Crop residue heterogeneity: Decomposition by potential indigenous ligno-cellulolytic microbes and enzymatic profiling.

The continuous depletion of fossil resources, energy-crisis and environmental pollution has gained popularity for careful selection of suitable microbial consortium to efficiently decompose crop residue and facilitate nutrient cycling. While crop residue is commonly incorporated into soil, the impact of the heterogeneity of residue on decomposition and biological mechanisms involved in extracellular carbon (C) cycle related enzyme activities remain not fully understood. To address this problem, an incubation study was conducted on chemical heterogeneity of straw and root residue with indigenous ligno-cellulolytic microbial consortium on extracellular enzymes as their activity is crucial for making in-situ residue management decisions under field condition. The activity of extracellular enzymes in different substrates showed differential variation with the type of enzyme and ranged from 16.9 to 77.6 µg mL-1, 135.7 to 410.8 µg mL-1, 66.9 to 177.1 µg mL-1 and 42.1 to 160.9 µg mL-1 for cellulase, xylanase, laccase and lignin peroxidase, respectively. Extracellular enzyme activities were sensitive to heterogeneity of biochemical constituent's present in straw and root residues and enhanced the decomposition processes with indigenous ligno-cellulolytic microbial consortium (Bacillus altitudinis, Streptomyces flavomacrosporus and Aspergillus terreus). Correlation matrix elucidated A. terreus and B. altitudinis as potential indigenous ligno-cellulolytic microbial inoculant influencing soil enzymatic activity (p < 0.001). This research work demonstrates a substantial impact of chemically diverse crop residues on the decomposition of both straw and root. It also highlights the pivotal role played by key indigenous decomposers and interactions between different microorganisms in governing the decomposition of straw and root primarily through release of extracellular enzyme. Consequently, it is novel bio-emerging strategy suggested that incorporation of the crop residues under field conditions should be carried out in conjunction with the potential indigenous ligno-cellulolytic microbial consortium for efficient decomposition in the short period of time under sustainable agriculture system.

Insights into adsorption performance and mechanism of chitosan-bentonite biocomposites for removal of imazethapyr and imazamox.

In the present study, chitosan-bentonite biocomposites were synthesised by ultrasonication, characterized using spectral techniques and assessed for their effectiveness in removing imazethapyr and imazamox from aqueous solution. The response surface methodology based box behnken design was utilized to generate optimum conditions viz. pH (1 to 9), adsorbent dose (0.01 to 1.0 g), contact time (0.5 to 48 h) and temperature (15 to 55 °C) for adsorption of herbicides on biocomposites. Based on model predictions, 60.4 to 91.5 % of imazethapyr and 31.7 to 46.4 % of imazamox was efficiently removed under optimal conditions. Adsorption data exhibited a strong fit to pseudo-second-order kinetic (R2 > 0.987) and Freundlich isotherm (R2 > 0.979). The adsorption capacity ranged from 3.88 to 112 µg1-ng-1mLn and order of adsorption was: low molecular weight chitosan-bentonite> medium molecular weight chitosan-bentonite> high molecular weight chitosan-bentonite> bentonite. Thermodynamic experiments suggested a spontaneous, exothermic process, reducing the system randomness during adsorption. Desorption experiments revealed successful desorption ranging from 91.5 to 97.0 % using 0.1 M NaOH. The adsorption mechanism was dominated by synergistic electrostatic interactions and hydrogen bonding. These results collectively indicated the potential environmental remediation application of chitosan-bentonite biocomposites to adsorb imazethapyr and imazamox from wastewaters.

Dissipation and phytotoxicity of imazethapyr and imazamox in soils amended with ß-cyclodextrin-chitosan biocomposite.

Use of imazethapyr and imazamox has been an environmental concern due to their high persistence, water solubility, residue build up and potential to injure the succeeding crops. Hence, it is necessary to develop effective decontamination technology. In present study, effect of ß-cyclodextrin-chitosan biocomposite (LCD) amendment in soil on dissipation of imazethapyr and imazamox and their phytotoxicity on succeeding crop was evaluated. The influence of different experimental variables viz. extractant solution and its concentration, liquid to soil ratio, amount of soil and soil type on dissipation of imazethapyr and imazamox was assessed through chemical assays. Irrespective of herbicide formulation and application rate, amendment of soils with LCD increased the dissipation rate of herbicide and the residues were below the detection limit (<0.005 µg g-1) within 5 to 15 days in aridisol, entisol, inceptisol A, inceptisol B, inceptisol C and 7 to 21 days in alfisol and vertisol. Amendment of soils with LCD significantly reduced the growth inhibition of Brassica juncea (L.) Czern and improved the soil biological activity as evident from increase in dehydrogenase activity and soil bacterial count. Amendment of soils with LCD could be a promising, economically feasible and environmentally benign soil decontamination strategy for imazethapyr and imazamox contaminated soils.

