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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, β 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 β-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., (© 2023 Wiley Periodicals LLC.)

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., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

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.

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 EC 50 concentration of alpha-endosulfan, beta-endosulfan, and endosulfan (total) and co-administrated with 1/50th EC 50 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., (Copyright © 2020. Published by Elsevier Inc.)

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 (k cat /K m  = 2.6 s -1 x μM -1 ) and isatin (k cat /K m  = 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 k cat /K m  = 0.23 s -1  μM -1 and k cat /K m  = 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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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.

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-, β-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/β-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 DT 50 are highly correlated (R = 0.9525; n = 28) and no significant difference (P = 0.05) for both methods.

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 N 2 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.

Objectives: To establish an analytical method of the endosulfan concentrations （α-endosulfan and β-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 β-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 β-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 β-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., Competing Interests: The authors of this article and the planning committee members and staff have no relevant financial relationships with commercial interests to disclose., (Copyright© by the Editorial Department of Journal of Forensic Medicine.)

Cytochrome P450 cam (a camphor hydroxylase) from the soil bacterium Pseudomonas putida shows potential importance in environmental applications such as the degradation of chlorinated organic pollutants. Seven P450 cam 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 k cat /K M 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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Abiotic and bacterial degradation is presented for the two isomers α- and β- 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.

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 β-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 β-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.

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 (φ atmosphere  = 64.5-72.5%), which is dominated by the indirect route of volatilization from crop plants (φ atmosphere, indirect  = 54.7-70.3%). In contrast, soil releases are minor (φ soil  = 10.8-20.5%), and are dominated by direct release during application (φ soil, 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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

TiO 2 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., (Copyright © 2015 Elsevier Inc. All rights reserved.)

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 LC 50 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 LC 50 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.

We analyzed concentrations, distribution characteristics, and health risks of endosulfan (α and β 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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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.

The environmental behavior of chlorpyrifos and endosulfan in soil was studied in the central-western region of Brazil by means of a field experiment. Sorption was evaluated in laboratory batch experiments. Chlorpyrifos and endosulfan were applied to experimental plots on uncultivated soil and the following processes were studied: leaching, runoff, and dissipation in top soil. Field dissipation of chlorpyrifos and endosulfan was more rapid than reported in temperate climates. Despite the high Koc of the studied pesticides, the two endosulfan isomers and endosulfan sulfate as well as chlorpyrifos were detected in percolated water. In runoff water and sediment, both endosulfan isomers and endosulfan sulfate were detected throughout the period of study. Observed losses of endosulfan by leaching (below a depth of 50 cm) and runoff were 0.0013 and 1.04% of the applied amount, whereas chlorpyrifos losses were 0.003 and 0.032%, respectively. Leaching of these highly adsorbed pesticides was attributed to preferential flow.

Cast iron has been a material of choice for in-situ remediation of groundwater. In this study interaction of endosulfan with High Carbon Iron Filings (HCIF) was studied in batch reactors. Decline in total concentration (Ct) could be related to aqueous concentration (Ca) by equation dCt/dt = k1.M.Ca(n), where reaction rate constant (k1) and order (n) were found to be 1.246 × 10(-4) L g(-1) iron h(-1) and 1.47, respectively. Partitioning of endosulfan to HCIF could be explained by Freundlich isotherm. The process of simultaneous reductive dehalogenation and adsorption/desorption was successfully modelled. The reductive dehalogenation of endosulfan resulted in by-products identified as [(3a, alpha,7beta,7a alpha,8s)-4,5,6,7,8 Pentachloro 3a,4,7,7a-tetrahydro] (C9H3Cl5O3) and Benzofuran,4,5,7-trichloro-2,3-dihydro-2-methyl (C9H7Cl3O)., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

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-/β-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 β-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 (β-endosulfan) for 72 h exposure. EC50s of α/β-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 β-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., (© 2014 Wiley Periodicals, Inc.)

