Effect of endosulfan tolerant bacterial isolates (Delftia lacustris IITISM30 and Klebsiella aerogenes IITISM42) with Helianthus annuus on remediation of endosulfan from contaminated soil.

Endosulfan contaminated soil has become an important risk to the environment and human health worldwide. In the present study, endosulfan tolerant bacterial strain Delftia lacustris IITISM30 and Klebsiella aerogenes IITISM42 were isolated from pesticide stressed agricultural soil and tested for plant growth promoting activities. A pot experiment was performed using Helianthus annuus, grown in soil supplemented with endosulfan and inoculated with pure and consortium of bacterial strain IITISM30 and IITISM42. Inoculation increased plant biomass production and endosulfan degradation, maximum degradation (90% at 5 mg kg-1 of soil) was observed by inoculation with a consortium of bacterial strain IITISM30 and IITISM42. Moreover, there was significantly less endosulfan accumulation was observed in roots and shoots of bacterial inoculated plants as compared to uninoculated plants. Decrease in production of malonialdehyde (MDA) was noticed on inoculation of a bacterial strain. The study demonstrated that inoculation of a consortium of endosulfan tolerant plant growth promoting bacterial isolates could more effectively remediate endosulfan contaminated soils and decrease endosulfan residues in plants, than individual strains. Moreover, it revealed that combined use of H. annuus and endosulfan tolerant bacterial isolates IITISM30 and IITISM42 has great potential for remediating endosulfan contaminated soil.

Structure-based design and application of an engineered glutathione transferase for the development of an optical biosensor for pesticides determination.

In the present work, a structure-based design approach was used for the generation of a novel variant of synthetic glutathione transferase (PvGmGSTU) with higher sensitivity towards pesticides. Molecular modelling studies revealed Phe117 as a key residue that contributes to the formation of the hydrophobic binding site (H-site) and modulates the affinity of the enzyme towards xenobiotic compounds. Site-saturation mutagenesis of position Phe117 created a library of PvGmGSTU variants with altered kinetic and binding properties. Screening of the library against twenty-five different pesticides, showed that the mutant enzyme Phe117Ile displays 3-fold higher catalytic efficiency and exhibits increased affinity towards α-endosulfan, compared to the wild-type enzyme. Based on these catalytic features the mutant enzyme Phe117Ile was explored for the development of an optical biosensor for α-endosulfan. The enzyme was entrapped in alkosixylane sol-gel system in the presence of two pH indicators (bromocresol purple and phenol red). The sensing signal was based on the inhibition of the sol-gel entrapped GST, with subsequent decrease of released [H+] by the catalytic reaction, measured by sol-gel entrapped indicators. The assay response at 562 nm was linear in the range pH = 4-7. Linear calibration curves were obtained for α-endosulfan in the range of 0-30 µΜ. The reproducibility of the assay response, expressed by relative standard deviation, was in the order of 4.1% (N = 28). The method was successfully applied to the determination of α-endosulfan in real water samples without sample preparation steps.

Chemotaxis-based endosulfan biotransformation: enrichment and isolation of endosulfan-degrading bacteria.

The study was conducted to isolate endosulfan biotransforming or biodegrading microbes based on chemotaxis. Pseudomonas aeruginosa strain KKc3, Ochrobactrum sp. strain KKc4, Achromobacter xylosoxidans strain KKc6 and Bacillus megaterium KKc7 were isolated based on their migration towards endosulfan in a soil column. Out of the four bacteria, B. megaterium converted endosulfan into toxic metabolite endosulfan sulphate, while the other three bacteria followed the non-toxic endosulfan diol pathway. The mixed culture system consisting of P. aeruginosa, Ochrobactrum sp and A. xylosoxidans could remove 94% of total endosulfan by using endosulfan as the sole source of sulphur.

[Elution of endosulfan from contaminated soil by surfactants and their combination].