Dissipation of Pendimethalin in Soil Under Direct Seeded and Transplanted Rice Field.

The dissipation of pendimethalin applied in direct seeded rice (DSR) and transplanted rice (TPR) field at 1.0 and 2.0 kg a.i. ha-1 followed biphasic first order kinetics (R2 > 0.91) and was comparatively faster under flooded TPR than DSR. The half-life (DT50) of pendimethalin in the soil ranged from 2.22 to 2.80 days in the initial phase and 23.51 to 24.66 days in the final phase in TPR for both application rates. However in DSR, DT50 varied from 3.67 to 4.35 days in the initial phase and 34.19 to 34.99 days in the final phase. Residues of pendimethalin in soil samples analyzed by HPLC and GC-MS/MS were below the detection limit (< 0.003 µg g-1) for both the application rates in DSR and TPR whereas 0.003-0.009 µg g-1 and 0.003-0.008 µg g-1 residues of pendimethalin were found in rice grain and straw samples, respectively.

ß-Cyclodextrin-chitosan biocomposites for synergistic removal of imazethapyr and imazamox from soils: Fabrication, performance and mechanisms.

The present study delineates to develop and explore the possibility of using chitosan-ß-cyclodextrin biocomposites as environmentally friendly decontamination agent for removal of imazethapyr and imazamox from soils. The biocomposites were synthesised using ultrasonic assisted technique and characterised by UV-Visible spectrophotometer. The quantification of imazethapyr and imazamox was done using liquid chromatography tandem mass spectrometry. The adsorption capacity for imazethapyr and imazamox ranged from 0.12 to 1.22 and 0.02 to 1.01 µg1-ng-1mLn, respectively in studied soils (p < .05) indicating strong influence of soil properties on adsorption. Desorption studies indicated that distilled water could desorb only 1.23 to 5.48 and 3.11 to 8.63% of adsorbed imazethapyr and imazamox, respectively at high concentrations (1.0 and 10 µg mL-1) whereas herbicides were not desorbed at low concentrations (0.01 and 0.1 µg mL-1). The removal of imazethapyr and imazamox from soils were carried out with ß-cyclodextrin, chitosan and their biocomposites and the influence of various parameters such as type and concentration of extractant, contact time, liquid to soil ratio, temperature and sequential extraction cycle was investigated. Under optimum conditions, herbicides were successfully desorbed from studied soils using low molecular weight chitosan-ß-cyclodextrin biocomposite (LCD) and removal rate varied from 59.42 to 99.44% at initial herbicide concentration of 0.01 to 10 µg mL-1. The highest removal rate of imazethapyr and imazamox was observed for inceptisol 3 followed by entisol, inceptisol 2, aridisol, inceptisol 1, vertisol and alfisol probably due to differential physico-chemical properties of soil which affected the herbicide-soil interactions. Based on these results, LCD can be regarded as effective and environmentally friendly in situ green extracting agent for remediating soils contaminated with imazethapyr and imazamox.

Time and temperature dependent adsorption-desorption behaviour of pretilachlor in soil.

Understanding and quantifying the adsorption-desorption behaviour of herbicide in soil is imperative for predicting their fate and transport in the environment. In the present study, the effect of time and temperature on the adsorption-desorption behaviour of pretilachlor in soils was investigated using batch equilibration technique. The adsorption-desorption kinetics of pretilachlor in soils was two step process and was well described by pseudo-second-order kinetic model. Freundlich model accurately predicted the sorption behaviour of pretilachlor. The adsorption-desorption of pretilachlor varied significantly with the concentration, temperature and properties of soil viz. organic matter and clay content. All the studied soils had non-linear slopes (n < 1) and degree of nonlinearity increased with increase in clay, organic matter content and temperature (p < 0.05). Desorption of pretilachlor was hysteretic in studied soils and hysteresis coefficient varied from 0.023 to 0.275. Thermodynamic analysis showed that pretilachlor adsorption onto soils was a feasible, spontaneous and endothermic process which becomes more favourable at high temperature. It could be inferred that the adsorption of pretilachlor on soils was physical in nature.

Temperature Dependent Adsorption-Desorption Behaviour of Pendimethalin in Punjab Soils.

