study indicates that most endosulfan enters the atmosphere (φatmosphere = 64.5-72.5%), which is dominated by the indirect route of volatilization from crop plants (φatmosphere, indirect = 54.7-70.3%). In contrast, soil releases are minor (φsoil = 10.8-20.5%), and are dominated by direct release during application (φsoil, direct = 8.0-18.0%). Under the practice of straw incorporation, the use of endosulfan posed an environmental risk to agricultural soil. In addition, the atmospheric deposition of endosulfan also posed an environmental risk to sediment. The study highlights the significance of the "receiving-retention-release" route by crop plants in determining the fate of POP pesticides associated with straw incorporation; hence complementing the current methodology for assessing the environmental risk of these compounds.

Evaluation of cytotoxicity and genotoxicity of pesticide mixtures on lymphocytes.

The cytotoxicity and genotoxicity of pesticide mixtures viz. endosulfan + chlorpyrifos, chlorpyrifos + profenofos, and endosulfan + profenofos were evaluated on cultured human peripheral blood lymphocytes using assays for cell viability, and genotoxicity using chromosomal aberrations test and comet assay. The LC50 values for cytotoxicity were 3.50 µM, 4.18 µM, and 10.5 µM for profenofos, endosulfan, and chlorpyrifos respectively. When combined in equimolar concentrations, the LC50 values for cytotoxicity were 1.4 µM, 1.8 µM, and 2.0 µM for endosulfan + chlorpyrifos, chlorpyrifos + profenofos, and endosulfan + profenofos, respectively. Higher concentrations of individual pesticides (0.5-4.0 µM) but very low concentrations of pesticide mixtures caused significant DNA damage. Additive index values indicated a synergistic effect of toxicity for endosulfan + chlorpyrifos combination (1.12 TTU). The binary mixture of chlorpyrifos + profenofos showed an additive toxicity (0.46 TTU) while an antagonistic effect was observed for endosulfan + profenofos combination. Synergism could be due to these complementary pesticides simultaneously acting in different ways, magnifying their efficacy, whereas an additive interaction would imply that the chemicals are acting by the same mechanism and at the same target. Analysis of toxicity of pesticide mixtures may serve as important biomarker for occupational and household exposure to pesticides, with different modes of action.

Spatial distribution, transport dynamics, and health risks of endosulfan at a contaminated site.

We analyzed concentrations, distribution characteristics, and health risks of endosulfan (α and ß isomers, and endosulfan sulfate) in soils (top soils and soil profiles) and air, at and around a typical endosulfan production site in Jiangsu, China. The air-soil surface exchange flux is calculated to investigate transport dynamics of endosulfan. Concentrations at the production site ranged from 0.01 to 114 mg/kg d.w. in soil and 4.81-289 ng/m(3) in air, with very high concentrations occurring at the location of endosulfan emulsion workshop. In the surrounding area, endosulfan was detected in all samples, with concentrations ranging from 1.37-415 ng/g d.w. in soil and 0.89-10.4 ng/m(3) in air. In the contaminated site, endosulfan concentrations fluctuated with depth in the upper soil layers, then decreased below 120 cm. Soil and air within a distance of 2.0 km appear to be affected by endosulfan originating from the site. Even the health risk at the location of the endosulfan emulsifiable solution workshop was over seven times the acceptable value, the risk to nearby adults and children was low.

Gamma radiolytic decomposition of endosulfan in aerated solution: the role of carbonate radical.

The present study elaborates the removal of endosulfan, an emerging water pollutant and potential carcinogenic, in aerated solution. The influence of Cl(-), NO3 (-), NO2 (-), CO3 (2-), HCO3 (-), SO3 (2-), and humic acid was assessed on the radiolytic degradation of endosulfan. A strong inhibition on the radiolytic degradation of endosulfan was observed in the presence of NO3 (-), NO2 (-), and SO3 (2-). Instead, a slight increase in the removal efficiency of endosulfan was observed at high concentrations of CO3 (2-) and HCO3 (-). The formation of CO3 (•-) in radiolytic degradation of endosulfan in the presence of CO3 (2-) and HCO3 (-) was demonstrated by adding SO3 (2-) that rapidly react with CO3 (•-). The results indicate that CO3 (•-) formed from the reactions of CO3 (2-) and HCO3 (-) and commonly found in natural water can play an important role in the degradation of endosulfan and other sulfur containing electron-rich compounds. The study showed faster degradation of endosulfan at lower concentration compared to high concentration and removal was found to follow pseudo-first-order kinetic. Endosulfan ether was found as the main degradation product and degradation pathway was found to be initiated at the S=O bond of endosulfan. The efficiency of gamma irradiation in the removal of endosulfan was examined in terms of formation of short chain organic acids and chloride ion accumulation.

Degradation of aldrin and endosulfan in rotary drum and windrow composting.