The present study deals with the investigation of existing pollution levels and potential ecological risk assessment of endocrine-disrupting organochlorine and organophosphorous pesticide residues in the Vasai Creek water near Mumbai. The average concentration of α- and β-endosulfan (137.75 ng·L(-1)) exceeds the chronic criteria level of α- and β-endosulfan (6.5 ng·L(-1)) set by US EPA for freshwater aquatic organisms. The concentration levels of aldrin (75.31 ng·L(-1)), dieldrin (71.19 ng·L(-1)) and endrin (76.60 ng·L(-1)) was found to exceed the respective criteria levels of <0.13, 65.1, and 61 ng·L(-1) as set by US EPA for protection of freshwater aquatic organisms. In addition, the level of chlorpyrifos (208.77 ng·L(-1)) exceeds the recommended concentration value of <35 ng·L(-1) set by Ministry of Environment of British Colombia. The results of our study give an indication of probable ecotoxicological risk to the marine breeding organisms of creek., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Removal efficiencies, kinetics and degradation pathways of aldrin, endosulfan α and endosulfan β in vegetable waste were evaluated during rotary drum and conventional windrow composting. The highest percentage removal of aldrin, endosulfan α and endosulfan β 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 β 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.

The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals.

In order to reveal the residual process of endosulfan in purple soil and protect soil ecological environment, the adsorption and desorption characteristics of endosulfan in purple soil were investigated, and effects of temperature, adsorbent amount, and initial pH of adsorption solution on the adsorption capacity were also examined by static adsorption and desorption experiments. The results showed that the adsorption kinetic process could be well described by the second-order kinetic equation with the initial rate constants of α-, β-endosulfan as 0. 157 and 0. 115 mg.(g.min)-1, respectively. The adsorption thermodynamic process could be well described by the Langmuir isotherm with the maximum adsorption capacities of α-, β-endosulfan as 0. 257 mg . g -1 and 0. 155 mg . g -1, respectively. The adsorption process of endosulfan in purple soil may be an exothermic physicochemical process, and is dominated by physical adsorption. Under the experimental conditions examined in this study, the initial pH of adsorption solution had a relative great influence on the adsorption capacity, whereas the temperature and adsorbent amount had no significant influence. The desorption experiments found that the maximum desorption capacities of α-, β-endosulfan adsorbed in purple soil were 0. 029 mg . g -1 and 0. 017 mg . g -1 at 6 and 4 h, and accounted for 10. 5% and 16. 1% in the maximum adsorption capacities, respectively.

Due to the widespread use of agricultural and residential pesticides, the potential for pesticide soil contamination is a worldwide concern. In response, regulatory jurisdictions in at least 54 nations have promulgated guidance values to specify the maximum allowable concentration of pesticides in soils. Guidance values may be found for more than 700 pesticides. A previous analysis examined the values applied to the original "dirty dozen" persistent organic pollutant (POP) pesticides that were addressed in the 2001 Stockholm Convention (Aldrin, Chlordane, DDT, Dieldrin, Endrin, Heptachlor, Mirex, and Toxaphene). Results are presented here for the "new POP" pesticides that were added to the Stockholm Convention in 2009 and 2011 (isomers of Hexachlorocyclohexane, Chlordecone, and isomers of Endosulfan). The guidance value extremes used worldwide for these pesticides vary by as much as 8.5 orders of magnitude and the randomness in their distributions resembles that of lognormal random variables. However, there are nonrandom value clusters in some distributions that may identify values around which consensuses are forming. The current value distributions imply that a wide range of human health risks are being accepted. Hopefully, the results presented will help regulatory jurisdictions and the regulated communities identify values that should be revised to be adequately protective of human health., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Persistence of delltamethrin, endosulfan, and triazophos in egg plant and tomato was studied following application of two ready mix formulations of insecticides viz. deltametrhin and endosulfan (Cobra 5000; 0.75% deltamethrin + 29.5% endosulfan) and deltamethrin and triazophos (Annaconda Plus; 1% deltamethrin + 35% triazophos) at recommended (1.0 L/ha and double dose 2.0 L/ha). The residues of deltamethrin persisted till 7 and 5 days in tomato and egg plant fruits, respectively, in the ready mix formulation of Cobra 5000 whereas endosulfan persisted till 15 and 10 days in tomato and egg plant fruits, respectively. Dissipation of the insecticides followed first-order kinetics with half-life values of deltamethrin and endosulfan ranged from 2.6 to 4.7 and 1.4 to 1.7 days, respectively, for both the vegetables. In case of combination mix of deltamethrin and triazophos (Annaconda Plus), deltamethrin persisted beyond 5 days in both tomato and egg plant fruits, while triazophos persisted till 10 days in both the vegetables. Residues of deltamethrin and triazophos dissipated with half-life of 2.6-4.2 and 1.7-4.1 days, respectively, on tomato and egg plant fruits. Based on the Codex MRL limits, a safe waiting period of 5 and 3 days is suggested for tomato and egg plant, respectively, for the ready mix formulation of deltamethrin and endosulfan (Cobra 5000), and 5-day waiting period is suggested for tomato and egg plant for the combination mix of deltamethrin and triazophos.

