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.     

Effects of in utero di-butyl phthalate and butyl benzyl phthalate exposure on offspring development and male reproduction of rat

The study was conducted to assess the effects of in utero di-butyl phthalate (DBP) and butyl benzyl phthalate (BBP) exposure during late gestation on offspring’s development and reproductive system of male rats. Pregnant rats were treated orally with DBP (2, 10, 50 mg/kg), BBP (4, 20, 100 mg/kg), and diethylstilbestrol (DES) 6 μg/kg (positive control) from GD14 to parturition. A significant reduction in dams’ body weight on GD21 in DBP-, BBP-, and DES-treated groups was observed. The gestation length was considerably elevated in the treated groups. Decline in male pups’ body weight was significant at PND75 in DBP- (50 mg/kg), BBP- (20,100 mg/kg), and DES-treated groups. The weight of most of the reproductive organs and sperm quality parameters was impaired significantly in DBP- (50 mg/kg) and BBP- (100 mg/kg) treated groups. Further, a non-significant decline in testicular spermatid count and daily sperm production was also monitored in treated groups. A significant reduction in serum testosterone level in BBP (100 mg/kg), whereas the testicular activity of 17β-HSD was declined non-significantly in the treated groups with respect to control. The data suggests that DBP and BBP exposure during late gestation period might have adverse effects on offspring’s development, spermatogenesis, and steroidogenesis in adult rats.     

Microscope and spectacle: On the complexities of using new visual technologies to communicate about wildlife conservation

Wildlife conservation-related organisations increasingly employ new visual technologies in their science communication and public engagement efforts. Here, we examine the use of such technologies for wildlife conservation campaigns. We obtained empirical data from four UK-based organisations through semi-structured interviews and participant observation. Visual technologies were used to provide the knowledge and generate the emotional responses perceived by organisations as being necessary for motivating a sense of caring about wildlife. We term these two aspects ‘microscope’ and ‘spectacle’, metaphorical concepts denoting the duality through which these technologies speak to both the cognitive and the emotional. As conservation relies on public support, organisations have to be seen to deliver information that is not only sufficiently detailed and scientifically credible but also spectacular enough to capture public interest. Our investigation showed that balancing science and entertainment is a difficult undertaking for wildlife-related organisations as there are perceived risks of contriving experiences of nature and obscuring conservation aims.     

Biodiesel production from a free fatty acid containing Karanja oil by a single-step heterogeneously catalyzed process

Karanja oil, containing 6.2% free fatty acids (FFAs), was considered for biodiesel production using a single-step solid-phase acid catalyzed process. Different types of zeolites and Amberlyst15 catalysts were tested and biodiesel was produced. Under similar conditions, the highest biodiesel yield was achieved using an Amberlyst15 catalyst, which contained 3–5% of moisture. The effects of operating parameters of the reaction such as reaction temperature, catalyst amount, and methanol-to-oil ratio were studied. An increase of methanol:oil ratio revealed a non-monotonic increase in biodiesel yields. Similar non-monotonic behavior was observed when Jatropha oil was used. Leaching and catalyst reusability were also considered. No significant effects of leaching were observed and catalyst reusability appeared to be affected by methanol interactions. The presence of a co-solvent, Tetrahydrofuran (THF), increased the biodiesel yield. Furthermore, an optimum amount of THF (THF:methanol volume ratio of 1:2) gave rise to the highest biodiesel yield. A biodiesel yield of 93% was achieved at 120 °C using a single-step process with Amberlyst15 as a catalyst, THF as a co-solvent, and a methanol:oil ratio of 30:1.     

Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate

1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al₂O₃ using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al₂O₃ and results were compared with well reported oxime impregnated Al₂O₃. Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al₂O₃ > 1-(4-chlorophenyl)-N-hydroxymethanimine/Al₂O₃ > 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al₂O₃ > Al₂O₃. From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al₂O₃ was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.     