Removal efficiencies, kinetics and degradation pathways of aldrin, endosulfan α and endosulfan ß in vegetable waste were evaluated during rotary drum and conventional windrow composting. The highest percentage removal of aldrin, endosulfan α and endosulfan ß in rotary drum composting was 86.8, 83.3 and 85.3% respectively, whereas in windrow composting, it was 66.6%, 77.7% and 67.2% respectively. The rate constant of degradation of aldrin, endosulfan α and endosulfan ß during rotary drum composting ranged from 0.410-0.778, 0.057-0.076 and 0.009-0.061 day(-1) respectively. The pathways of degradation of these pesticides in composting process were proposed. Metabolites dieldrin and 1 hydroxychlorodene formed during composting of aldrin in the vegetable waste indicated the occurrence of epoxidation reaction and oxidation of bridge carbon of aldrin containing the methylene group. Formation of chloroendic acid and chloroendic anhydride during composting of endosulfan containing vegetable waste support the occurrence of endosulfan sulfate and dehydration reaction respectively.

Chlorpyrifos and Endosulfan degradation studies in an annular slurry photo reactor.

TiO2 is one of those compounds which are highly used in photocatalytic degradation of substrates using UV radiation. The substrates are degraded oxidatively and hence finds an important position in advanced oxidation for water/wastewater treatment processes. The thrust of this research was to evaluate the effectiveness of Heterogeneous Photocatalysis (HP) technique, for the removal of pesticides from water/wastewater. The photo-catalytic degradation of two pesticides, widely used in India, viz., Endosulfan (ES) and Chlorpyriphos (CPS) was studied in an annular slurry photo reactor under UVillumination at 254nm. Results revealed that the degradation rate is significantly affected by the initial pesticide concentration, pH of the solution and catalyst concentration. Batch degradation studies on Endosulphan and Chlorpyrifos were conducted in the concentration range from 5 to 25mg/L at a pH ranging from 3.5 to 10.5 and at a catalyst loading of 0.5-2g/L. Endosulphan removal efficiency was about 80-99% and chlorpyrifos removal efficiency was about 84-94%. L-H rate constants were determined using L-H kinetics. High removal efficiencies obtained (80-99%) indicate the effectiveness of this process and its potential for practical application.

Residues of endosulfan in surface and subsurface agricultural soil and its bioremediation.

The persistence of many hydrophobic pesticides has been reported by various workers in various soil environments and its bioremediation is a major concern due to less bioavailability. In the present study, the pesticide residues in the surface and subsurface soil in an area of intense agricultural activity in Pakkam Village of Thiruvallur District, Tamilnadu, India, and its bioremediation using a novel bacterial consortium was investigated. Surface (0-15 cm) and subsurface soils (15-30 cm and 30-40 cm) were sampled, and pesticides in different layers of the soil were analyzed. Alpha endosulfan and beta endosulfan concentrations ranged from 1.42 to 3.4 mg/g and 1.28-3.1 mg/g in the surface soil, 0.6-1.4 mg/g and 0.3-0.6 mg/g in the subsurface soil (15-30 cm), and 0.9-1.5 mg/g and 0.34-1.3 mg/g in the subsurface soil (30-40 cm) respectively. Residues of other persistent pesticides were also detected in minor concentrations. These soil layers were subjected to bioremediation using a novel bacterial consortium under a simulated soil profile condition in a soil reactor. The complete removal of alpha and beta endosulfan was observed over 25 days. Residues of endosulfate were also detected during bioremediation, which was subsequently degraded on the 30th day. This study revealed the existence of endosulfan in the surface and subsurface soils and also proved that the removal of such a ubiquitous pesticide in the surface and subsurface environment can be achieved in the field by bioaugumenting a biosurfactant-producing bacterial consortium that degrades pesticides.

Isomers and their metabolites of endosulfan induced cytotoxicity and oxidative damage in SH-SY5Y cells.

As an organochlorine insecticide, endosulfan has been widely banned or restricted, but it is still largely used in many developing countries. Previous studies have shown multiple adverse health effects of endosulfan. However, the neurotoxicity of endosulfan has not been fully elucidated. In this study, endosulfan isomers (α-/ß-endosulfan) and their major metabolites (endosulfan sulfate, endosulfan diol, and endosulfan lactone) were, respectively, exposed to human neuroblastoma SH-SY5Y cells. Results showed that both α-endosulfan and ß-endosulfan caused decrease of cell viability and morphological damages in a dose-dependent manner. Their median effective concentrations (EC50s) were respectively 79.6 µM (α-endosulfan) and 50.37 µM (ß-endosulfan) for 72 h exposure. EC50s of α/ß-endosulfan mixture were lower than that of the single isomer. However, EC50s of its metabolites were higher than that of technical endosulfan. Endosulfan and its metabolites caused increases of reactive oxygen species and the lipid peroxidation, but decrease of superoxide dismutase in a dose-dependent manner. These results indicate that α-endosulfan exhibits higher neurotoxicity than ß-endosulfan. Mixture of endosulfan isomers shows stronger cytotoxicity than the single isomer. After endosulfan is degraded, cytotoxicity of its metabolites decreases gradually. The neurotoxicity of endosulfan and its metabolites is closely related to oxidative damage and antioxidative deficit.