Occurrence, distribution and possible sources of organochlorine pesticide residues in tropical coastal environment of India: an overview

Organochlorine pesticides (OCPs) are an important potential component of chemical pollutants used extensively for agriculture and sanitation purposes in India as these are comparatively cheap and effective. These persistent organic compounds such as HCH isomers, DDT and its metabolites are the predominant chemical contaminants found along the Indian coast and thus constitute both alluring and grave areas of scientific research. Our objective in the paper is to provide a comprehensive account of the distribution of organochlorine pesticides in biotic and abiotic compartments of the Indian coastal environment, make some comments on their environmental sources, their movement through the food chain and possible ecotoxicological risk of health in biota including humans. The prevalent HCH, DDT and HCB concentrations differ markedly in eastern and western coast of India reflecting differing agricultural and other usage and their ultimate input into the coastal environment by several rivers and the bioturbation activities of macrozoobenthos (bivalve mollusks, polychaetous annelids, etc.). In several cases, the DDT levels exceeded the effects range-low (ER-L) and could thus cause acute biological impairments, in comparison with the sediment quality guidelines. Contributions of DDT metabolites (DDT, DDD and DDE residues) vary in different Indian coastal regions predominated by pp'-DDT and pp'-DDD. Measured concentrations of HCHs were lower than DDTs that might be due to higher water solubility, vapor pressure and biodegradability of the latter. HCH and DDT residues in fish in India were lower than those in the temperate countries indicating a lower accumulation in tropical fish, which might be related to rapid volatilization of this insecticide in the tropical environment. The concentrations of other chlorinated pesticides (aldrin, dieldrin, eldrin, methoxychlor, endosulfan sulphate) were lower and not generally of great concern.     

Organochlorine pesticide residues in sediments of a tropical mangrove estuary,India: implications for monitoring

The paper examines the concentrations of isomers of hexachlorocyclohexane (HCHs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), alpha-endosulfan and endosulfan sulfate in surface sediment samples collected from the mouth of Hugli estuary in the vicinity of Sundarban mangrove environment, eastern part of India. An overall pattern of accumulation of these pesticides was in the order of: SigmaHCH>endosulfan sulfate>SigmaDDT>alpha-endosulfan. The concentration of these compounds was quite low. An elevated level of SigmaHCH, SigmaDDT and endosulfan sulfate were marked during premonsoon months, a period characterized by high salinity and pH values. Among the isomers and metabolites of HCH and DDT, beta-HCH, pp'-DDT and pp'-DDE were found to be dominant. The sources of contamination are closely related to human activities, such as domestic and industrial discharges, agricultural chemical applications and soil erosion due to deforestation. The study is compared to other estuarine environment in India and abroad. The present data will serve as a baseline against which future anthropogenic effects may be assessed.     

Studies on arsenic transforming groundwater bacteria and their role in arsenic release from subsurface sediment

Ten different Gram-negative arsenic (As)-resistant and As-transforming bacteria isolated from As-rich groundwater of West Bengal were characterized to assess their role in As mobilization. 16S rRNA gene analysis confirmed the affiliation of these bacteria to genera Achromobacter, Brevundimonas, Rhizobium, Ochrobactrum, and Pseudoxanthomonas. Along with superior As-resistance and As-transformation abilities, the isolates showed broad metabolic capacity in terms of utilizing a variety of electron donors and acceptors (including As) under aerobic and anaerobic conditions, respectively. Arsenic transformation studies performed under various conditions indicated highly efficient As³⁺ oxidation or As⁵⁺ reduction kinetics. Genes encoding As³⁺ oxidase (aioA), cytosolic As⁵⁺ reductase (arsC), and As³⁺ efflux pump (arsB and acr3) were detected within the test isolates. Sequence analyses suggested that As homeostasis genes (particularly arsC, arsB, and acr3) were acquired by most of the bacteria through horizontal gene transfer. A strong correlation between As resistance phenotype and the presence of As³⁺ transporter genes was observed. Microcosm study showed that bacterial strain having cytosolic As⁵⁺ reductase property could play important role in mobilizing As (as As³⁺) from subsurface sediment.     

