Identification of degradation products of thiram in water, soil and plants using LC-MS technique

In order to evaluate the deleterious effects of exposure to pesticides on a target population, a comprehensive study on their degradation in the various segments of ecosystem under varying environmental conditions is needed. In view of this, a study has been carried out on the metabolic pathways of thiram, a dithiocarbamate fungicide, in a variety of matrices namely water and soil under controlled conditions and plants in field conditions. The identification of degradation products was carried out in samples collected at various time points using LC-MS. The degradation products identified can be rationalized as originating by a variety of processes like hydrolysis, oxidation, N-dealkylation and cyclization. As a result of these processes the presence of some metabolites like dimethyl dithiocarbamate, bis(dimethyl carbamoyl) disulphide, bis(dimethyl dithiocarbamoyl) trisulphide and N-methyl-amino-dithiocarbamoyl sulphide was observed in all the cases. However, some different metabolites were observed with the change in the matrix or its characteristics such as cyclised products 2(N, N-dimethyl amino)thiazoline carboxylic acid and 2-thioxo-4-thiazolidine were observed only in plants. The investigations reflect that degradation initiates with hydrolysis, subsequently oxidation/dealkylation, followed by different types of reactions. The pathways seem to be complex and dependent on the matrices. Dimethyl dithiocarbamate and oxon metabolites, which are more toxic than parent compound, seem to persist for a longer time. Results indicate persistence vis-a-vis toxicity of pesticide and its metabolites and also provide a data bank of metabolites for forensic and epidemiological investigations.     

The recent occurrence of exotic freshwater fishes in the tributaries of river Ganga basin: abundance, distribution, risk, and conservation issues

We record here the recent occurrence, abundance and distribution of six exotic fish species, viz. Oreochromis mossambicus, Cyprinus carpio, Hypopthalmicthys molitrix, Ctenopharyngodon idellus, Clarias gariepinus, and Pterygoplichthys disjunctivus (a new exotic in India) distributed through the four important tributaries of river Ganga basin in India. From the total catch, the abundance index of all exotic species in different rivers ranged from 1.1 to 14.5?% with highest value in River Gomti. The relative abundance of the exotic species in all the four tributaries demonstrated that a single species C. carpio contributed a considerable abundance (43.3?C83?%) than that of the remaining exotic fishes. The Common Carp, C. carpio, was ubiquitous in all the four tributaries of Ganges basin studied and had the highest local distribution (52.63?%). Smaller size groups of endangered (Chagunius chagunio, Chitala chitala, and Tor tor) and migratory species (Bagarius bagarius, Ompok pabda, Wallago attu, and Sperata aor) in the four tributaries were recorded, and the increasing appearance of Common Carp and other exotic fishes is signaling biological invasion. Possible threats to the indigenous fish fauna, as a result of the invasion and proliferation of these exotics, are discussed.     

Assessment of habitat quality with relation to fish assemblages in an impacted river of the Ganges basin, northern India

In this work, we examined water-quality assessment in relation to fish assemblage of Gomti River, a large tributary of the Ganges River basin in northern India. Principal component analysis was performed for 18 environmental variables which produced three axes that cumulatively explained 60.23% of the environmental variation in sites. Fifteen variables (fine substrate fine gravel, coarse gravel, cobble, sand substrate water flow, conductivity, TDS, total hardness, temperature, dissolved oxygen, pH, and overhanging vegetation) had high loadings on at least one of the principal component axes interpreted. The canonical correspondence analysis was used to establish the relationship between important fish species and environmental variables. Species were distributed within four groups with respect to the significant habitat characteristics. The Pearson correlation coefficient was calculated between the water-quality parameters. We concluded that the level of species richness is mostly dependent on abiotic factors like temperature, dissolved oxygen, TDS, conductivity, depth, pH, and water current in the Gomti River, of the Ganges basin.     

Solvent tolerant marine bacterium Bacillus aquimaris secreting organic solvent stable alkaline cellulase

The organic solvent tolerant bacteria with their physiological abilities to decontaminate the organic pollutants have potentials to secrete extracellular enzymes of commercial importance. Of the 19 marine bacterial isolates examined for their solvent tolerance at 10 vol.% concentration, one had the significant tolerance and showed a relative growth yield of 86% for acetone, 71% for methanol, 52% for benzene, 35% for heptane, 24% for toluene and 19% for ethylacetate. The phylogenetic analysis of this strain using 16S rDNA sequence revealed 99% homology with Bacillus aquimaris. The cellulase enzyme secreted by this strain under normal conditions showed an optimum activity at pH 11 and 45 °C. The enzyme did show functional stability even at higher pH (12) and temperature (75 °C) with residual activity of 85% and 95% respectively. The enzyme activity in the presence of different additives were in the following order: Co⁺² > Fe⁺² > NaOCl₂ > CuSO₄ > KCl > NaCl. The enzyme stability in the presence of solvents at 20 vol.% concentration was highest in benzene with 122% followed by methanol (85%), acetone (75%), toluene (73%) and heptane (42%). The pre-incubation of enzyme in ionic liquids such as 1-ethyl-3-methylimidazolium methanesulfonate and 1-ethyl-3-methylimidazolium bromide increased its activity to 150% and 155% respectively. The change in fatty acid profile with different solvents further elucidated the physiological adaptations of the strain to tolerate such extreme conditions.     

