Optimization of isotherm models for pesticide sorption on biopolymer-nanoclay composite by error analysis.

A carboxy methyl cellulose-nano organoclay (nano montmorillonite modified with 35-45 wt % dimethyl dialkyl (C14-C18) amine (DMDA)) composite was prepared by solution intercalation method. The prepared composite was characterized by infrared spectroscopy (FTIR), X-Ray diffraction spectroscopy (XRD) and scanning electron microscopy (SEM). The composite was utilized for its pesticide sorption efficiency for atrazine, imidacloprid and thiamethoxam. The sorption data was fitted into Langmuir and Freundlich isotherms using linear and non linear methods. The linear regression method suggested best fitting of sorption data into Type II Langmuir and Freundlich isotherms. In order to avoid the bias resulting from linearization, seven different error parameters were also analyzed by non linear regression method. The non linear error analysis suggested that the sorption data fitted well into Langmuir model rather than in Freundlich model. The maximum sorption capacity, Q0 (µg/g) was given by imidacloprid (2000) followed by thiamethoxam (1667) and atrazine (1429). The study suggests that the degree of determination of linear regression alone cannot be used for comparing the best fitting of Langmuir and Freundlich models and non-linear error analysis needs to be done to avoid inaccurate results.

Simultaneous removal of pesticides from water by rice husk ash: batch and column studies.

The present study evaluated rice husk ash (RHA) as an adsorbent for simultaneous removal of a mixture of seven different pesticides (alachlor, metolachlor, chlorpyriphos, fipronil, α-endosulfan, ß-endosulfan, and p,p'-DDT) and two metabolites (p,p'-DDE and endosulfan sulfate) from water. The adsorbent RHA was prepared in the laboratory and characterized by techniques such as X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectrometry. Adsorption kinetics were well described by the pseudo-second-order kinetic model. The Freundlich isotherm model fitted the equilibrium data better than the Langmuir model, and the maximum sorption capacity varied from 0.078 to 0.166 mg/g. The column elution studies showed that 10 L of mixed pesticide-contaminated water (0.05 mg/L) can be treated with only 10 g of RHA at a removal efficiency of 90%. The results implied that RHA can be used as a low-cost, easily available, and efficient adsorbent for the simultaneous removal of pesticides from contaminated water.

Simultaneous removal of multiple pesticides from water: effect of organically modified clays as coagulant aid and adsorbent in coagulation-flocculation process.

Contamination of drinking water sources with agrochemical residues became a major concern in the twenty-first century. Coagulation-flocculation is the most widely used water-treatment process, but the efficiency to remove pesticides and other organic pollutants are limited compared to adsorption process. Thus, simultaneous action of adsorption on normal bentonite or organo-modified montmorillonite clays [modified with octadecylamine (ODA-M) and octadecylamine + amino-propyltriethoxysilane (ODAAPS-M)] followed by coagulation-flocculation by alum and poly aluminium chloride has been evaluated for removal of 10 different pesticides, namely atrazine, lindane, metribuzin, aldrin, chlorpyriphos, pendimethalin, alpha-endosulphan, beta-endosulphan, p,p'-DDT, cypermethrin and two of its metabolites, endosulphan sulphate and p,p'-DDE, from water. The coagulation without integration of adsorption was less effective (removal % varies from 12 to 49) than the adsorption-coagulation integrated system (removal % varies from 71 to 100). Further, coagulation integrated with adsorption was more effective when organically modified montmorillonite was used as adsorbent compared to normal bentonite. The removal efficiency of organic clay depends upon the concentration of pesticides, doses of clay minerals, and efficiency was more for ODAAPS-M as compared to ODA-M. The combination of ODAAPS-M-clay with coagulants was also used efficiently for the removal of pesticides from natural and fortified natural water collected and the results exhibit the usefulness of this remediation technique for application in water decontamination and in treatment of industrial and agricultural waste waters.

Removal of mixed pesticides from aqueous solutions using organoclays: evaluation of equilibrium and kinetic model.

Removal of mixed pesticides, namely alachlor, metolachlor, chlorpyriphos, fipronil, α-endosulfan, ß-endosulfan, p,p'-DDT and two metabolites p,p'-DDE and endosulfan sulphate from aqueous solution by batch adsorption onto three commercial organo-modified montmorillonite clays [modified with octadecylamine (ODA-M), modified with dimethyl- dialkylamine (DMDA-M) and modified with octadecylamine and aminopropyltriethoxysilane (ODAAPS-M)] were investigated. Effect of process variables, mainly contact time and initial concentration of mixed pesticides, on adsorption phenomenon were evaluated. To understand the adsorption kinetic pseudo-first-order and pseudo-second-order models were tested. The pseudo-second-order model provided the best fit for explaining adsorption kinetics, on the basis of high correlation coefficient (r) and normalized percent deviation values. The adsorption equilibrium was explained by the Freundlich isotherm (r = 0.951-0.992). High values (0.17-0.52 mg g⁻¹) of Freundlich constant (K(f)) indicated higher affinity of pesticides towards all three organoclays, as a result of hydrophobic interaction between the adsorbent/adsorbate systems. Pesticides with high octanol-water partition coefficient (K(ow)) and low water solubility showed faster adsorption with higher K(f) values as compared to the pesticides with low K(ow) and high water solubility. The order of organoclays for removal efficiency of mixed pesticide was ODAAPS-M > DMDA-M > ODA-M. These findings may find application to decontaminate or treat mixed pesticide contaminated industrial/agricultural waste waters.

