The fate of endosulfan in aquatic ecosystems

Endosulfan, one of the major pesticides used in cotton-growing, is of environmental concern because of its toxicity to fish and its apparent persistence in the environment. This study examines the distribution and degradation pathways for endosulfan in an aquatic system and the processes by which it is removed. In the alkaline waters of the cotton region, hydrolysis is the dominant degradation process. By this mechanism alone, the expected half-lives for the alpha- and beta-endosulfan isomers were found to be 3.6 days and 1.7 days, respectively. Partitioning studies showed, however, that the major proportion of endosulfan would associate with the sediments (log Koc(alpha) 3.6 and log Koc(beta) 4.3). Field studies confirmed the presence of high concentrations in sediments. Microcosm experiments showed that loss of endosulfan was slower than predicted from hydrolysis rates. Models are presented to explain how desorption from sediment limits the loss of endosulfan from a system.     

The fate of acephate and carbaryl in water.

Acephate was resistent to hydrolysis in distilled, buffered water at pH 4.0 to 6.9, but not at pH 8.2, held for 20 days at 20 or 30 degrees C. The maximum conversion to methamidophos was 4.5% of the added acephate at pH 8.2 and 20 degrees C. The persistence of acephate in two natural waters, held at 9 degrees C for up to 42 and 50 days varied: 80% were recovered from pond water after 42 days, and 45% from creek water after 50 days. Rates of acephate degradation increased greatly when treated water samples were incubated in the presence of sediments, but not if water and sediment were autoclaved prior to treatment and incubation. The greatest conversion to methamidophos, 1.3% of the added acephate, had occurred after 42 days in pond water without sediment. Under the same conditions, carbaryl was less persistent than acephate in the natural waters: 18 to 20% were recovered from pond water after 42 days, and 37 to 40% from creek water after 50 days. The presence of sediment did not affect its degradation significantly. But more than 55% were recovered after 50 days if water and sediment were autoclaved prior to treatment and incubation. Neither acephate, methamidophos, nor carbaryl could be shown to escape from water into the atmosphere.     

Adsorbent selection for endosulfan removal from water environment

In the present study, an attempt was made to select a low cost adsorbing material for the removal of endosulfan [C,C'-(1,4,5,6,7,7-hexachloro-8,9,10- trinorborn-5-en-2,3-ylene)(dimethylsulphite)] from water. Various low cost adsorbents like wood charcoal, kimberlite tailings, silica, macro fungi sojar caju were tried with activated charcoal as reference material. The above materials were selected from various sources encompassing organic, inorganic, clayey, and biological sources. For the selection of suitable adsorbent for endosulfan uptake, maximum adsorption capacity (Qmax) was chosen as the parameter. Kinetic profiles of removal were generated for all the materials to assess the equilibrium time. Equilibrium studies were carried out for all materials to assess the adsorption equilibrium model that they followed. The model that gave the best correlation coefficient by linear regression analysis, was adopted for the calculation of Qmax of the corresponding adsorbent material. Using linearised forms of equilibrium models like Langmuir, BET, and Freundlich, maximum adsorptive capacities were determined. Activated charcoal showed the best adsorptive capacity with Qmax of 2.145 mg/g followed by wood charcoal 1.773 mg/g, sojar caju 1.575 mg/g, kimberlite tailings 0.8821 mg/g, and silica 0.3231 mg/g. Albeit activated charcoal gave better performance, it was not considered as a candidate material because of its high cost. Wood charcoal was the next best adsorbent with Qmax 1.773 mg/g. Therefore, wood charcoal was chosen as the best material for endosulfan removal. The study of physical and chemical characteristics of wood charcoal revealed that it is a potential adsorbent and can even be improved further.     