This study shows the effect of soil type and temperature on the adsorption and desorption behaviour of pendimethalin using a batch equilibration technique. Adsorption kinetics followed pseudo-second-order-model (R2 > 0.99). The shape of adsorption curve for studied soils was S-type at 30 and 40°C and L-type at 50°C. The isotherms were nonlinear and were well described by Freundlich equation. Adsorption capacity ranged from 1.4 to 2.2 µg1 - 1/n g-1 mL1/n and the order of adsorption was: clay loam > sandy loam > loamy sand indicating strong affinity of pendimethalin towards organic matter and clay content. Irrespective of soil type, the adsorption of pendimethalin increased with increase in temperature suggesting endothermic process. Freundlich desorption coefficient was greater than adsorption in all soils at studied temperatures indicating hysteresis. Thermodynamic parameters revealed spontaneous adsorption process which becomes more favourable at high temperature. The adsorption of pendimethalin was dominated by surface adsorption at lower equilibrium concentration and partition at high concentrations.

Effect of light conditions and chemical characteristics of water on dissipation of glyphosate in aqueous medium.

The present study was conducted to determine the effect of light conditions and chemical properties of water on dissipation of glyphosate. The residues of glyphosate and aminomethylphosphonic acid (AMPA) were quantified using fluorescence spectrophotometer after derivatization with 9-fluoroenylmethoxycarbonyl chloride (FMOC-Cl) and orthopthaldehyde (OPA). Average percent recoveries of glyphosate and AMPA from distilled, tap, and ground water ranged from 87.5 to 94.9, 87.3 to 93.7, and 80.6 to 92.0, respectively, with relative standard deviation less than 10%. The limit of detection and limit of quantification of glyphosate and AMPA from different water matrices ranged from 0.001 to 0.03 µg mL-1 and 0.003 to 0.01 µg mL-1, respectively. The dissipation of glyphosate followed the first-order kinetics, and half-life varied from 1.56 to 14.47 and 13.14 to 42.38 days under UV and sunlight, respectively. The pH and electrical conductivity (EC) of water has differential influence on dissipation of glyphosate, and it increased with increase in pH and EC.

Effect of long-term application of pretilachlor on its persistence and residues in paddy crop.

The effect of long-term application of pretilachlor to paddy in rice-wheat cropping system was investigated from 1997 to 2015. Additionally, in 2013, field experiment was also conducted where pretilachlor was applied to paddy field having no background of its application. The residues of pretilachlor were quantified using high-performance liquid chromatography (HPLC). The average recoveries of pretilachlor from paddy soil, paddy grain and straw samples ranged from 80.7% to 93.8% using HPLC with standard deviation less than 10%. The dissipation rate of pretilachlor in paddy soil followed first-order kinetics and half-life ranged from 9.58 to 21.19 days. In 2015, HPLC was compared with gas chromatography-tandem mass spectrometry (GC-MS/MS) for quantification of residues. Average recoveries of pretilachlor using GC-MS/MS from paddy soil, paddy grain and straw samples ranged from 81.4% to 98.3% with standard deviation less than 10%. Both HPLC and GC-MS/MS offered high reproducibility; however GC-MS/MS was more sensitive and the limit of detection was 3.0 and 1.0 ng g-1 for HPLC and GC-MS/MS, respectively. At harvest, the residues of pretilachlor in the paddy soil and crop were below the maximum residue limit and no dangerous accumulation was observed after its prolonged application.

Persistence behaviour of pretilachlor in puddled paddy fields under subtropical humid climate.

The paper delineates the field trials conducted to investigate the persistence behaviour and dissipation kinetics of pretilachlor in puddled paddy fields under subtropical humid climatic region. Matrix solid phase dispersion (MSPD) method was used for extraction of the pretilachlor from paddy grain and paddy soil samples collected from the experimental field. Pretilachlor residues were quantified using high-performance liquid chromatography (HPLC) with UV/Vis detector at 210 nm. The average recoveries of pretilachlor extracted from matrix ranged from 80.3 to 103.3% with standard deviation less than 10% and sensitivity of 0.01 µg g(-1). The dissipation rate of pretilachlor in paddy field soil and paddy field water followed first-order kinetics with decrease in pretilachlor residues as a function of time. Faster dissipation of pretilachlor was observed in paddy field water than in paddy field soil with half life of 1.89-2.97 days and 7.52-9.58 days, respectively. At harvest, the residues of pretilachlor in the paddy soil and paddy crop samples were below the detection limit.