Endosulfan has been included in the list of persistent organic pollutants (POPs) in 2011. The degradation of endosulfan by zero-valent zinc in water and soil was first investigated. The results showed that >90% endosulfan could be degraded in 180 min. The degradation was accelerated under acidic conditions with the absence of dissolved oxygen, while the nature of the soil only exhibited a negligible effect. The half-life was decreased from 130.75 min to 41.75 min with the increment of Zn(0) from 0.1 g to 1 g in soil. The use of Zn(0) was more effective than Fe(0) for the degradation of endosulfan with a half-life of 110 min and 330 min. The cationic surfactant was more effective at enhancing the degradation of endosulfan than anionic and nonionic surfactant. The degradation pathway was speculated, and four chlorine of endosulfan were proposed to be reduced. The method exhibited obvious advantages over traditional endosulfan treatments, and the research results will lay a foundation for practical application of the method., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Endosulfan is enlisted as one of the persistent organic pollutants (POPs) and exists in the form of its α and β isomers in the environment as well as in the form of endosulfan sulfate, a toxic metabolite. General endosulfan toxicity has been investigated in various organisms, but the effect of the isomers and sulfate metabolites on reproductive function is unclear. This study was aimed at studying the reproductive dysfunction induced by endosulfan isomers and its sulfate metabolite in Caenorhabditis elegans (C. elegans). We also determined a role for the DNA-damage-checkpoint gene hus-1. Compared to β-endosulfan and its sulfate metabolite, α-endosulfan caused a dramatically higher level of germ cell apoptosis, which was regulated by DNA damage signal pathway. Both endosulfan isomers and the sulfate metabolite induced germ cell cycle arrest. Loss-of-function studies using hus-1, egl-1, and cep-1 mutants revealed that hus-1 specifically influenced the fecundity, hatchability, and sexual ratio after endosulfan exposure. Our data provide clear evidence that the DNA-checkpoint gene hus-1 has an essential role in endosulfan-induced reproductive dysfunction and that α-endosulfan exhibited the highest reproductive toxicity among the different forms of endosulfan.

The absorption of pesticide endosulfan on the surface of gold nanoparticles results from the formation of micrometric structures (1-10 μm) with irregular shape because of the aggregation of individual particles. Such aggregation of gold nanoparticles after absorption of pesticide shows a surface-enhanced Raman scattering (SERS) spectrum, whose intensity depends on the concentration of endosulfan. In addition, the discoloration of the colloidal solution and a diminishing of the intensity of the surface plasmon resonance absorption from individual particles were observed by UV-visible spectroscopy. At the same time, a second band between 638 and 700 nm confirms the formation of aggregates of gold nanoparticles as the concentration of endosulfan increases. Finally, we used the SERS intensity of the S-O stretching vibration at 1239 cm(-1) from the SO3 group as a measure of concentration of pesticide endosulfan. This method could be used to estimate the level of pollution in water by endosulfan in a simple and practical form.

The removal of endosulfan, an emerging water pollutant, from water was investigated using gamma irradiation based advanced oxidation and reduction processes (AORPs). A significant removal, 97% of initially 1.0 μM endosulfan was achieved at an absorbed dose of 1020 Gy. The removal of endosulfan by gamma-rays irradiation was influenced by an absorbed dose and significantly increased in the presence of aqueous electron (eaq(-)). However, efficiency of the process was inhibited in the presence of eaq(-) scavengers, such as N2O, NO3(-), acid, and Fe(3+). The observed dose constant decreased while radiation yield (G-value) increased with increasing initial concentrations of the target contaminant and decreasing dose-rate. The removal efficiency of endosulfan II was lower than endosulfan I. The degradation mechanism of endosulfan by the AORPs was proposed showing that reductive pathways involving eaq(-) started at the chlorine attached to the ring while oxidative pathway was initiated due to attack of hydroxyl radical at the SO bond. The mass balance showed 95% loss of chloride from endosulfan at an absorbed dose of 1020 Gy. The formation of chloride and acetate suggest that gamma irradiation based AORPs are potential methods for the removal of endosulfan and its by-products from contaminated water., (Copyright © 2014. Published by Elsevier B.V.)