Persistence of insecticides in ready-mix formulations and their efficacy against Lipaphis erysimi (Kalt) in cauliflower.

Persistence of cypermethrin, deltamethrin, profenofos, and triazophos in cauliflower curd was studied, following application of two premix formulations viz: Roket 44EC (profenofos 40 % + cypermethrin 4 %) and Anaconda Plus 36EC (triazophos 35 % + deltamethrin 1 %) at recommended (1.0 L ha(-1)) and double doses (2.0 L ha(-1)). In the case of Roket 44EC, residues of cypermethrin dissipated with the half-life values of 1.5-2.1 days, whereas residues of profenofos dissipated with the half-life of 2.9-3.3 days on cauliflower curd. In the case of Anaconda, residues of triazophos and deltamethrin dissipated from curd with the half-life values of 2.6-3.0 and 2.2-2.6 days, respectively. Both the combination mix significantly reduced the aphid population up to 14 days after spray and increased the yield by 155-160 % over control. Anaconda (2.0 L ha(-1)) treated plots yielded the highest number of marketable curds. Based on risk assessment analysis, safe waiting period of 3 and 5 days has been suggested for Roket 44EC and Anaconda Plus 36EC, respectively, in cauliflower at recommended dose of application.

Persistence of new insecticides and their efficacy against insect pests of okra.

Persistence and efficacy of bifenthrin (25 and 50 g ai ha(-1)), fipronil (50 and 100 g ai ha(-1)) and indoxacarb (70 and 140 g ai ha(-1)) has been studied in okra fruits. The initial deposits varied from 0.259-0.382 microg g(-1) at low and 0.461-0.688 microg g(-1) at high rate of application. The residues persisted upto 10 days with half-life of 1.32-1.58 days for bifenthrin, 0.65-1.12 days for fipronil and 0.58-1.02 days for indoxacarb. Based on ADI, the suggested waiting period was 1 day for bifenthrin and indoxacarb and 3 days for fipronil. All the insecticides were found effective against leafhopper and shoot and fruit borer.

Effect of light on the degradation of two neonicotinoids viz acetamiprid and thiacloprid in soil.

Persistence of two neonicotinoids viz thiacloprid and acetamiprid in soil as affected by UV and sunlight exposure was studied. Treated soil was placed in petri-plates, brought to field capacity moisture and then exposed to UV and sunlight. Dissipation for both the pesticides followed monophasic first order kinetics under sunlight, however under UV-light biphasic dissipation was recorded. Residues of acetamiprid and thiacloprid in soil dissipated with half-lives of 11.1 and 12.8 days under UV light and 25.1 and 19.1 days under sunlight, respectively. Residues of both the neonicotinoids dissipated quickly under UV light as compared to sunlight. Exposure of thin film of acetamiprid and thiacloprid to UV and sunlight revealed that acetamiprid is more photo labile than thiacloprid. More than 95% acetamiprid dissipated within 24 h as compared to approximately 70% dissipation observed for thiacloprid.

Soil dissipation and leaching behavior of a neonicotinoid insecticide thiamethoxam.

Persistence and leaching of thiamethoxam in soil were studied under laboratory conditions. The persistence studies carried out at two fortification levels and under three moisture regimes revealed that thiamethoxam persisted beyond 90 days in all the treatments with half-life varying from 46.3 to 301.0 days. Under dry conditions, the dissipation was faster at 10 mg kg(-1) level as compared to 1 mg kg(-1), whereas the reverse trend was observed under field capacity moisture and submerged conditions. The effect of moisture was prominent and longer persistence was observed under dry conditions (t1/2 200.7-301.0 days) followed by field capacity moisture (t1/2 91.2-94.1 days) and submerged condition (t1/2 46.3-75.3 days). The leaching experiment carried out under laboratory conditions showed that on leaching the soil column with water equivalent to 65 cm rainfall, 66-79% of the applied thiamethoxam was recovered from leachate and no residues were detected in soil. Results showed that thiamethoxam has a potential to leach down under heavy rainfall conditions.

Adsorption-desorption, persistence, and leaching behavior of dithiopyr in an alluvial soil of India.