The fate and importance of organics in drinking water treatment: a review

In the pioneer days, the main driving forces for research of organics in drinking water treatment (DWT) were human health risks and optimisation of technology. The focus was on natural organic matter (NOM) structure, disinfection by-products (DBPs) formation, NOM removal by means of coagulation, adsorption, and oxidation, and development of the most efficient water treatment trains. Surprisingly, after decades of research, rapid development of analytical techniques and progress in risk assessment, the same driving forces are still in the limelight — although the topics have changed slightly. The attention switched from trihalomethanes to a new generation of DBPs. The definition of hydrophilic/hydrophobic NOM depends on the technique used for characterisation. It has become evident that numerous organic compounds can threaten water supply sources. Some of them had been ignored or overlooked in the past, but have recently been detected by advanced analytical tools even in drinking water. Prioritisation becomes priority per se. As far as processes are concerned, mainstream research has been following three lines: fouling mechanisms, application of hybrid processes and interactions between synthetic organic chemicals, other water constituents and materials used in DWT. Significant development has been made in membrane technology. This paper presents a broad overview of the recent organics research. Although the state-of-the-art technologies seem to have an answer to each and every question raised, it is still necessary to deal with specific problems on a case-by-case basis mainly due to the unique nature of NOM and different xenobiotics that may appear in various types of waters. In the end, human health risk, which derives from the presence/absence of organics, is only the tip of the iceberg — underneath lies a whole new universe — the socio-economic aspect of water treatment and quality that deserves much more attention.     

The study of distribution and fate of nitrobenzene in a water/sediment microcosm

In November 2005, an explosion occurred at a petrochemical plant of the Jilin Petrochemical Corporation in Jilin Province, China. A nearby water body was seriously polluted with a large spill of toxic substances made up of a mixture of benzene, aniline, and nitrobenzene (NB). To understand the long term impact of NB on public health and ecosystem around the Songhua River, it was necessary to investigate its fate in the environment. In this study, a microcosm was used to mimic the polluted water system and to study the transport and fate of NB in the river water body. The volatility and biodegradation of NB was investigated and a Markov model was applied to predict the fate of NB in the environment. The simulated results matched very well with the results obtained from the microcosm experiment. The model indicated that at room temperature and after around 500 h, there was only residual NB in the water and sediment. Most of the NB (around 82%) evaporated into the air and 18% was degraded by microorganisms.     

Oryzalin fate and transport in runoff water in Mediterranean vineyards

An experimental study was conducted in a 91.4-ha Mediterranean vineyard catchment in southern France to characterize the fate and transport of oryzalin in runoff water and thus to assess the risk of contamination of surface waters. Oryzalin concentrations in soil were monitored on two fields, one no-till and one tilled from March 1998 to March 2000. Concentrations in solution and on solid phase of runoff water were measured at the outlets of both fields and the catchment. The droughts in the two summer periods reduced the dissipation of oryzalin and increased its field half-life up to 35 days. Consequently, oryzalin was detected throughout the year in runoff water, with maximum dissolved concentrations > 600 microg l(-1) at the field scale. Oryzalin transport essentially occurred in solution. At the no-till field, seasonal losses were 2.29% and 1.89% of the applied amount in 1998 and 1999, respectively. The corresponding values at the tilled field were 1.56% and 0.29%, since tillage reduced total losses by reducing surface runoff. At the catchment scale, oryzalin concentrations were smaller than those at the field scale, due to dilution effects and staggering of application. Large part of the overland flow from the fields reinfiltrated in the ditches before reaching the outlet of the catchment. As a result, seasonal oryzalin losses were <0.2% of the applied amount.     