The elution efficiency and dynamic characteristic of endosulfan from the contaminated soil were studied using non-ionic surfactants and anionic/non-ionic surfactants in the presence or absence of Na2SiO3 with batch experiment and parallel desorption experiment. The results showed that the elution percents of alpha-, beta-endosulfan followed a decreasing order of Tween 80/SDS, Tween 80 and Triton X-100 in the absence of Na2SiO3, while that by Triton X-100/SDS at low concentration (100-500 mg x L(-1)) and high concentration (800-1000 mg x L(-1)) were lower and higher than those by the corresponding concentrations of Triton X-100, respectively. The elution efficiencies for four elution modes obviously increased in the presence of Na2SiO3, and the elution percents of alpha-, beta-endosulfan followed a decreasing order of Tween 80/SDS, Tween 80, Triton X-100/SDS and Triton X-100, and that of alpha-endosulfan were as 1.17-2.73, 1.87-4.02, 1.85-6.56 and 1.87-2.85 times as that in the absence of Na2SiO3. The elution process of endosulfan could be described by a 4-parameter biphasic first-order kinetic model, and obviously showed a rapid elution phase and a slow elution phase. Both of the elution percent and elution rate of beta-endosulfan were lower than those of alpha-endosulfan, which indicated that beta-endosulfan was difficult to be eluted from soil. The addition of Na2SiO3 could increase the rate constants of rapid elution and slow elution, and decrease the slow elution percent. Compared with other elution modes, Tween 80/SDS in the presence of Na2SiO3 could elute endosulfan from soil more effectively and rapidly, and shown as a fine mixed eluent for endosulfan.

Mycoremediation of endosulfan and its metabolites in aqueous medium and soil by Botryosphaeria laricina JAS6 and Aspergillus tamarii JAS9.

Microbial degradation offers an efficient and ecofriendly approach to remove toxicants from the contaminated environments. Botryosphaeria laricina JAS6 and Aspergillus tamarii JAS9 were capable of degrading endosulfan and their metabolites which were isolated through enrichment technique. Both the strains were able to withstand an exposure of 1300 mg/L and showed luxuriant growth at 1000 mg/L of endosulfan. The change in pH in the culture broth was from 6.8 to 3.4 and 3.8 during growth kinetic studies of JAS6 and JAS9 strains, respectively upon biological degradation of endosulfan. The degradation of endosulfan by JAS6 and JAS9 strains were examined by HPLC. The biodegradation rate constant (k) and the initial concentration were reduced by 50% (DT50) which was determined by first and pseudo first order kinetic models. In the present investigation it has been revealed that Botryosphaeria laricina JAS6 and Aspergillus tamarii JAS9 possessing endosulfan degrading capability are being reported for the first time. These findings confirm the degradation of endosulfan by JAS6 and JAS9 strains which were accompanied by significant reduction in the toxicity and could be used as remedial measure in contaminated environments.

Retention of pesticide Endosulfan by nanofiltration: influence of organic matter-pesticide complexation and solute-membrane interactions.

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.

[Study on removal rule of endosulfan in surface flow constructed wetland].

Endosulfan is a kind of widespread organochlorine pollutant in the environment. The removal rule of three different concentrations of endosulfan in different parts of a surface flow constructed wetland was investigated. The concentrations of endosulfan in water, plants, non-rhizosphere sediments and rhizosphere sediments were determined by the Soxhlet extraction-GC method. The results showed that constructed wetland was efficient in endosulfan removal. The removal rate of endousulfan in water, non-rhizosphere sediments and rhizosphere sediments was 87.9%, 63.0% and 70.9%, respectively. In this system, alpha-endosulfan was removed faster than beta-endosulfan and the metabolite accumulated was mainly endosulfan sulfate. The adsorption of sediments played an important role in the removal of endosulfan. About 80.0% of endosulfan in water could be adsorbed by sediments within three days. The removal rate of endosulfan could be enhanced by plants. Because of the effect of plants, the average removal rate of endosulfan in rhizosphere sediments was 7.9% higher than that in non-rhizosphere sediments.

Adsorptive removal of α-endosulfan from water by hydrophobic zeolites. An isothermal study.