Monitoring changes in soil organic carbon pools, nitrogen, phosphorus, and sulfur under different agricultural management practices in the tropics

Soil organic matter not only affects sustainability of agricultural ecosystems, but also extremely important in maintaining overall quality of environment as soil contains a significant part of global carbon stock. Hence, we attempted to assess the influence of different tillage and nutrient management practices on various stabilized and active soil organic carbon pools, and their contribution to the extractable nitrogen phosphorus and sulfur. Our study confined to the assessment of impact of agricultural management practices on the soil organic carbon pools and extractable nutrients under three important cropping systems, viz. soybean–wheat, maize–wheat, and rice–wheat. Results indicated that there was marginal improvement in Walkley and Black content in soil under integrated and organic nutrient management treatments in soybean–wheat, maize–wheat, and rice–wheat after completion of four cropping cycles. Improvement in stabilized pools of soil organic carbon (SOC) was not proportional to the applied amount of organic manures. While, labile pools of SOC were increased with the increase in amount of added manures. Apparently, green manure (Sesbania) was more effective in enhancing the lability of SOC as compared to farmyard manure and crop residues. The KMnO₄-oxidizable SOC proved to be more sensitive and consistent as an index of labile pool of SOC compared to microbial biomass carbon. Under different cropping sequences, labile fractions of soil organic carbon exerted consistent positive effect on the extractable nitrogen, phosphorus, and sulfur in soil.     

Seasonal and spatial variation of Yamuna River water quality in Delhi, India

Street dust was collected from five roads with different traffic volumes in the metropolitan area of Beijing and separated into five size fractions. Concentrations of polycyclic aromatic hydrocarbons (PAHs) adsorbed on street dust in different size ranges and their correlation with specific surface area and total organic carbon (TOC) were investigated. Results show that the concentration of 16-PAHs of sieved samples ranges from 0.27 to 1.30 mg/kg for all the sampling sites. Particles smaller than 40 μm in diameter have the highest 16-PAHs concentration among all of the size ranges for street dust from the four sampling sites with vehicles running on. PAHs with three or four rings account for 68% of the overall 16-PAHs on average. Remarkable positive correlation exists between 16-PAHs concentration and specific surface area with R ² values from 0.7 to 0.96 for the four sampling sites with vehicles running on. The relationship between the concentration of 16-PAHs and TOC is less clear.     

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.     

Monitoring the sedimentary carbon in an artificially disturbed deep-sea sedimentary environment

An area of 0.6 km(2) in the manganese nodule field of the Central Indian Basin was physically disturbed and sediments discharged in the near bottom waters to simulate seabed mining and study its impact on benthic ecosystem. An estimated 2 to 3 tonnes of sedimentary organic carbon (C(org)) was resuspended into the water column during a 9-day experiment. The majority of the sediment cores from within the disturbed area and areas towards the south showed a ~30% increase in C(org) content as well as an increase in carbon burial rates after disturbance, though with a reduction in carbon/phosphorus ratios. High specific surface area (SSA~25 m(2) g(-1)) and low C(org)/SSA ratios (mostly <0.5) are typical of deep-sea sediments. The increased C(org) values were probably due to the organic matter from dead biota and the migration and redeposition of fine-grained, organic-rich particles. Spatial distribution patterns of C(org) contents of cores taken before and after disturbance were used to infer the direction of plume migration and re-sedimentation. A positive relationship was observed between total and labile C(org) and macrobenthos density and total bacterial numbers prior to disturbance, whereas a negative relationship was seen after disturbance owing to drastic reduction in the density of macrofauna and bacteria. Overall decrease in labile organic matter, benthic biota and redistribution of organic matter suggest that the commercial mining of manganese nodules may have a significant immediate negative effect on the benthic ecosystem inducing changes in benthic community structure.     

Limnochemistry and nutrient dynamics in Upper Lake, Bhopal, India

In limnetic ecosystem, water quality depends upon physical, chemical, and biological factors. Effects of temperature, light scattering, and absorption by suspended and dissolved matter, transport, and mixing of nutrients within the lake are the significant factors as far as water quality is concerned. Nutrient loading into the lake and internal cycling of nutrients is always a matter of concern and critical to number of processes. During the winter season, heat and momentum transfer at the lake surface and the temperature-density relation of water destabilize the water column and drive vertical mixing and transport processes. The deepening of the surface layer produces nutrient transfer from the hypolimnion into the euphotic zone of epilimnion. It may also resuspend sediments that would have settled under stratified conditions, or redistribute particles that may still be in suspension. Thus, there exists a complex connection between the hydrodynamics and water quality issues. Present study is an effort to understand how seasonal changes in the limnetic ecosystem regulate the limnochemistry and movement of nutrient. The study revealed that significant variations of nutrients and organic load were observed between epilimnion and hypolimnion during summer season, and the lake was found in hyper-eutrophic condition throughout the study period.