Study focused on effects of temperature, moisture and pH on degradation and degradation kinetics of aldrin, endosulfan (α), endosulfan (β) and lindane during vegetable waste composting using full-scale continuous rotary drum composter (FSCRDC). Extraction, concentration and quantification of pesticides were made from waste material at different stages by ultra-sonification, silica gel column and GC-MS analysis. Removal efficiency of aldrin, endosulfan α, endosulfan β and lindane was found 85.67%, 84.95%, 83.20% and 81.36% respectively due to optimum temperature, moisture, pH and enhanced microbial activity. Maximum temperature in inlet zone was found 60-65°C which is most suitable for complex microbial population. After feeding and turning in inlet zone, temperature reduced to 38°C from 60 to 65°C and regained it within 7-8h, and pH reduced to 5.3±0.2 from 7.5±0.3 in 4h and regained it in 10h. Heterotrophic bacteria Bacillus sp., Pseudomonas sp. and Lactobacillus sp. also decreased from 4.4×10(3) to 7.80×10(2)CFU g(-1) in 2 h due to gradual variation in temperature and pH. No significant temperature change was found in middle and outlet zones during feeding and turning. Degradation of pesticides was observed as first order kinetics and half-life of aldrin, endosulfan α, endosulfan β and lindane was reduced to 25.54, 18.43, 18.43 and 27.43 d from 1095, 60, 270 and 160 d respectively. Thus, the observations in contrast of removal and degradation kinetics of organochlorine pesticides residues in vegetable waste though full-scale rotary drum composting proved it the best suited technique., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

A simple, rapid, accurate and sensitive method using microextraction by packed sorbent (MEPS) followed by GC-MS has been pursued for the determination of organochlorine insecticide endosulfan isomers (α and β) and their metabolites (ether, lactone and sulfate). MEPS is a miniaturised version of SPE employing C18 packing material. It is very efficient technique as it employs as low as 10 μL of sample volume. The distinct feature of MEPS is the magnitude of the elution volume that could be directly injected to GC system. Various parameters such as extraction cycles, washing solvent, elution solvent, elution volume and pH, which influenced the MEPS performance, were tested and optimised. The calibration curves were obtained in the concentration range 1-500 ng/mL. The results showed a close correlation coefficient (R(2) > 0.991) for all analytes in the calibration range studied. The LOD and LOQ obtained for GC-MS under selected ion monitoring acquisition are between 0.0038-0.01 and 0.0125-0.033 ng/mL, respectively. The developed method is applicable for the quantification of these compounds in tap water and commercial samples. This method has been shown to be selective as no interferences from endogenous substances were detected by analysis. This method not only decreases sample preparation time but is cheaper, eco-friendly and easier to perform compared to traditional techniques., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Endosulfan (6,7,8, 9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) is a broad-spectrum, organochlorine insecticide used on numerous crops since the 1950s. It is has been identified as a persistent organic pollutant (POP) due to its persistence, bioaccumulation, long-range transport, and adverse effects to human health and aquatic ecosystems; it will be phased out in the United States in 2016. Endosulfan consists of two diastereomers, α and β; α-endosulfan exists as two asymmetrical, twist-chair enantiomers which interchange, while β-endosulfan has a symmetrical-chair conformation. β-Endosulfan has been shown to isomerize to α-endosulfan. Here we document the previously proposed isomerization mechanism using temperature-dependent Raman (TDR) spectroscopy. The bending frequencies in the fingerprint region were assigned to specific bonds. Changes in the signal intensity as a function of temperature were used to identify detailed ring movements and thus conversion of β to α. These movements cannot occur simultaneously nor symmetrically, precluding conversion of α-endosulfan to β-endosulfan.