This paper deals with the removal of α-endosulfan from water over HY and steamed HBEA zeolites. Experiments were performed to understand the adsorption mechanisms of α-endosulfan on zeolites and to determine the most efficient adsorbent for the purification of water contaminated by this pesticide. The experiments exhibit that α-endosulfan was adsorbed in the micropores. In the case of HY zeolites an adsorption of α-endosulfan molecules on BrØnsted sites was pointed out, due to a preferential water adsorption in mesopores. Moreover a physisorption of α-endosulfan occurred in micropores. For steamed HBEA zeolites physisorption in micropores was pointed out as the adsorption mode. For both types of zeolites a decrease of the adsorption capacities was noticed when the acidity of zeolites increased. There was also a linear relation between the adsorption capacities of α-endosulfan and the hydrophobicity (HI) of the samples and by determining the values of HI for a type of zeolite it was possible to deduce the uptake of α-endosulfan. The HY(40) sample was the most efficient for the removal of α-endosulfan from water because of preferential adsorption of water molecules in mesopores and lower acidity. For this sample the adsorption capacity for α-endosulfan was about 833.33 mg/g where for the most effective HBEA sample (St700(3)) the adsorption capacity was about 793.65 mg/g.

An efficient calix[4]arene based silica sorbent for the removal of endosulfan from water.

The present work explores sorption behavior of calix[4]arene based silica resin to remove α and ß endosulfan isomers from aqueous solution. The efficiency of resin was checked through both batch and column sorption methods. In both methods, the sorption parameters, i.e. pH, equilibrium time, shaking speed and sorbent dosage were optimized as 2, 60 min, 125 rpm and 50 mg, respectively. Freundlich and Langmuir sorption isotherm models were applied to validate the sorption process. The data obtained in both models reveal that the sorption is favorable. Column sorption data were analyzed through Thomas model to calculate kinetic coefficient k(TH) and maximum sorption capacity q(o) of the resin, which were found to be 6.18 and 5.83 cm(3) mg(-1) min(-1) as well as 1.11 and 1.08 mg g(-1) for α and ß endosulfan, respectively. Kinetics of sorption shows that it follows pseudo second order rate equation. The optimized method has also been applied to real water samples and the results show that calix[4]arene based silica resin is an effective sorbent to remove endosulfan from waste waters.

Fate of pesticides in the arid subtropics, Botswana, Southern Africa.

Despite a history of pesticide usage, few data exist on their concentrations in air and soil of Southern Africa. To add to the understanding of the processes controlling the fate of organic contaminants in arid regions, the levels, spatial trends, and seasonal variability of pesticides were studied in air and soil from Botswana. XAD resin-based passive air samplers (PAS) were deployed at 15 sites across the country from May 2006 to May 2007. Soil samples were collected from the vicinity of nine of the PAS sampling sites. In addition, 27 24-h high-volume air samples were collected in Maun, at the southeastern edge of the Okavango Delta, every two weeks for one year. Levels of pesticides in PAS were low, with α-endosulfan and lindane being most abundant. Concentrations in soils were extremely low and only soils with high organic carbon contained notable amounts of dieldrin and traces of other pesticides. In particular, air and soil from the Okavango Delta had very low levels even though the area had repeatedly been sprayed with DDT and endosulfan in the past. Air samples from Eastern Botswana, where the majority of the population lives, contained higher levels. Higher air concentrations of α-endosulfan occurred during summer and higher HCB levels occurred in winter. This seasonality was related with neither minor seasonal changes in temperature nor hydrological seasonal events such as the rainy season or the flooding of the Okavango Delta. Thus, the observed spatial and seasonal patterns are more likely related to pesticide usage pattern than to environmental factors or historical use. High temperature and low organic matter content limit the uptake capacity of most subtropical soils for pesticides. No evidence was found that sorption to dry mineral matter plays a major role. Arid soils in subtropical regions are therefore neither a major reservoir of organic contaminants nor do they constitute a significant long-term source of pesticides to the atmosphere.

