Biodegradation of Endosulfan by a Soil Bacterium

A bacterium capable of metabolizing endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine3-oxide) was isolated from cotton-growing soil and effectively shown to degrade endosulfan into endosulfan sulfate. The bacterium degraded 50% of the compound within 3 days of incubation. Endosulfan sulfate was the only terminal product and no other metabolites were formed during the incubation. Endosulfan and its metabolites were analyzed by gas chromatography. The metabolites formed indicated that the organism follows an oxidative pathway for metabolism of this pesticide. Therefore, the present study, microbial degradation of endosulfan by a soil bacterium, may provide a basis for the development of bioremediation strategies to remediate the pollutants in the environment.     

Endosulfan and Quinalphos Residues and Toxicity to Soil Microarthropods after Repeated Applications in a Field Investigation

Endosulfan (1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-en-2,3-ylenedimethylsulphite) and quinalphos (O,O-diethyl O-quinoxalin-2-yl phosphorothioate) persistence and their effect on soil microarthropods were studied after repeated applications in cotton fields. Dissipation behavior of insecticides after repeated applications was observed from 78 to 292 days after the first insecticide treatment. At any given time the concentrations of endosulfan β residues were always higher as compared to endosulfan α. From 78 to 85 days, 5.0% and 20.4% decrease in α and β endosulfan residues was observed, respectively. Endosulfan β isomer decreased up to 93.0% in 292 days. Endosulfan sulfate was detected as a major metabolite in the soil samples. Total endosulfan residues decreased by 86.6% from 78 to 292 days. The amounts of quinalphos residues were less as compared to endosulfan at any given time. The residues observed after 78 days of application were 0.88 ng g^?1 d wt. soil. At the end of 145 days, a 35.0% decrease in quinalphos residue was observed, which decreased further by 50.9% in 292 days. Among the soil microarthropods studied, Acarina was more sensitive to the applied insecticides as compared to Collembola. Three days after the last treatment, up to 94.5% (p < 0.01) and 71.2% (p < 0.05) decrease in Acarina population was observed in endosulfan and quinalphos treated fields, respectively, compared to control field. In general, no noticeable change in Collembola population was observed after the insecticide treatments.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Endosulfan induces changes in spontaneous swimming activity and acetylcholinesterase activity of Jenynsia multidentata (Anablepidae, Cyprinodontiformes)

We assessed changes in spontaneous swimming activity and acetylcholinesterase (AchE) activity of Jenynsia multidentata exposed to Endosulfan (EDS). Females of J. multidentata were exposed to 0.072 and 1.4 μg L⁻¹ EDS. Average speed and movement percentage were recorded during 48 h. We also exposed females to EDS at five concentrations between 0.072 and 1.4 μg L⁻¹ during 24 h, and measured the AchE activity in brain and muscle. At 0.072 μg L⁻¹ EDS swimming motility decreased relative to the control group after 45 h, while at 1.4 μg L⁻¹ EDS swimming motility decreased after 24 h. AchE activity significantly decreased in muscle when J. multidentata were exposed to EDS above 0.072 μg L⁻¹, while no significant changes were observed in brain. Thus, changes in swimming activity and AchE activity in muscle are good biomarkers of exposure to EDS in J. multidentata.     

Bioconcentration and depuration of endosulfan sulfate in mosquito fish (Gambusia affinis)

Endosulfan is an insecticide which has been widely used in agriculture. The technical grade material consists of two isomers (alpha and beta). Under natural environmental conditions, endosulfan is metabolized through oxidation and the main metabolite in the environment is endosulfan sulfate. Most ecotoxicology research has been conducted with technical grade endosulfan to determine effects on non-target aquatic organisms. Little data on the effects of endosulfan sulfate on aquatic organisms are available in the literature. This study characterizes endosulfan sulfate bioconcentration and depuration in mosquito fish (Gambusia affinis). During the study, G. affinis was exposed to an environmentally relevant endosulfan sulfate concentration of 0.25 μg L⁻¹ for 5 weeks (uptake phase) followed by a 3-week period (depuration phase) in clean water. This study found that G. affinis bioconcentrated endosulfan sulfate. During the exposure phase, fish tissue concentrations of endosulfan sulfate increased with time up to 730 μg kg⁻¹ dw or 215 μg kg⁻¹ ww. The bioconcentration data followed Michaelis-Menten kinetics better than the one-compartment first order kinetics (1-CFOK). Using these models, the bioconcentration factors for endosulfan sulfate-exposed G. affinis were from 687 to 888  L kg⁻¹ in wet weight or 2263 to 2936 L kg⁻¹ in dry weight. During the depuration phase, endosulfan sulfate concentrations in tissue significantly decreased and the data followed first order kinetics. The half-life of endosulfan sulfate in G. affinis was about 9 d. There was no significant difference in standard length or weight between control and exposed fish. The growth data followed the von Bertalanffy growth model. However, the condition factor of exposed fish increased with time during the exposure phase.     

