Neera Singh

Adsorption of herbicides on coal fly ash from aqueous solutions.

Development of low cost adsorbent for pesticide retention is an important area of research in environmental sciences. The present study reports the sorption potential of coal fly ash, a waste from power stations, for removal of metribuzin, metolachlor and atrazine from water. Batch sorption method was used to study the sorption of herbicides from water. The amount of herbicides sorbed increased with increase in the amount of fly ash in the suspension. The maximum capacity of the fly ash to adsorb metribuzin, metolachlor and atrazine was found to be 0.20, 0.28 and 0.38 mg/g by Freundlich equation and 0.56, 1.0 and 3.33 mg/g by Langmuir equation. Freundlich adsorption equation better explained the results of herbicides sorption in fly ash as regression coefficient (R(2)) values were higher from Freundlich equation than the Langmuir equation. Adsorption isotherms were L-type suggesting that the herbicide sorption efficiency of fly ash depend on the initial concentration of herbicide in the solution and maximum removal of herbicide was observed at concentrations less than 10 microg/ml. The results of this study have implications in using the fly ash for removal of these herbicides from industrial and agricultural waste water and can find use as a material in the preparation of biobeds to minimize environmental contamination from pesticide use.

Effect of organic manure on sorption and degradation of azoxystrobin in soil.

Information on pesticide degradation and factors influencing are important in predicting the levels of pesticide remaining in soils and allow assessment of potential risk associated with exposure. The present study reports the sorption and degradation of azoxystrobin [methyl (E)-2-{2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl}-3-methoxyacrylate] in a sandy loam soil. The fungicide was moderately sorbed, and the Freundlich adsorption parameter K(f) (1/n) values in natural and 5% compost-amended soils were 9.31 and 13.72, respectively. Sorption showed hysteresis with 32.5 and 14.7% of sorbed fungicide desorbed from the natural and 5% compost-amended soils, respectively. Azoxystrobin was more persistent in the aerobic soil than the anaerobic soil with half-life values of 107.47 and 62.69 days, respectively. Amendment of compost (5%) to the soil enhanced the degradation of fungicide, and the respective half-life values in aerobic and anaerobic soils were 73.39 and 38.58 days, respectively. Azoxystrobin acid was recovered as the only metabolite of azoxystrobin degradation in soils. Both sunlight and UV light affected the persistence of azoxystrobin with fungicide degraded at a faster rate in UV light than in sunlight. Soil acts as a screen and slows the fungicide degradation under sunlight and UV light.

Movement of metolachlor and terbuthylazine in core and packed soil columns.

Movement of metolachlor and terbuthylazine including a bromide tracer was studied in core and packed soil columns in PVC pipes (80 mm diameter, 15 mm depth) with two German soil types viz: silt loam and loamy silt. The breakthrough curves (BTCs) for bromide indicated some preferential flow of water both under conventional tillage (CN) and no-till (NT) simulation with silt loam soil. The herbicides leached to a greater extent in NT columns than in CN columns. Leaching was higher in loamy silt soil than in silt loam soil under CN conditions. This result is in agreement with the higher sorption capacity of silt loam having higher organic carbon compared to loamy silt having low organic carbon. Adsorption strength of the herbicides did not affect their breakthrough time, but was reflected in the slope and maximum height of the BTCs. The BTCs showed the expected inverse relationship between leaching and adsorption with greater mobility of the weakly-sorbed metolachlor than the more strongly sorbed terbuthylazine. Maximum amounts of the applied herbicides were recovered from the top soil layer in intact columns. Metolachlor was more mobile in packed columns than in core columns.