Endosulfan sulfate sorption on natural organic substances.

This work proposes a viable remediation method based on the use of natural organic substances (NOSs) that characterize the Mediterranean region to improve the ecological system. A series of experiments, including variable conditions, such as temperature, pH, contact time, and pesticide concentration, were performed to demonstrate the efficiency of endosulfan sulfate removal from water by NOSs. Experimental results showed that the pH and temperature of pesticide solutions negatively affect the adsorption process. The maximum adsorption capacity for a specific initial concentration of endosulfan sulfate (0.5 microg/L) was achieved with Origanum compactum (75%), followed by Cistus ladaniferus and Raphanus raphanistrum (72 and 68%, respectively). The adsorption tests gave very satisfying results and point to the possible application of these supports as a remediation technique to prevent pesticide contamination of aquatic ecosystems.

Removal of endosulfan and methoxychlor from water on carbon slurry.

A carbon slurry, produced in generators of fuel-oil-based industrial generators was converted into an effective and efficient adsorbent for the removal of endosulfan and methoxychlor from aqueous solution. The adsorbent was chemically treated, activated, characterized, and used for the adsorption of endosulfan and methoxychlor pesticides. The maximum adsorption was found at 90 min, 6.5 pH, 0.025 g/L dose, and 25 degrees C temperature. Langmuir and Freundlich adsorption models were applied to analyze adsorption data, and the former was found applicable to this adsorption system in terms of relatively high regression values. The thermodynamic aspect of the process was also investigated by evaluating certain important parameters (enthalpy, free energy, and entropy of system). Kinetics of adsorption was found to follow the pseudo second order rate equation. The diffusion of pesticides into carbon slurry pores was suggested to be the rate controlling step by applying Bangham's equation. Adsorption on a column was also investigated in a continuous flow system. Adsorption efficiencies of endosulfan and methoxychlor were 34.11 and 36.06 mg/g in batch processes and 32.62 and 33.52 mg/g in column operations, respectively.

Biodegradation and bioremediation of endosulfan contaminated soil.

Among the three mixed bacterial culture AE, BE, and CE, developed by enrichment technique with endosulfan as sole carbon source, consortium CE was found to be the most efficient with 72% and 87% degradation of alpha-endosulfan and beta-endosulfan, respectively, in 20 days. In soil microcosm, consortium AE, BE and CE degraded alpha-endosulfan by 57%, 88% and 91%, respectively, whereas beta-endosulfan was degraded by 4%, 60% and 67% after 30 days. Ochrobacterum sp., Arthrobacter sp., and Burkholderia sp., isolated and identified on the basis of 16s rDNA gene sequence, individually showed in situ biodegradation of alpha-endosulfan in contaminated soil microcosm by 61, 73, and 74, respectively, whereas degradation of beta-endosulfan was 63, 75, and 62, respectively, after 6 weeks of incubation over the control which showed 26% and 23 % degradation of alpha-endosulfan and beta-endosulfan, respectively. Population survival of Ochrobacterum sp., Arthrobacter sp., and Burkholderia sp., by plate count on Luria Broth with carbenicillin showed 75-88% survival of these isolates as compared to 36-48% of survival obtained from PCR fingerprinting. Arthrobacter sp. oxidized endosulfan to endosulfan sulfate which was further metabolized but no known metabolite of endosulfan sulfate was detected.

Removal of endosulfan by sal wood charcoal.

The removal efficiency of endosulfan from water by two low cost adsorbents viz. sal wood (Shorea robusta, family-Diptero carpaceae) charcoal and sand along with activated charcoal as the reference was investigated. For the selection of the suitable adsorbent for endosulfan uptake, the maximum adsorption capacity (Q(max)) was chosen as the main parameter. Using linearized forms of equilibrium models like Langmuir, BET, Freundlich, the maximum adsorptive capacities were determined. It was observed that the efficiency for removal of pesticide is higher in activated charcoal with 94% followed by sand 90%. The efficiency of sal wood charcoal is moderately high with 87% which can be regenerated after treatment with dilute HCl and HNO(3). Though the efficiency of sand is better than sal wood charcoal, it cannot be regenerated.