茭白田坑面水和渗漏水中氮素变化动态研究

茭白是黄浦江上游地区广泛种植的一种水田蔬菜.通过测坑定位试验,研究了茭白田坑面水和渗漏水中氮素变化动态和流失规律.结果表明,各处理茭白田坑面水中氮素形态以NH+4\|N为主,施肥后1～3 d,其占TN比例可达90%以上;渗漏水中氮素形态主要以NO-3\|N为主,施肥后呈现先上升后下降的趋势.通过增施有机肥、减少20%的无机氮肥用量可使坑面水TN减少20.74%,渗漏水中NO-3\|N减少16.10%,减少了氮素流失,且对茭白产量没有显著影响.、＝     

The fate of dichlorvos in soil

Experiments were conducted to determine the factors responsible for the loss (adsorption, chemical hydrolysis, microbial degradation, etc.) of dichlorvos (2,2-dichlorovingl $\text{0}$,$\text{0}$-dimethyl phosphate) in soil perfusion systems of Houston Black clay. The rate of disappearance from the perfusate (hence the rate of dichlorvos degradation in soil) was related directly to the presence of $\text{Bacillus}$$\text{cereus}$ in the perfusion system, the pH of the system, and the extent of dichlorvos adsorption. Gas liquid chromatographic analyses of the perfusates showed that dichlorvos disappearance was rapid when $\text{B}$. $\text{cereus}$ was added to a previously sterilized soil perfusion system (50% in 3.9 days). Under sterile conditions, 50% of the added dichlorvos was recovered after 10 days. When $\text{B}$. $\text{cereus}$ was added to a mineral salts medium containing dichlorvos as sole ccrbon source, 49% of the initial dichlorvos concentration was degraded in 4 days. The organism was not capable of utilizing dichlorvos as a sole phosphorus source. Chemical hydrolysis of dichlorvos in aqueous, buffered, soil-free systems showed that hydrolysis did not occur in very acid systems (<pH 3.3), but increased with increasing pH values (26% in 4 days at pH 6.9), and was rapid at pH 9.3 (> 99% in 2 days). The extent of dichlorvos adsorption was determined by comparing the initial loss of dichlorvos in a sterile, soil-free extract solution with the initial loss in a sterile soil perfusion system. The rapid initial disappearance of dichlorvos in the presence of sterilized soil was attributed to soil adsorption of the pesticide. After 10 days both systems contained equal concentrations (50%) of dichlorvos. Non-biological mechanisms accounted for 70% of the total degradation of dichlorvos, while bacterial degradation accounted for 30% in the soil perfusion systems.     

Halogenated acetaldehydes: analysis, stability and fate in drinking water

In our previous studies, chloral hydrate has been the only chlorinated acetaldehyde determined in drinking water because authentic standards of other related haloacetaldehydes were not available. Recently, standards of dichloroacetaldehyde, bromochloroacetaldehyde, dibromoacetaldehyde, bromodichloroacetaldehyde, chlorodibromoacetaldehyde, and tribromoacetaldehyde have become available commercially. They were obtained and verified for purity and stability using a dual-column GC-ECD system. Each commercial standard was found to contain small amounts of the other target haloacetaldehydes (HAs). The stability of the HAs stock solutions was solvent dependent: in acetone, the brominated species partially degraded to bromoacetone, while all target HAs were stable in MTBE for up to 8 months. The analytical parameters, required for the quantification of HAs in water, were determined and used to evaluate the stability of the HAs in water. Under the conditions of the sampling protocol (field pH adjustment to pH 4.5 and storage at 4 degrees C), the target HAs were stable in water for up to 14 days. However, at typical drinking water pH and temperature conditions, the stability varied with the HA species, pH, temperature and storage period. The trihalogenated acetaldehydes degraded, in part, to their corresponding trihalomethanes (THMs) at increasing pH and temperature. Most target HAs were detected in drinking water samples collected from various Canadian drinking water systems, and the speciation was dependent on water parameters (e.g. bromide concentration) and treatment processes. From the water samples analysed, chloral hydrate ranged between 7% and 51% of the total HAs (w/w). The weigh ratio of total HAs to total THMs (10-46%) indicated that HAs contributed significantly to the pool of DBPs in drinking water.     

