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.     

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.     

Calibration and Validation of SWAP to Simulate Conjunctive Use of Fresh and Saline Irrigation Waters in Semi-Arid Regions

Soil–Water–Atmosphere–Plant (SWAP) version 2.0 was evaluated for its capability to simulate crop growth and salinity profiles at Agra (India) located in a semi-arid region having deep water table and monsoon climate. The data of 12 conjunctive use treatment combinations simulating cyclic and mixing modes of fresh and saline water for wheat were used to calibrate and validate the model. Absolute deviations between the SWAP simulated and observed relative yields during calibration ranged from 2.5 to 2.9 %. A close agreement in the trend and values of measured and simulated soil salinity profiles was observed. Scenario building simulations carried out with the validated SWAP revealed that the maximum crop yields varied from 97 to 99 % with the best available water (EC 3.6 dS m^?1) while the minimum ranged from 65 to 79 % in the treatment with all saline water. Other than this, the relative yield varied from 80 to 98 % in 10 other cyclic and mixing mode treatments. It was established that notwithstanding the seasonal build-up of salts due to saline water use, there would be no long-term build-up of salts as leaching during the monsoon season would render the soil profile salt free at the time of sowing of rabi (winter) crops. Thus, short-term field observations could be used in conjunction with SWAP to show that there seems to be an assured long-term sustainability when saline water is used in conjunctive mode with fresh water in monsoon climatic conditions with deep water table. These results are in conformity with the observation that many farmers in India are using saline and fresh water in conjunctive mode on a long-term basis.     

Enrichment and fractionation of heavy metals in bed sediments of River Narmada, India

A metal fractionation study on bed sediments of River Narmada in Central India has been carried out to examine the enrichment and partitioning of different metal species between five geochemical phases (exchangeable fraction, carbonate fraction, Fe/Mn oxide fraction, organic fraction and residual fraction). The river receives toxic substances through a large number of tributaries and drains flowing in the catchment of the river. The toxic substances of particular interest are heavy metals derived from urban runoff as well as municipal sewage and industrial effluents. Heavy metals entering the river get adsorbed onto the suspended sediments, which in due course of time settle down in the bottom of the river. In this study fractionation of metal ions has been carried out with the objective to determine the eco-toxic potential of metal ions. Although, in most cases (except iron) the average trace/heavy metal concentrations in sediments were higher than the standard shale values, the risk assessment code as applied to the present study reveals that only about 1–3% of manganese, <1% of copper, 16–19% of nickel, 4–20% of chromium, 1–4% of lead, 8–13% of cadmium and 1–3% of zinc exist in exchangeable fraction and therefore falls under low to medium risk category. According to the Geo-accumulation Index (GAI), cadmium shows high accumulation in the river sediments, rest of other metals are under unpolluted to moderately polluted class.     

Particle size distribution of aerosols and associated heavy metals in kitchen environments

Mass size distributions of total suspended particulate matter (TSPM) was measured from Sep 2002 to April 2003 in indoor kitchen environments of five locations in Jawaharlal Nehru University (JNU), New Delhi, with the help of a high volume cascade impactor. Particulate matters were separated in five different size ranges, i.e. >10.9 microm, 10.9-5.4 microm, 5.4-1.6 microm, 1.6-0.7 microm and <0.7 microm. The particle size distribution at various sites appears to follow uni-modal trend corresponding to fine particles i.e. size range <0.7 microm. The contributions of fine particles are estimated to be approximately 50% of TSPM and PM10.9, while PM10.9 comprises 80% of TSPM. Good correlations were observed between various size fractions. Regression results reveal that TSPM can adequately act as a surrogate for PM10.9 and fine particles, while PM10.9 can also act as surrogate for fine particles. The concentrations of heavy metals are found to be dominantly associated with fine particles. However, the concentration of some metals and their size distribution, to some extent is also site specific (fuel type used).     

Long-term effect of rice-based farming systems on soil health

Integrated rice–fish culture, an age-old farming system, is a technology which could produce rice and fish sustainably at a time by optimizing scarce resource use through complementary use of land and water. An understanding of microbial processes is important for the management of farming systems as soil microbes are the living part of soil organic matter and play critical roles in soil C and N cycling and ecosystem functioning of farming system. Rice-based integrated farming system model for small and marginal farmers was established in 2001 at Central Rice Research Institute, Cuttack, Odisha. The different enterprises of farming system were rice–fish, fish–fingerlings, fruits, vegetables, rice–fish refuge, and agroforestry. This study was conducted with the objective to assess the soil physicochemical properties, microbial population, carbon and nitrogen fractions, soil enzymatic activity, and productivity of different enterprises. The effect of enterprises induced significant changes in the chemical composition and organic matter which in turn influenced the activities of enzymes (urease, acid, and alkaline phosphatase) involved in the C, N, and P cycles. The different enterprises of long-term rice-based farming system caused significant variations in nutrient content of soil, which was higher in rice–fish refuge followed by rice–fish enterprise. Highest microbial populations and enzymatic properties were recorded in rice–fish refuge system because of waterlogging and reduced condition prolonged in this system leading to less decomposition of organic matter. The maximum alkaline phosphatase, urease, and FDA were observed in rice–fish enterprise. However, highest acid phosphatase and dehydrogenase activity were obtained in vegetable enterprise and fish–fingerlings enterprise, respectively.     

Thiamethoxam degradation by <Emphasis Type="Italic">Pseudomonas</Emphasis> and <Emphasis Type="Italic">Bacillus</Emphasis> strains isolated from agricultural soils

Twelve bacterial species were evaluated to know the degradation pattern of thiamethoxam in liquid medium. All the bacterial species could actively degrade phorate in a mineral salt medium containing phorate (50 μg ml^–1) as sole carbon source. As these species have ability to degrade, we used these for the degradation of thiamethoxam—a neonicoitinoids. Screening of 12 active phorate-metabolizing bacterial species resulted in selection of Bacillus aeromonas strain IMBL 4.1 and Pseudomonas putida strain IMBL 5.2 causing 45.28 and 38.23 % thiamethoxam (50 μg ml^?1) reduction, respectively, in 15 days as potential thiamethoxam degrading species. These two bacterial species grew optimally at 37 °C under shake culture conditions in MSMT medium raised with initial pH of 6.0–6.5 and use of these optimum cultural conditions resulted in improved thiamethoxam degradation by these bacterial species. These species caused maximum thiamethoxam degradation only in the presence of thiamethoxam as sole source of carbon and energy and the same was reduced in the presence of easily metabolize able carbon (C₀ and C₁) and nitrogen ((N₀, N₁ and N₂) sources. This could be attributed to involvement of repressible metabolic pathways, reactions of which are inhibited by the presence of easily available nutrients for growth. Besides above, qualitative analysis of thiamethoxam residues by gas liquid chromatography revealed complete metabolization of thiamethoxam without detectable accumulation of any known thiamethoxam metabolites.     

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.     

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.     

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.