Pesticide removal from cotton farm tailwater by a pilot-scale ponded wetland.

A pilot-scale, ponded wetland consisting of an open pond and a vegetated pond in series was constructed on a cotton farm in northern New South Wales, Australia, and assessed for its potential to remove pesticides from irrigation tailwater. Ten incubation periods ranging from 7 to 13 days each were conducted over two cotton growing seasons to monitor removal of residues of four pesticides applied to the crop. Residue reductions ranging 22-53% and 32-90% were observed in the first and second seasons respectively. Average half-lives during this first season were calculated as 21.3 days for diuron, 25.4 days for fluometuron and 26.4 days for aldicarb over the entire wetland. During the second season of monitoring, pesticide half-lives were significantly reduced, with fluometuron exhibiting a half-life of 13.8 days, aldicarb 6.2 days and endosulfan 7.5 days in the open pond. Further significant reductions were observed in the vegetated pond and also following an algal bloom in the open pond, as a result of which aldicarb and endosulfan were no longer quantifiable. Partitioning onto sediment was found to be a considerable sink for the insecticide endosulfan. These results demonstrate that macrophytes and algae can reduce the persistence of pesticides in on-farm water and provide some data for modelling.

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil.

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.

Detection and extraction of endosulfan by metal nanoparticles.

One of the most common pesticides in the developing world, endosulfan, can be detected in ppm levels using gold nanoparticles. Endosulfan adsorbs on the nanoparticle surface and upon interaction for a long time, the nanoparticles precipitate from the solution. Interaction with silver is weak, yet adsorption occurs leading to removal of endosulfan from the solution. A multilayer assembly of gold nanoparticles prepared on a glass substrate shows excellent spectrophotometric response suggesting potential applications.

Beta-endosulfan removal from water by ozone oxidation.

Beta-endosulfan solutions were ozonated in a lab scale semi-batch reactor in various experimental conditions. Ozonation kinetics of beta-endosulfan and effects of some parameters such as pH, temperature, partial pressure and ozone dosage on oxidation were investigated. Increasing ozone dosage and decreasing of temperature and pH increased the oxidation rate of beta-endosulfan. Maximum 97% of beta-endosulfan could be removed at both 16-mg/min ozone dosages and pH = 4 for 60 minutes of ozonation. The order of the reaction is determined as pseudo first order. Although the rate of reaction was lower than other pesticide oxidation rates cited in the literature, beta-endosulfan reaction to ozonation was achieved with almost 90% removal rate. The temperature dependent rate constant for beta-endosulfan oxidation was determined as kd = 0.947 exp(-2.16 x 10(-3)/T).

Optimization of solid-phase extraction and solid-phase microextraction for the determination of alpha- and beta-endosulfan in water by gas chromatography-electron-capture detection.

Water contamination due to the wide variety of pesticides used in agriculture practices is a global environmental pollution problem. The 98/83/European Directive requires to measure residues of pesticides at a target concentration of 1.0 microg/l in surface water and 0.1 microg/l in drinking water. In order to reach the level of detection required, efficient extraction techniques are required. Although solid-phase extraction (SPE) is the most common technique for isolation and concentration of pesticides from water, solid-phase microextraction (SPME) is being increasingly applied for this purpose. In this study, a direct-SPME procedure has been developed for the determination of alpha-endosulfan and beta-endosulfan in waters; experimental parameters such as selection of SPME coating, effect of temperature, effect of salt addition, optimization of the sample volume, adsorption and desorption profiles and desorption temperature were studied and optimized. Analytical parameters such as linearity, precision, detection and quantitation limits, and matrix effects for SPE and SPME methods were evaluated for comparison purposes with the aim of selecting the most appropriate for a certain application. Both extraction techniques, SPE and SPME, were followed by gas chromatography with electron-capture detector.