Environmental fate of tetracycline resistance genes originating from swine feedlots in river water

Tetracyclines are antibiotics commonly used in swine farms to treat disease and promote growth. However, there are growing concerns regarding the discharge of animal feces into the environment owing to the potential for development and dissemination of tetracycline resistance genes (TRGs). In this study, farming wastewater from one Chinese swine farm as well as river water from seven locations downstream of the farm was sampled. Polymerase chain reaction (PCR) showed that 12 TRGs, including six efflux pump genes (tet(B), tet(C), tet(D), tet(E), tet(G) and tet(L)), five ribosomal protection proteins (RPPs) genes (tet(O), tet(M), tet(Q), tet(W) and tet(S)), and one enzymatic modification gene (tet(X)), were present in all wastewater and river water samples. Quantitative real-time PCR (qPCR) showed that the abundance of tet(C), tet(X), tet(O), tet(M), tet(Q) and tet(W) decreased with downstream flow. Among the detected TRGs, tet(C) had the highest abundance, ranging from 459.5 copies/16S rRNA gene copies in wastewater to 33.8 copies/16S rRNA gene copies in river water samples collected from the last location. Furthermore, pig-specific Bacteroidales 16S rRNA genetic marker was quantified by qPCR to determine the level of fecal pollution in the river water. Bivariate correlation analysis confirmed that the total relative abundance of the six TRGs was significantly correlated with the level of swine feces in the aquatic environment (R² = 0.63, P < 0.05), suggesting that swine feces mainly contributed to the spread of TRGs in the river water.

Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Environmental Science and Health, Part A to view the free supplemental file.     

Effect of endosulfan on blood glucose

Endosulfan was administered to cats intravenously at different doses. The compound (3 and 4 mg/kg) showed marked rise in blood glucose level after 15 and 30 minutes of treatment with a gradual fall upto 4 hrs. No change in blood glucose was observed at 2.0 mg/kg dose. Adrenalectomy prevented this rise in glucose level.     

The dissipation,distribution and fate of a branched 14C-nonylphenol isomer in lake water/sediment systems

A single tertiary isomer which is believed to be one of the major branched isomers of the isomeric nonylphenol was synthesized for use in investigations on its metabolism and estrogenicity in aquatic organisms. The physico-chemical properties of the isomer were determined to enable the prediction of its behaviour in aquatic environments. From laboratory investigations on its dissipation and distribution in lake water, which are reported in this paper, it was found that it had a half-life of dissipation of 38.1 days and 20.1 days in an open lake water and in an open lake water/ sediment system, respectively, and to be rapidly partitioned in to sediment giving a high concentration factor of 1.76 after 28 days with an initial dose concentration of 2.52 ppm. The main dissipation route was found to occur through volatilization and co-distillation. The isomer was, however, found to be resistant to biodegradation in both the lake water and sediment, showing only a slight 9% loss (after 56 days) and 4.2% loss (after 28 days), of the 14C-residues in lake water and lake water/sediment systems, respectively, by microbial activity. Transformation to other more polar metabolites possibly by hydroxylation was also found to be minimal in both lake water and sediment samples after 14 days by HPLC analysis. After 7 days, only 2.25 and 7.4% transformation to a more polar metabolite was detected in lake water and sediment samples, respectively.     

Ozonation of aqueous solution of alpha endosulfan

Ozonation of alpha endosulfan and the effects of some parameters such as pH, temperature and partial pressure on ozonation were investigated and the kinetic constants were calculated in this study. Alpha endosulfan solutions were ozonated in a lab-scale semi-batch reactor under variable experimental conditions. Increase in dissolved ozone concentration had a positive effect on oxidation rate. Alpha endosulfan could be removed up to 94% at pH 4 for an ozonation time of 60 minutes. The oxidation reaction was found to be of second order and of first order with respect to both ozone and alpha endosulfan. The temperature dependent reaction expression of alpha endosulfan was obtained as kd = (1.889 exp(- 2.21 x 10(-3)/T). It was concluded that, although the rate of reaction was lower than the rate of other pesticide oxidation reported in the literature. alpha endosulfan presented an obvious reaction to ozonation.     