Enrichment and Isolation of a Mixed Bacterial Culture for Complete Mineralization of Endosulfan

In the present study, we isolated three novel bacterial species, namely, Staphylococcus sp., Bacillus circulans–I, and Bacillus circulans–II, from contaminated soil collected from the premises of a pesticide manufacturing industry. Batch experiments were conducted using both mixed and pure cultures to assess their potential for the degradation of aqueous endosulfan in aerobic and facultative anaerobic condition. The influence of supplementary carbon (dextrose) source on endosulfan degradation was also examined. After four weeks of incubation, mixed bacterial culture was able to degrade 71.82 ± 0.2% and 76.04 ± 0.2% of endosulfan in aerobic and facultative anaerobic conditions, respectively, with an initial endosulfan concentration of 50 mg l^?1. Addition of dextrose to the system amplified the endosulfan degradation efficiency by 13.36 ± 0.6% in aerobic system and 12.33 ± 0.6% in facultative anaerobic system. Pure culture studies were carried out to quantify the degradation potential of these individual species. Among the three species, Staphylococcus sp. utilized more beta endosulfan compared to alpha endosulfan in facultative anaerobic system, whereas Bacillus circulans–I and Bacillus circulans–II utilized more alpha endosulfan compared to beta endosulfan in aerobic system. In any of these degradation studies no known intermediate metabolites of endosulfan were observed.     

Uptake, tissue distribution and metabolism of the insecticide endosulfan in Jenynsia multidentata (Anablepidae, Cyprinodontiformes)

The study reports the accumulation, distribution and metabolism of technical endosulfan in Jenynsia multidentata. Adult females were exposed to acute sublethal concentrations (0.072, 0.288 and 1.4 μg L⁻¹). After 24 h, fish were sacrificed and gills, liver, brain, intestine and muscle were removed. Results show that both isomers of technical-grade endosulfan (α- and β-) are accumulated in fish tissues and biotransformation to endosulfan sulfate occurs at all concentrations tested. Significantly differences in endosulfan accumulation were only found at 1.4 μg L⁻¹ but not between the lowest concentrations. However a similar distribution pattern was observed at all exposure levels where liver, intestine and brain had the highest levels of α-, β-endosulfan and endosulfan sulfate. Moreover, liver and brain showed the highest endosulfan sulfate:α-endosulfan ratios due to high biotransfomation capacity. J. multidentata demonstrated to be a sensitive species under exposure to technical endosulfan and, therefore, could be used to assess aquatic pollution.     

富营养化供水中的藻类控制与去除

综述了富营养化的供水原水中，藻类控制与去除方法的国内外研究进展。首先扼要介绍藻类过度繁殖对原水处理工艺的诸多影响。然后叙述富营养化湖泊中，藻类生物量的控制方法和给水原水处理的藻类去除工艺，并就此技术现状提出若干结论和建议。     

Urban Water Resources Quota Management: The Core Strategy for Water Demand Management in China

Since China has the largest population in the world, the available water resources per capita in China are very limited. With the rapid economic development that is currently occurring, the shortage of water resources at the national level has become extremely critical. How to solve the problems due to water scarcity and water pollution has received increasing attention from the Chinese government and various communities. In order to provide a sustainable development environment for 1.6 billion people in the future, the whole country has started to reform urban water resources management systems in terms of related policies, regulations, methodologies, and technologies focusing on improving the efficiency and effectiveness in water use. Urban water quota management has now become a core strategy in developing a water resources governance model for water demand management aiming at establishing a water-saving society. This paper introduces the main stages and the processes of implementing water quota management in China, analyzes the basic principles, and expounds the elements, information foundation, core module and operational model of the urban water quota management system. It has been demonstrated that urban water quota management has made some remarkable contribution not only in transforming the pattern of water mode and strengthening water management enforcement but also in integrating various management methods in saving water and preventing pollution.     

Fate and transport of fragrance materials in principal environmental sinks

Fragrance materials are widely present in the environment, such as air, water, and soil. Concerns have been raised due to the increasing utilization and suspected impact on human health. The bioaccumulating property is considered as one of the causes of the toxicity to human beings. The removal of fragrance materials from environmental sinks has not been paid enough attention due to the lack of regulation and research on their toxicity. This paper provides systematic information on how fragrance materials are transferred to the environment, how do they affect human lives, and what is their fate in water, wastewater, wastewater sludge, and soil.     

Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH₂N-C(N-NO₂)-CHN-CHO or its isomer N(NO₂)CH-CHN-CO-CHNH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.     

Fate of metolachlor under subirrigation in a sandy soil: A lysimeter study

Abstract

A three‐year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2‐chloro‐N‐(2‐ethyl‐6‐methlphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography.