Optimization of nitrate reduction by EDTA catalyzed zero-valent bimetallic nanoparticles in aqueous medium

The present study aims to investigate the EDTA catalyzed reduction of nitrate (NO ₃ ^? ) by zero-valent bimetallic (Fe?CAg) nanoparticles (ZVBMNPs) in aqueous medium and to enumerate the effect of temperature, solution pH, ZVBMNPs dose and EDTA concentration on NO ₃ ^? reduction. Batch experimental data were generated using a four-factor Box?CBehnken design. Optimization modeling was performed using the response surface method for maximizing the reduction of NO ₃ ^? by ZVBMNPs. Significance of the independent variables and their interactions were tested by the analysis of variance and t test statistics. The model predicted maximum reduction capacity (340.15?mg?g^?1 NO ₃ ^? ) under the optimum conditions of temperature, 60?°C; pH?4; dose, 1.0?g?l^?1; and EDTA concentration, 2.0?mmol?l^?1 was very close to the experimental value (338.62?mg?g^?1) and about 16?% higher than the experimentally determined capacity (291.32?mg?g^?1). Study demonstrated that ZVBMNPs had higher reduction efficiency than Fe⁰ nanoparticles for NO ₃ ^? . EDTA significantly enhanced the NO ₃ ^? reduction by ZVBMNPs. The EDTA catalyzed reduction of NO ₃ ^? by ZVBMNPs can be employed for the effective decontamination of water.     

Modeling and optimization of reductive degradation of chloramphenicol in aqueous solution by zero-valent bimetallic nanoparticles

Purpose

The present study aims to investigate the individual and combined effects of temperature, pH, zero-valent bimetallic nanoparticles (ZVBMNPs) dose, and chloramphenicol (CP) concentration on the reductive degradation of CP using ZVBMNPs in aqueous medium.

Method

Iron?Csilver ZVBMNPs were synthesized. Batch experimental data were generated using a four-factor statistical experimental design. CP reduction by ZVBMNPs was optimized using the response surface modeling (RSM) and artificial neural network-genetic algorithm (ANN-GA) approaches. The RSM and ANN methodologies were also compared for their predictive and generalization abilities using the same training and validation data set. Reductive by-products of CP were identified using liquid chromatography-mass spectrometry technique.

Results

The optimized process variables (RSM and ANN-GA approaches) yielded CP reduction capacity of 57.37 and 57.10?mg?g^?1, respectively, as compared to the experimental value of 54.0?mg?g^?1 with un-optimized variables. The ANN-GA and RSM methodologies yielded comparable results and helped to achieve a higher reduction (>6%) of CP by the ZVBMNPs as compared to the experimental value. The root mean squared error, relative standard error of prediction and correlation coefficient between the measured and model-predicted values of response variable were 1.34, 3.79, and 0.964 for RSM and 0.03, 0.07, and 0.999 for ANN models for the training and 1.39, 3.47, and 0.996 for RSM and 1.25, 3.11, and 0.990 for ANN models for the validation set.

Conclusion

Predictive and generalization abilities of both the RSM and ANN models were comparable. The synthesized ZVBMNPs may be used for an efficient reductive removal of CP from the water.     

Changes in the activities of some digestive enzymes of Channa punctatus,exposed chronically to mercuric chloride

Abstract

The effect of a chronic exposure to sublethal concentration of mercuric chloride (0.3 mg/1) on the activities of some enzymes in the digestive system of the teleost fish Channa punctatus was examined after 15 and 30 days of treatment. Glucose‐6‐phosphatase was significantly inhibited in the intestine and pyloric caeca. No marked alterations were observed in the activities of maltase and lactase except for elevation in maltase activity and inhibition in lactase activity in the intestine and pyloric caeca after 15 days of treatment. Three peptidases (aminotripeptidase, glycylglycine dipeptidase and glycyl‐1‐leucine dipeptidase) showed decreased activities in all parts of the digestive system. A decrease was also observed in the activity of lipase except for the stomach where inhibition after 15 days was insignificant. The results indicate that the activities of all the enzymes examined are inhibited in intestine and pyloric caeca and digestion of proteins and lipids may be more affected by mercury than the digestion of some carbohydrates.     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

Novel Renewable Polyols Based on Limonene for Rigid Polyurethane Foams

Novel renewable polyols based on limonene were synthesized using thiol-ene “click” chemistry. These limonene based polyols were structurally characterized using wet methods (hydroxyl number, acid value and viscosity), gel permeation chromatography and spectroscopic methods. The results indicated that high yield of polyols from limonene based materials can be obtained using thiol-ene reaction. These limonene based polyols were used successfully for preparation of rigid polyurethane foams. These foams had regular shape cells and uniform cell size distribution. Thermal studies on these foams indicated that foams were thermally stable up to 250 °C. The glass transition temperature of the foams was higher than 200 °C. These rigid polyurethane foams had high compressive strength and the highest compressive strength of 195 kPa was observed. These foams have good physical–mechanical characteristics and could be suitable for all the applications of rigid polyurethane foams such as thermal insulation of freezers, storage tanks for the chemical and food industries, and packing materials for food industries.