This study explored the efficiency of UV-C-based advanced oxidation processes (AOPs), i.e., UV/S2O8(2-), UV/HSO5(-), and UV/H2O2 for the degradation of endosulfan, an organochlorine insecticide and an emerging water pollutant. A significant removal, 91%, 86%, and 64%, of endosulfan, at an initial concentration of 2.45 μM and UV fluence of 480 mJ/cm(2), was achieved by UV/S2O8(2-), UV/HSO5(-), and UV/H2O2 processes, respectively, at a [peroxide]0/[endosulfan]0 molar ratio of 20. The efficiency of these processes was, however, inhibited in the presence of radical scavengers, such as alcohols (e.g., tertiary butyl alcohol and isopropyl alcohol) and natural organic matter (NOM). The inhibition was also influenced by common inorganic anions in the order of nitrite > bicarbonate > chloride > nitrate ≈ sulfate. The observed pseudo-first-order rate constant decreased while the degradation rate increased with increasing initial concentration of the target contaminant. The degradation mechanism of endosulfan by the AOPs was evaluated revealing the main by-product as endosulfan ether. Results of this study suggest that UV-C-based AOPs are potential methods for the removal of pesticides, such as endosulfan and its by-products, from contaminated water., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The recently discovered endosulfan-degrading bacterial strain Alcaligenesfaecalis JBW4 was isolated from activated sludge. This strain is able to use endosulfan as a carbon and energy source. The optimal conditions for the growth of strain JBW4 and for biodegradation by this strain were identified, and the metabolic products of endosulfan degradation were studied in detail. The maximum level of endosulfan biodegradation by strain JBW4 was obtained using broth at an initial pH of 7.0, an incubation temperature of 40 degreeC and an endosulfan concentration of 100 mg/L. The concentration of endosulfan was determined by gas chromatography. Strain JBW4 was able to degrade 87.5% of alpha-endosulfan and 83.9% of beta-endosulfan within 5 days. These degradation rates are much higher than the previously reported bacterial strains. Endosulfan diol and endosulfan lactone were the major metabolites detected by gas chromatography-mass spectrometry; endosulfan sulfate, which is a persistent and toxic metabolite, was not detected. These results suggested that A. faecalis JBW4 degrades endosulfan via a non-oxidative pathway. The biodegradation of endosulfan by A. faecalis is reported for the first time. Additionally, the present study indicates that strain JBW4 may have potential for the biodegradation of endosulfan residues.