Co-pyrolysis of paper waste and mustard press cake in a semi-batch pyrolyzer—optimization and bio-oil characterization

Under the present research study, the co-pyrolysis of paper waste and mustard press cake was conducted in a 50 mm diameter and 640 mm long semi-batch pyrolyzer in the temperature range of 673 to 1173 K in nitrogen atmosphere and synergistic relationship between the pyrolysis of two feed stocks has been observed. The paper wastes were composed of local packing paper, newspaper-based food packets of grocery, and printing paper in the ratio of 6:3:1. During co-pyrolysis, response surface methodology (RSM) technique has been employed using Design Expert Version 7.0.0 to determine the collective effects of factors, namely, A: ratio of paper waste to mustard press cake and B: pyrolysis temperature, on the yield of bio-oil, energy yield, and oxygen content of bio-oil. Optimization has been done by using RSM to identify the individual sets of values of independent parameters corresponding to maximum bio-oil yield (A: 9.0:1, B: 874.75 K), energy yield (A: 8.80:1, B: 812 K), and minimum oxygen content of bio-oil (A: 2.75:1, B: 883.06 K). Bio-oil obtained at maximum energy yield condition has been characterized using the Gas chromatography–mass spectrometry (GC-MS) and Fourier transform infrared spectroscopy (FTIR) spectroscopic analyses. The array of compounds present in the bio-oil compounds has been compared with literature data available on pyro-oil obtained from similar feed stocks.     

Impact of raking and bioturbation-mediated ecological manipulation on sediment–water phosphorus diagenesis: a mesocosm study supported with radioactive signature

The study examined the impact of raking and fish bioturbation on modulating phosphorus (P) concentrations in the water and sediment under different trophic conditions. An outdoor experiment was set to monitor physicochemical and microbiological parameters of water and sediment influencing P diagenesis. A pilot study with radioactive ³²P was also performed under the agency of raking and bacteria (Bacillus sp.). Raking was more effective in release of P under unfertilized conditions by significantly enhancing orthophosphate (35%) and soluble reactive phosphate (31.8%) over respective controls. Bioturbation increased total and available P in sediments significantly as compared to control. The rates of increase were higher in the unfertilized conditions (17.6–28.4% for total P and 12.2 to 23.2% for available P) than the fertilized ones (6.5–12.4% for total P and 9.1 to 15% for available P). The combined effects of raking and bioturbation on orthophosphate and soluble reactive phosphate were also stronger under unfertilized state (54.5 and 81.8%) than fertilized ones (50 and 70%). The tracer signature showed that coupled action of introduced bacteria and repeated raking resulted in 59.2, 23 and 16% higher counts of radioactive P than the treatments receiving raking once, repeated raking and bacteria inoculation, respectively. Raking alone or in sync with bioturbation exerted pronounced impact on P diagenesis through induction of coupled mineralization and nutrient release. It has significant implication for performing regular raking of fish-farm sediments and manipulation of bottom-grazing fish to regulate mineralization of organic matter and release of obnoxious gases from the system. Further, they synergistically can enhance the buffering capacity against organic overload and help to maintain aquatic ecosystem health.

     

Use of fly ash for the removal of phenol and its analogues from contaminated water

This work attempts to elucidate the effects of different operational variables affecting the mechanistic function of fly ash for removal of some priority organic pollutants viz. phenol and its analogues. Thermodynamic parameters like free energy change, enthalpy and entropy of the process, as well as the sorption isotherms for phenols on fly ash, were measured and the most suitable isotherm was determined. Results of the study indicate that the extent of solute removal is determined by the initial solute concentration, molecular size and molecular arrangement of the solute. At the fixed set of experimental conditions, a model equation can be developed from which the percent removal corresponding to the load of the particular solute is determined. It is assumed that the mechanism of adsorption is governed by the surface characteristics of fly ash; pH has a vital role in influencing the solute removal as both the ionizing power (acidity, pKa) of the solutes and the zero point charge of fly ash (pH(ZPC)) depend on the solution pH. Isotherm pattern and the free energy change indicate that the process is favorable, as well as spontaneous. The information gathered from the study will serve as a predictive modeling procedure for the analysis and design of the removal of organic pollutants and decontamination of water. The leaching experiment indicates that the retained solutes do not release from fly ash. The retained solutes can be recovered and utilized as industrial raw material.     