Results obtained in this three year study, (1993–1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

水中有机成分及其对饮用水质的影响

微量有机污染物和氯化消毒副产物对饮用水构成直接威胁,是饮用水中要重点控制的;天然大分子有机物对水质构成间接影响,导致胶体稳定性提高、增加药耗;藻类和代谢产物影响常规处理工艺效果,对水质产生不良影响。     

Butachlor Degradation in Tropical Soils: Effect of Application Rate,Biotic-Abiotic Interactions and Soil Conditions

The degradative characteristics of butachlor (N-Butoxymethyl-2-chloro-2′,6′-diethyla- cetanilide) were studied under controlled laboratory conditions in clay loam alluvial (AL) soil (Typic udifluvent) and coastal saline (CS) soil (Typic endoaquept) from rice cultivated fields. The application rates included field rate (FR), 2-times FR (2FR) and 10-times FR (10FR). The incubation study was carried out at 30°C with and without decomposed cow manure (DCM) at 60% of maximum water holding capacity (WHC) and waterlogged soil condition. The half-life values depended on the soil types and initial concentrations of butachlor. Butachlor degraded faster in AL soil and in soil amended with DCM under waterlogged condition. Microbial degradation is the major avenue of butachlor degradation from soils.     

测定地表水及饮用水中硫酸盐的两种方法探讨

通过比较两种监测分析方法,分析了测定硫酸盐分光光度法的影响因素、存在问题,以及火焰原子吸收法的优点,提出对不同浓度范围的硫酸盐,宜采用合适的分析方法,以减小测定的误差,提高测定结果的准确性和科学性。     

Optimization and validation of enzyme-linked immunosorbent assay for the determination of endosulfan residues in food samples

In this study, an enzyme-linked immunosorbent assay (ELISA) was optimized and applied to the determination of endosulfan residues in 20 different kinds of food commodities including vegetables, dry fruits, tea and meat. The limit of detection (IC₁₅) was 0.8 μg kg^?1 and the sensitivity (IC₅₀) was 5.3 μg kg^?1. Three simple extraction methods were developed, including shaking on the rotary shaker at 250 r min^?1 overnight, shaking on the rotary shaker for 1 h and thoroughly mixing for 2 min. Methanol was used as the extraction solvent in this study. The extracts were diluted in 0.5% fish skin gelatin (FG) in phosphate-buffered saline (PBS) at various dilutions in order to remove the matrix interference. For cabbage (purple and green), asparagus, Japanese green, Chinese cabbage, scallion, garland chrysanthemum, spinach and garlic, the extracts were diluted 10-fold; for carrots and tea, the extracts were diluted 15-fold and 900-fold, respectively. The extracts of celery, adzuki beans and chestnuts, were diluted 20-fold to avoid the matrix interference; ginger, vegetable soybean and peanut extracts were diluted 100-fold; mutton and chicken extracts were diluted 10-fold and for eel, the dilution was 40-fold. Average recoveries were 63.13–125.61%. Validation was conducted by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The results of this study will be useful to the wide application of an ELISA for the rapid determination of pesticides in food samples.     

The Water Table: The Shifting Foundation of Life on Land

Hyperarid, arid, and semi-arid lands represent over a third of the Earth’s land surface, and are home to over 38 % of the increasing world population. Freshwater is a limiting resource on these lands, and withdrawal of groundwater substantially exceeds recharge. Withdrawals of groundwater for expanding agricultural and domestic use severely limit water availability for groundwater dependent ecosystems. We examine here, with emphasis on quantitative data, case histories of groundwater withdrawals at widely differing scales, on three continents, that range from the impact of a few wells, to the outcomes of total appropriation of flow in a major river system. The case histories provide a glimpse of the immense challenge of replacing groundwater resources once they are severely depleted, and put into sharp focus the question whether the magnitude of the current and future human, economic, and environmental consequences and costs of present practices of groundwater exploitation are adequately recognized.     

Genotoxicity evaluation of the insecticide endosulfan in the wetland macrophyte Bidens laevis L

The frequency of micronuclei (MN) and chromosome aberrations in anaphase-telophase (CAAT) was determined in root tips of the wetland macrophyte Bidens laevis exposed to environmentally relevant concentrations of endosulfan (0.01, 0.02, 0.5 and 5microg/L) for 48h. MN frequency varied from 0 in negative controls and plants exposed to 0.01microg/L endosulfan to 0-3 in plants exposed to 5microg/L. Moreover, a significant concentration-dependent increase of CAAT was observed. The higher proportion of laggards and vagrand chromosomes observed at 5microg/L would indicate that endosulfan interacts with the spindle interrupting normal chromosome migration. Endosulfan resulted genotoxic to B. laevis, a species of potential value for bioassays and in situ monitoring of environmental contamination by pesticides.     

Recent progress on application of UV excilamps for degradation of organic pollutants and microbial inactivation

Excilamps as modern mercury-free sources of narrow-band UV radiation represent an attractive alternative in environmental applications. This review focuses on recent studies on the water and surface decontamination with excilamps by means of direct photolysis and advanced oxidation processes. To date, direct photolysis and advanced oxidation processes (AOPs) such as UV/H₂O₂, UV/Fenton and UV/O₃ have been applied for degradation of organic compounds (mainly, phenols, dyes and herbicides) in model aqueous solutions. Special emphasis is placed on studies combining UV irradiation (as a pre-treatment or post-treatment step) with biological treatment. In this review, the efficiencies of direct UV, UV/H₂O₂ and UV/TiO₂ processes for inactivation of a variety of pathogenic microorganisms in water and on surfaces are discussed. The analysis of the literature shows that more works need to be done on scaling up the processes, degradation/mineralization of target pollutant(s) in real effluents and evaluation of energy requirements.