Nanofiltration (NF) is a well-established process used in drinking water production to effectively remove Natural Organic Matter (NOM) and organic micropollutants. The presence of NOM has been shown to have contrasting results on micropollutant retention by NF membranes and removal mechanisms are to date poorly understood. The permeate water quality can therefore vary during operation and its decrease would be an undesired outcome for potable water treatment. It is hence important to establish the mechanisms involved in the removal of organic micropollutants by NF membranes in the presence of NOM. In this study, the retention mechanisms of pesticide Endosulfan (ES) in the presence of humic acids (HA) by two NF membranes, TFC-SR2 and TFC-SR3, a "loose" and a "tight" membrane, respectively, were elucidated. The results showed that two mechanisms were involved: (1) the formation of ES-HA complexes (solute-solute interactions), determined from solid-phase micro-extraction (SPME), increased ES retention, and (2) the interactions between HA and the membrane (solute-membrane interactions) increased membrane molecular weight cut-off (MWCO) and decreased ES retention. HA concentration, pH, and the ratio between micropollutant molecular weight (MW) and membrane MWCO were shown to influence ES retention mechanisms. In the absence of HA-membrane interactions at pH 4, an increase of HA concentration increased ES retention from 60% to 80% for the TFC-SR2 and from 80% to 95% for the TFC-SR3 due to ES-HA complex formation. At pH 8, interactions between HA and the loose TFC-SR2 increased the membrane MWCO from 460 to 496 g/mol and ES retention decreased from 55% to 30%, as HA-membrane interactions were the dominant mechanism for ES retention. In contrast, for the "tight" TFC-SR3 membrane the increase in the MWCO (from 165 to 179 g/mol), was not sufficient to decrease ES retention which was dominated by ES-HA interactions. Quantification of the contribution of both solute-solute interactions and solute-membrane interactions is hence fundamental in understanding the removal mechanisms of micropollutant by NF membranes in the presence of NOM in order to optimize the treatment process., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The efficiencies of reductive transformation of endosulfan by bimetallic systems consisting of zerovalent magnesium (Mg(0)) as the electron donor and three forms of palladium as the catalyst (Pd(0)-alumina, Pd(0)-carbon and Pd-K(2)PdCl(6)) were compared in this investigation. Results revealed that both Pd(0)-alumina and Pd(0)-carbon were able to remove 90 and 93% of 10 mg L(-1) of endosulfan, respectively in 30 min with the concomitant accumulation of trace concentrations of partially chlorinated compounds in the reaction medium. Removal of endosulfan followed first-order kinetics and the rate constant (k(obs)) value was computed to be 0.2 min(-1) for both Pd(0)-alumina and Pd(0)-carbon. Pd(0)-carbon was relatively more stable and reusable in comparison to Pd(0)-alumina. More than 99% of 10 mg L(-1) endosulfan was converted to hydrocarbon end product by Pd-K(2)PdCl(6) system within 6 min of reaction. The formation of hydrocarbon end product suggested desulfurization and complete dechlorination of endosulfan. The efficiencies of removal of α and β endosulfan isomers were nearly the same in reaction media containing acetone or Tween 80 as the pesticide solubilizing agents. Results obtained in this study suggest the possibility of developing a reactor containing immobilized palladium for the treatment of water contaminated with endosulfan., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A general procedure to study the biodegradation of endosulfan under laboratory conditions by white rot fungi isolated from native sources growing in YNB (yeast nitrogen base) media with 1% of glucose is presented. The evaluation of endosulfan biodegradation as well as endosulfan sulfate, endosulfan ether and endosulfan alcohol production throughout the whole bioremedation process was performed using an original and straightforward validated analytical procedure with recoveries between 78 and 112% at all concentration levels studied except for endosulfan sulfate at 50 mg L(-1) that yielded 128% and RSDs<20%. Under the developed conditions, the basidiomycete Bjerkandera adusta was able to degrade 83% of (alpha+beta) endosulfan after 27 days, 6 mg kg(-1) of endosulfan diol were determined; endosulfan ether and endosulfan sulfate were produced below 1 mg kg(-1) (LOQ, limit of quantitation)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The fact that ozone is a very powerful oxidizing agent (E0 = +2.07 V) was harnessed to degrade endosulfan and lindane in the present study. An ozone dosage of 57 mg min(-1) was found to be optimal for the degradation of both endosulfan (89%) and lindane (43%). The pH of the reaction mixtures play a profound role on the extent of degradation and it was observed that alkaline conditions favours the generation of hydroxyl radicals and thus a pH of 10 was chosen as the optimum for endosulfan degradation as the degradation efficiency was found to be 93%. A pH value of 12 was chosen as the optimum for lindane degradation as the degradation efficiency was observed to be 82%. Kinetics of degradation was performed and the set of data was fitted into first-order kinetics of the reaction for both endosulfan and lindane. The observed rate constants (k(obs')) for 5, 7.5 and 10 ppm initial endosulfan concentrations were 0.0274, 0.0273 and 0.0161 min(-1), respectively. While for initial lindane concentrations of 5, 7.5 and 10 ppm, the observed rate constants were 0.0243, 0.0333 and 0.056 min(-1), respectively. Gas chromatography mass spectroscopy analysis revealed that endosulfan was degraded into methyl cyclohexane and o-xylene which disappeared as reaction proceeded and lindane was degraded to 1-hexene indicating the ring fission mechanism.

Aerobic bacteria degrading endosulfan were isolated from contaminated sludge. One of the isolates, LD-6, was identified as Stenotrophomonas sp. The bacterium could utilize endosulfan as the sole source of carbon and sulfur. 100 mg/l endosulfan was completely degraded within 10 days, and endosulfan diol and endosulfan ether were detected as major metabolites with a slight decrease in culture pH. The results indicated that Stenotrophomonas. sp. LD-6 might degrade endosulfan by a non-oxidative pathway. Biodegradation of both isomers was relatively better at a temperature range of 25-35 degrees C, with a maximum at 30 degrees C. In addition, cell crude extract of strain LD-6 could metabolize endosulfan rapidly, and degradative enzymes were intracellular distributed and constitutively expressed. Besides, application of the strain was found to promote the removal of endosulfan in soil. This study might help with the future research in better understanding of the biodegradation.

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre(-1). Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T(1/2) = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T(1/2) = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.

Sorption of endosulphan sulphate in soil organic matter was investigated using Standard Elliot soil humic acid (HA) and soil fulvic acid (FA) at two ionic strengths (0.001 and 0.01). It was observed that divalent calcium ion and ionic strength affect the sorption of endosulphan sulphate in HA. All the experiments were carried out at pH 6.7 +/- 0.1. In the presence and absence of calcium (ionic strength 0.001), the solubility enhancement method was used to estimate the sorption coefficients of endosulphan sulphate in HA. For FA, the solubility enhancement method was used to estimate the sorption coefficients at an ionic strength of 0.001 (in the presence of calcium) and 0.01. The presence of calcium was found to significantly enhance (alpha = 0.01) the solubility of endosulphan sulphate in HA. Sorption coefficients at pH 6.7, obtained using the solubility enhancement method, were found to be 10-21 L/g in HA and 6 L/g in FA (in the presence of calcium). Increase in ionic strength from 0.001 to 0.01 decreased the sorption of endosulphan sulphate in HA. The effect of ionic strength and calcium on the sorption of endosulphan sulphate was most satisfactorily explained on the basis of the Donnan volume.