Characterization of pesticide sorption behaviour of slow pyrolysis biochars as low cost adsorbent for atrazine and imidacloprid removal

Agri-wastes biochars viz. eucalyptus bark (EBBC), corn cob (CCBC), bamboo chips (BCBC), rice husk (RHBC) and rice straw (RSBC) and acid treated RSBC (T-RSBC), were characterized for their physico-chemical properties and sorption behaviour of atrazine and imidacloprid was studied. Kinetics study suggested that except atrazine adsorption on RSBC, which was best explained by the pseudo second order model, sorption of atrazine and imidacloprid on biochars was well explained by the modified Elovich model. Among the five normal biochars, the RSBC showed the maximum atrazine (37.5-70.7%) and imidacloprid (39.9-77.8%) sorption. The phosphoric acid treatment of RSBC further enhanced the sorption of both pesticides in T-RSBC. The Freundlich adsorption isotherms were highly nonlinear and percent adsorption decreased with increase in pesticide concentration in solution. Pesticide adsorption on biochars was affected by their aromaticity, polarity, pore diameter, pH and weak acid fraction. Thus, rice straw biochars have great potential for environmental implications and can be exploited as adsorbents for pesticide industry spewed waste water purification.

Hydrolysis of fenamiphos and its oxidation products by a soil bacterium in pure culture, soil and water

Abstract. A bacterium, identified as Brevibacterium sp. MM1, readily hydrolysed fenamiphos, a widely used organophosphorus insecticide and its toxic oxides (fenamiphos sulfoxide, fenamiphos sulfone), which all contain a common P–O–C bond, in a mineral salts medium. The bacterium also hydrolysed fenamiphos and its oxides in soil and groundwater. Interestingly, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, formed during bacterial hydrolysis of fenamiphos and its oxides, persisted in the mineral salts medium, but were transitory in soil and groundwater due to their further metabolism by indigenous micro-organisms. The cell-free preparation (crude enzyme) of this bacterium was very effective in hydrolysing fenamiphos. This is the first report on exceptionally rapid hydrolysis of fenamiphos by a bacterium in pure cultures, soil and groundwater.

Metabolism of 14C-azoxystrobin in water at different pH

Metabolism of 14C-azoxystrobin was studied in water at pH 4, 7 and 9. The study suggested that volatilization losses of azoxystrobin were very low (3%) during 130 days of incubation. Only 2.5–4.2% of azoxystrobin was mineralised to CO2 and pH of water did not have much effect on rate of mineralisation. The dissipation of azoxystrobin in water of all the three pHs followed first order kinetic with half-life values ranging from 143 to158 d; degradation was the fastest at pH 9. Azoxystrobin acid, a major metabolite, was detected 4–7 day onwards and its concentration increased up to 130 days. The formation of azoxystrobin acid was more and faster under alkaline (pH 9) condition than neutral (pH 7) or acidic (pH 4) conditions.

Effect of soil organic matter chemistry on sorption of trinitrotoluene and 2,4-dinitrotoluene

The sorption of organic contaminants in soil is mainly attributed to the soil organic matter (SOM) content. However, recent studies have highlighted the fact that it is not the total carbon content of the organic matter, but its chemical structure which have a profound effect on the sorption of organic contaminants. In the present study sorption of two nitroaromatic contaminants viz. trinitrotoluene (TNT) and 2,4-dinitrotoluene (2,4-DNT) was studied in different SOM fractions viz. a commercial humic acid, commercial lignin and humic acid and humin extracted from a compost. (13)C-DP/MAS NMR studies indicated that the structural composition of the organic carbon in different SOM fractions was different. The order of sorption of the nitroaromatics in the different sorbents was: humic acid-commercial>humic acid-compost>humin approximately lignin. Among the aliphatic and aromatic carbon fractions (representing bulk of SOM matrix), adsorption parameter K(f)(1/n) for nitroaromatics sorption correlated well with the aliphatic carbon (r=0.791 for TNT and 0.829 for 2,4-DNT) than the aromatic carbon (r=0.634 for TNT and r=0.616 for 2,4-DNT). However, among carbon containing functional groups, carbonyl carbon showed strong positive correlation with sorption of TNT (r=0.991) and 2,4-DNT (r=0.967) while O-alkyl carbon showed negative correlation (r=0.832 for TNT and r=0.828 for 2,4-DNT). The study indicates that aliphatic domains in the SOM significantly affect the non-specific sorption of both the nitroaromatic contaminants.

Biocompost from sugar distillery effluent: effect on metribuzin degradation, sorption and mobility.