Effectiveness of urea in enhancing the extractability of 2,4,6-trinitrotoluene from chemically variant soils

One of the major challenges in developing an effective phytoremediation technology for 2,4,6-trinitrotoluene (TNT) contaminated soils is limited plant uptake resulting from low solubility of TNT. The effectiveness of urea as a solubilizing agent in increasing plant uptake of TNT in hydroponic systems has been documented. Our preliminary greenhouse experiments using urea were also very promising, but further characterization of the performance of urea in highly-complex soil-solution was necessary. The present study investigated the natural retention capacity of four chemically variant soils and optimized the factors influencing the effectiveness of urea in enhancing TNT solubility in the soil solutions. Results show that the extent of TNT sorption and desorption varies with the soil properties, and is mainly dependent on soil organic matter (SOM) content. Hysteretic desorption of TNT in all tested soils suggests irreversible sorption of TNT and indicates the need of using an extractant to increase the release of TNT in soil solutions. Urea significantly (p < 0.0001) enhanced TNT extraction from all soils, by increasing its solubility at the solid/liquid interface. Soil organic matter content and urea application rates showed significant effects, whereas pH did not exert any significant effect on urea catalysis of TNT extraction from soil. The optimum urea application rates (125 or 350 mg kg⁻¹) for maximizing TNT extraction were within the limits set by the agronomic fertilizer-N rates used for major agricultural crops. The data obtained from this batch study will facilitate the optimization of a chemically-catalyzed phytoremediation model for cleaning up TNT-contaminated soils.     

Threatened access, risk of eviction and forest degradation: case study of sustainability problem in a remote rural region in India

Degradation of common pool resource (CPR) in developing countries has often been traced to high rate attached by poor people in discounting future flow of benefits, market failure, pressure on carrying capacity or sometimes property right failure. However, the concept of poorly enforced property right and particularly risk of eviction as a measure of insecurity of land tenure has not been adequately examined in the context of degradation of CPR. A game theoretic framework is developed where degradation of forest grazing land is explained in terms of changes in perceived risk of eviction from the encroached land. Logit regression is applied to empirically analyse the impact of perceived fear of reduced access and other variables on the state of degradation. For this purpose, a sample of seven villages is considered in tribal dominated region in West Bengal, India. It is observed that apart from a number of socio-economic variables like poverty, mutual trust and other incomes, perceived fear of eviction (represented as a dummy variable) arising from insecurity of forest land tenure, has a significant impact on forest degradation status in the study region.     

Amperometric Detection of Pesticides Using Polymer Electrodes

Abstact The real time monitoring of some organophosphorus based pesticides is of great concern to environmentalists because the widespread use of pesticides is causing severe health hazards to all living beings and also hampering our ecological balance. The traditional methods of measurement of pesticide residues are time consuming, need sample pre-treatment, and lack desired specificity and accuracy. We have developed an amperometric biosensor for indirect measurement of the pesticide concentration precisely in ppb level. The method is based on the action of two enzymes namely acetylcholine esterase and choline oxidase which are uniquely immobilized in a polymeric porous network directly on the working electrode of a screen-printed sensor. Polyacrylamide matrix has been prepared by copolymerisation of acrylamide andN,N′-methylenebisacrylamide using Potassium peroxodisulphate (K₂S₂O₈) as initiator. A linear relationship was obtained between the range of 0 to 10 ppb.     

Turbulent flow characteristics and drag over 2-D forward-facing dune shaped structures with two different stoss-side slopes

The present paper explores the characteristics of turbulent flow and drag over two artificial 2-D forward-facing waveform structures with two different stoss side slopes of $50^{\circ }$ and $90^{\circ },$ respectively. Both structures possessed a common slanted lee side slope of $6^{\circ }.$ Flume experiments were conducted at the Fluvial Mechanics Laboratory of Indian Statistical Institute, Kolkata. The velocity data were analyzed to identify the spatial changes in turbulent flow addressing the flow separation region with recirculating eddy, the Reynolds stresses, the turbulent events associated with burst-sweep cycles and the drag over two upstream-facing bedforms for Reynolds number $Re_h=1.44\times 10^5.$ The divergence at the stoss side slope between the two structures revealed significant changes in the mean flow and turbulence. Comparison showed that during the flood-tide condition there was no flow separation region on the gentle lee side of the structure with smaller slope at the stoss side, while for the other structure with vertical stoss side slope a thick flow separation region with recirculating eddy was observed at the gentle lee side just downstream of the crest. The recirculating eddy induced on the lee-side had a strong influence on the resistance that the structure exerts to the flow due to loss of energy through turbulence. In contrast, a great amount of reduction in drag was observed in the case of smaller stoss side sloped structure as there was no flow separation. The quadrant analysis was also used to highlight the turbulent event evolution along the bed form structures under flood-tide conditions.