A Mg0/Pd(+4) bimetallic system was evaluated to dechlorinate endosulfan and lindane in the aqueous phase. Studies were conducted with endosulfan and lindane separately, with or without acid in a 1:1 (v/v) water:acetone phase. In the absence of any acid, higher degradation of endosulfan and lindane was observed using Mg0/Pd(+4) doses of 10/0.5 and 4/0.1 mg/mL, respectively. Acetone plays an important role in facilitating the dechlorination reaction by increasing the solubilities of pesticides. Dechlorination kinetics for endosulfan and lindane (30 and 50 mg/L [30 and 50 ppm] concentration of each pesticide) were conducted with varying Mg0/Pd(+4) doses, and the time-course profiles were well-fitted into exponential curves. The optimum observed rate constants (k(obs)) for endosulfan and lindane were obtained with Mg0/Pd(+4) doses of 5/0.5 and 4/0.1 mg/mL, respectively. Gas chromatography-mass spectrometry analyses revealed that endosulfan and lindane were dechlorinated completely into their hydrocarbon skeletons-Bicyclo [2,2,1] hepta 2-5 diene and benzene, respectively.

Concentrations of the insecticide endosulfan (α- and β-isomer) and its degradation product endosulfan sulfate in air, seawater and soil are calculated with the global environmental fate model CliMoChem. As model input, physicochemical properties of all three compounds were assembled and a latitudinally and temporally resolved emission inventory was generated. For concentrations in air, model and measurements are in good agreement; a bimodal seasonality with two peaks in spring and fall as it is observed in Arctic air is reproduced by the model. For seawater, the agreement of model and measurements depends on the values of the hydrolysis activation energy of endosulfan used in the model; with relatively high values around 100 kJ/mol, model results match field data well. The results of this assessment of the levels, persistence, and global distribution of endosulfan are also relevant for the evaluation of endosulfan as a Persistent Organic Pollutant under the Stockholm Convention., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The organochlorine chemicals endosulfan, dieldrin, and γ-hexachlorocyclohexane (lindane) are persistent pesticides to which people are exposed mainly via diet. Their antagonism of the γ-aminobutyric acid-A (GABA(A)) receptor makes them convulsants. They are also endocrine disruptors because of their interaction with the estrogen receptor (ER). Here, we study the effects of dieldrin, endosulfan, and lindane on ERs in primary cultures of cortical neurons (CN) and cerebellar granule cells (CGC). All the compounds tested inhibited the binding of [(3)H]-estradiol to the ER in both CN and CGC, with dieldrin in CGC showing the highest affinity. We also determined the effects of the pesticides on protein kinase B (Akt) and extracellular-regulated kinase 1 and 2 (ERK1/2) phosphorylation. Dieldrin and endosulfan increased Akt phosphorylation in CN, which was inhibited by the ERβ antagonist 4-[2-phenyl-5,7-bis(trifluoromethyl)pyrazolo[1,5-a]pyrimidin-3-yl]phenol. Instead, Akt and ERK1/2 phosphorylation induced by dieldrin in CGC was mediated by multiple activation of ERα, ERβ, and G protein-coupled receptor 30. Lindane did not activate these pathways, but it inhibited estradiol-mediated Akt and ERK1/2 activation. In CN, all the chemicals activated ERK1/2 through a mechanism involving GABA(A) and glutamate receptors. Long-term exposure to these pesticides reduced the levels of ERα, but not of ERβ. Moreover, extracts of CN treated with endosulfan, dieldrin, or lindane induced cell proliferation in MCF-7 human breast cancer-derived cells, whereas only extracts of CGC treated with dieldrin induced MCF-7 cell proliferation. Overall, the observed alterations on ER-mediated signaling and ER levels in neurons might contribute to the neurotoxicity of these organochlorine pesticides.