Investigations were undertaken to determine the adsorption-desorption, persistence and leaching of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethyl pyridine-3,5-dicarbothioate) in an alluvial soil under laboratory condition. The adsorption-desorption studies were carried out using batch equilibration technique. The mass balance studies showed that 83-97% of the pesticide was recovered during adsorption-desorption studies. The results revealed strong adsorption of dithiopyr in alluvial soil with Kd values ranging from 3.97-5.78 and Freundlich capacity factor (KF) value of 2.41. The strong adsorption was evident from the hysteresis effect observed during desorption. The hysteresis coefficients ranged from 0.17-0.40. The persistence studies were carried out at two concentrations (1.0 and 10.0 microg g(-1) level) under field capacity moisture and submerged condition by incubating the treated soil at 25 +/- 1 degrees C. In general, dithiopyr persisted beyond 90 days with half-life varying from 11.5-12.9 days under different conditions. The rate of application and moisture regimes had no overall effect on the persistence. The leaching studies carried out in packed column under saturated flow condition revealed that dithiopyr was highly immobile in alluvial soil. Only small amounts (0.02-0.04%) were recovered from leachate whereas major portion (99.9%) remained in top layer of the soil column. The data suggest that strong adsorption of dithiopyr will cause a greater persistence problem in the soil. However, the chances of its movement to ground water will be negligible due to its immobility.

Adsorption-desorption behaviour of flufenacet in five different soils of India.

Adsorption-desorption of the herbicide flufenacet (FOE 5043) has been studied in five soils from different locations in India (Delhi, Ranchi, Nagpur, Kerala and Assam) varying in their physicochemical properties. The organic matter (OM) content varied from 0.072 to 0.864%, clay content from 2.5 to 43.7% and pH from 4.45 to 8.35. The adsorption studies were carried out using a batch equilibration technique. Ten grams of soil were equilibrated with 20 ml of aqueous 0.01 M CaCl2 solution containing different concentrations (0-30 mg litre-1) of flufenacet. After equilibration, an aliquot of supernatant was taken out for analysis. During desorption, the amount withdrawn for analysis was replenished with fresh 0.01 M CaCl2 solution and further equilibrated. Desorption studies were carried out with the 30 mg litre-1 concentration of flufenacet only. The adsorption studies revealed that there was moderate to high adsorption of flufenacet considering the comparatively low organic carbon content in the five test soils. Average Kd values ranged from 0.77 to 4.52 and Freundlich KF values from 0.76 to 4.39. The highest adsorption was observed in Kerala soil (OM 0.786%; clay 25%; pH 4.45) followed by Ranchi, Nagpur and Delhi soils, and the lowest in Assam soil (OM 0.553%; clay 2.5%; pH 6.87). The trend in adsorption could be attributed to the chemical nature of flufenacet and the physicochemical properties of the soil such as pH, OM and clay contents. OM and clay contents were positively correlated whereas pH was negatively correlated. Soils having low pH, high OM and high clay contents showed higher adsorption. Desorption studies revealed that there was a hysteresis effect in all the soils. Hysteresis coefficient values (ratio of n(ad) and n(des)) varied from 0.09 to 0.45. The study implies that, because of its moderate to high adsorption, flufenacet is likely to persist in soil for some time. However, the possibility of its movement by leaching or surface run off is less.

Organochlorine insecticide residues in agricultural soils of the indo-gangetic plain.

Multiple residues of organochlorine insecticides were monitored in the agricultural fields near Farrukhabad in the vicinity of the River Ganga in northern India for one year (1991-1992). Almost all soil samples were found to be contaminated with residues of hexachlorocylohexane (HCH) and dichlorodiphenyl-trichloroethane (DDT). Residues of aldrin and endosulfan were also detected in a large number of samples. Heptachlor residues were scarcely detected. Alpha-HCH, pp'-DDT and alpha-endosulfan were found to dominate over the other isomers/metabolites of HCH, DDT and endosulfan, respectively. The average concentration of dieldrin was more than that of aldrin. The concentrations of residues progressively increased up to a depth of 1 m.

Ground water contamination by organochlorine insecticide residues in a rural area in the indo-gangetic plain.

Residues of several organochlorine insecticides were monitored in the ground water from a rural area near Farrukhabad in the vicinity of the Ganga River in northern India for one year (1991-1992). Almost all the samples were found to be contaminated with residues of Hexachlorocyclohexane (HCH) and Dichloro-diphenyl-trichloroethane (DDT). Residues of Aldrin, endosulfan and heptachlor were also detected in a large number of samples. The concentrations of aldrin residues greatly exceeded the WHO guideline value for drinking water, concentrations of heptachlor and DDT residues also occasionally exceeded the specified limits. Migration of pollutants through ground water recharge with polluted Ganga River water and monsoon rains carrying undergraded residues downwards from the soil surface are throught to be important sources of insecticide contamination of ground water in the region.

Organochlorine insecticide residues in Ganga river water near Farrukhabad, India.

Multiple residues of organochlorine insecticides were monitored in Ganga river water in the district of Farrukhabad in northern Indian for one year (1991-1992). Almost all the samples were found to be contaminated with residues of HCH and DDT. Residues of aldrin, endosulfan and heptachlor were also detected in a larger number of samples. Alpha-HCH, pp'-DDT and alpha-endosulfan were found to dominate over the other isomers of HCH, DDT and endosulfan, respectively. Enhanced percentage of beta-HCH suggests accumulation of this isomer in the aquatic environment. The average concentration of aldrin was more than that of dieldrin. Aldrin residues often exceeded the WHO guideline value for drinking water and the concentration of heptachlor occasionally exceeded the specified limits.