BACKGROUND Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one) is weakly sorbed in soils and therefore leaches easily to lower soil profiles and results in loss of activity. Soil amendments play an important role in the management of runoff and leaching losses of pesticides from agricultural fields. Therefore, the effect of biocompost from sugarcane distillery effluent on metribuzin degradation and mobility was studied in a sandy loam soil. RESULTS Metribuzin was more persistent in biocompost-unamended (T-0) flooded soil (t(1/2)-41.2 days) than in non-flooded (t(1/2) - 33.4 days) soil. Biocompost application at the rate of 2.5 and 5.0% (T-1 and T-2) in non-flooded soils increased metribuzin persistence, but no significant effect was observed on persistence in flooded soils. Freundlich adsorption constants (K(f)) for treatments T-0, T-1 and T-2 were 0.43, 0.64 and 1.13 respectively, suggesting that biocompost application caused increased metribuzin sorption. Leaching studies in packed soil columns indicated that biocompost application affected both metribuzin breakthrough time and maximum concentration in the leachate. Leaching losses of metribuzin were drastically reduced from 93% in control soil (T-0) to 65% (T-1) and 31% (T-2) in biocompost-amended soils. CONCLUSION Biocompost from sugarcane distillery effluent can be used effectively to reduce downward mobility of metribuzin in low-organic-matter sandy loam soil.

Leaching behaviour of azoxystrobin and metabolites in soil columns.

BACKGROUND Azoxystrobin [methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate], a strobilurin fungicide, is a broad-spectrum, systemic and soil-applied fungicide. Azoxystrobin has been registered for rice cultivation in India, but no information is available on its leaching behaviour in Indian soils. Therefore, leaching behaviour of azoxystrobin was studied in packed and intact soil columns under different irrigation regimes. RESULTS Azoxystrobin did not leach out of the 300 mm long columns after 126 and 362 mm rainfall. After percolating water equivalent to 362 mm rainfall, azoxystrobin leached down to 10-15 cm (packed columns) and 15-20 cm (intact columns) depth. Azoxystrobin was not detected in the leachate from the packed column leached with 94.5 mL water every week (140 mm rainfall per month) during the 28 weeks of the study period. However, azoxystrobin acid, formed by azoxystrobin degradation, was detected in the leachate after 18 weeks. At the end of the study, azoxystrobin had leached down to 5-10 cm depth, and only 60% of initially applied azoxystrobin was recovered from the soil. CONCLUSION The results indicate that azoxystrobin is fairly immobile in sandy loam soil, but azoxystrobin acid, a major metabolite of azoxystrobin, is quite mobile and may pose a threat of soil and groundwater contamination.

Organo-mineral interactions mask the true sorption potential of biochars in soils.

The sorption of carbaryl (1-naphthyl methyl carbamate) and ethion [O,O,O′,O′-tetraethyl S,S′-methylene bis(phosphorodithioate)] was studied in whole soils as well as after treatment of soil with 2% hydrofluoric acid (HF) to remove paramagnetic materials and to oxidize most forms of labile carbon by photo-oxidation with high energy (UV) on < 53 μ m fractions. The sorption coefficient (Kd) values for carbaryl and ethion in soils did not follow the order of their organic carbon (OC) content, and specially their char content However, the Koc values in < 53 μ m fractions after hydrofluoric acid/photo-oxidation with high energy (hydrofluoric acid/ultraviolet; HF/UV) treatment were found to be much higher than those in bulk untreated soils. The effect of organic matter chemistry was determined by correlating Koc values of contaminants in bulk soils or 53 μ m fractions against sample aromaticity. A poor correlation of Koc in bulk soil and aromatic C values of both carbaryl and ethion was observed. However, the correlation between the Koc and the aromatic fraction of C after the HF/UV treatment improved significantly, reflecting the contribution of char fraction of carbon in soils towards sorption of pesticides. The increase in sorption after HF/UV treatment suggested that the sorption potential of biochars, which are expected to contribute significantly to contaminant sorption due to their high surface area, can remain masked by the organo-mineral interactions of char in whole soils. This has implications for the modification of surfaces of the freshly applied biochars in soils due to organo-mineral interactions.