In the present study, Mg 0/ZnCl 2 bimetallic system was evaluated for its efficiency to dechlorinate endosulfan and lindane in aqueous phase. Presence of acetone in the reaction mixture played an important role by increasing the solubilities of both pesticides and thereby accelerating its mass transfer. Water acetone ratio of 2:1 and 1:1 (v/v) was found optimum for the dechlorination of endosulfan and lindane respectively. Presence of H+ ions in the reaction mixture (50 μl ml(-1) of glacial acetic acid) accelerated the degradation efficiency of 30 ppm initial concentration of endosulfan (96% removal) and lindane (98% removal) at Mg 0/ZnCl 2 dose of 5/1 mg ml(-1) within 30 min of reaction. Dechlorination kinetics for endosulfan and lindane (10, 30 and 50 ppm initial concentration of each pesticide) with varying Mg 0/ZnCl 2 doses and the time course profiles of each pesticide were well fitted into the first order dechlorination reaction. The optimum observed rate constant (k(obs)') values for endosulfan (0.2168, 0.1209 and 0.1614 min(-1) for 10, 30 and 50 ppm initial concentration respectively) and lindane (0.1746, 0.1968 and 0.2253 min(-1) for 10, 30 and 50 ppm initial concentration respectively) dechlorination were obtained when the reactions were conducted with doses of 7.5/1 mg ml(-1) and 5/1 mg ml(-1) Mg 0/ZnCl 2 respectively. Endosulfan and lindane were completely dechlorinated into their hydrocarbon skeletons namely, Bicyclo [2,2,1] hepta 2-5 diene and Benzene respectively as revealed by GCMS analysis., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The metabolizing potential of a bacterial strain Rhodococcus MTCC 6716, isolated from the gut of an Indian earthworm (Metaphire posthuma) was studied for endosulfan bioremediation. In the present work, the optimum conditions for the maximum growth, kinetic of endosulfan degradation, regression equation, half life and correlation coefficient were studied. Endosulfan induced alterations in the expression of mRNA and protein of specific endosulfan metabolizing marker gene (Esd) was studied. Maximum growth of bacteria was observed at pH 7.0, 30°C and 0.085 M sodium chloride concentration in a liquid culture medium. Endosulfan was degraded by Rhodococcus strain up to 97.23% within 15 days without producing toxic metabolite and with strong correlation coefficient (-0.728) and half life 5.99 days. Endosulfan degradation was mediated through gene(s) present in genomic DNA. Expression of marker gene was found endosulfan concentration dependent. The results suggest that this novel strain (Rhodococcus) may be utilized for bioremediation of endosulfan., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatography--mass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L⁻¹ and 0.02 mg kg⁻¹, respectively.

Pesticide distribution in the soil profile depends on soil and pesticide properties as well as on the composition of irrigation water. Water containing surfactants, acids or solvents, may alter pesticide desorption from soil. The distribution of organochlorine pesticides (OCPs) in two Argentinean agricultural areas, Pampa and Patagonia, was evaluated. Furthermore, pesticide desorption from aged and freshly spiked soils was performed by the batch technique, using solutions of sodium oxalate and citrate, dissolved organic carbon (DOC), wastewater and surfactants. Patagonian soil showed the highest OCP levels (46.5-38.1 μg g(-1) OC) from 0 to 30 cm depth and the predominance of p,p'-DDE residues reflected an extensive and past use of DDT. Pampean soil with lower levels (0.039-0.07 μg g(-1) OC) was mainly polluted by the currently used insecticide endosulfan. Sodium citrate and oxalate, at levels usually exuded by plant roots, effectively enhanced desorption of p,p'-DDT, p,p'-DDE and α-cypermethrin, while no effects were observed for α-endosulfan and endosulfan sulfate. The non-ionic surfactant Tween 80 behaved similarly to the acids, whereas the anionic sodium dodecyl sulfate enhanced desorption of all pesticides. Increased desorption of the hydrophobic pesticides also occurred when DOC from humic acids but not from sewage sludge or wastewater were used. Soil profile distribution of pesticides was in accordance with results from desorption studies. Data suggest pesticide leaching in Pampean and Patagonian soils, with risk of endosulfan to reach groundwater and that some organic components of wastewaters may enhance the solubilisation and leaching of recalcitrant compounds such as p,p'-DDT and p,p'-DDE., (Copyright © 2010 Elsevier Ltd. All rights reserved.)