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.     

The anaerobic degradation of endosulfan by indigenous microorganisms from low-oxygen soils and sediments

Indigenous mixed populations of anaerobic microorganisms from an irrigation tailwater drain and submerged agricultural chemical waste pit readily biodegraded the major isomer of endosulfan (endosulfan I). Endosulfan I was biodegraded to endosulfan diol, a low toxicity degradation product, in the presence of organic carbon sources under anaerobic, methanogenic conditions. While there was extensive degradation (>85%) over the 30 days, there was no significant enhancement of degradation from enriched inocula. This study demonstrates that endosulfan I has the potential to be biodegraded in sediments, in the absence of enriched microorganisms. This is of particular importance since such sediments are prevalent in cotton-growing areas and are typically contaminated with endosulfan residues. The importance of minimizing non-biological losses has also been highlighted as a critical issue in determining anaerobic biodegradation potential. Seals for such incubation vessels must be both oxygen and pollutant impermeable. Teflon-lined butyl rubber provides such a seal because of its resistance to the absorption of volatiles and in preventing volatilization. Moreover, including a 100 mM phosphate buffer in the anaerobic media has reduced non-biological losses from chemical hydrolysis, allowing biodegradation to be assessed.     

Occurrence of polycyclic musks in wastewater and receiving water bodies and fate during wastewater treatment

The occurrence of cashmerane (DPMI), celestolide, phantolide, traesolide (ATII), galaxolide (HHCB) and tonalide (AHTN) in sewage and surface waters and their fate during wastewater treatment and anaerobic sludge digestion is investigated. AHTN and HHCB are the most important representatives and influent concentrations of 0.41-1.8 and 0.9-13 μg L⁻¹ are observed. DPMI is detected in influent and effluent samples but in notably lower concentrations than AHTN and HHCB. Major sources of polycyclic musks are households, whereas industrial emitters seem to be of minor importance. This conclusion is supported by the analysis of selected industrial wastewaters (metal, textile and paper industry). Specific emissions of 0.36 ± 0.19 and 1.6 ± 1.0 mg cap⁻¹ d⁻¹ for AHTN and HHCB are calculated. Overall removal efficiencies between approx 50% and more than 95% are observed during biological wastewater treatment and removal with the excess sludge is the major removal pathway. Log K_D values of 3.73-4.3 for AHTN, 3.87-4.34 for HHCB and 2.42-3.22 for DPMI are observed in secondary sludge. During sludge digestion no or only slight removal occurred. Mean polycyclic musk concentrations in digested sludge amounted to 1.9 ± 0.9 (AHTN), 14.2 ± 5.8 (HHCB), 0.8 ± 0.4 (ATII) and 0.2 ± 0.09 (DPMI) mg kg⁻¹ dry matter. In the receiving water systems a comparable distribution as during wastewater treatment is observed. AHTN, HHCB and DPMI are detected in surface waters (ND (not detected) - < 0.04, ND - 0.32 and ND - 0.02 μg L⁻¹) as well as AHTN and HHCB in sediments (ND - 20, ND - 120 μg kg⁻¹). For HHCB an apparent K_OC value of 4.1-4.4 is calculated for sediments. Major source for polycyclic musks in surface waters are discharges from wastewater treatment plants. For HHCB and DPMI 100% of the load observed in the sampled surface waters derive from discharges of treated wastewater.     

Methodology for management of endosulfan contaminated eluent.

Management of Endosulfan contaminated eluent (24 mg/l) resulting from a treatment process to remove Endosulfan from water with wood charcoal, was attempted using various methods viz. volatilisation, hydrolysis and sorption by viable cell bacteria with and without acclimatisation. Volatilisation failed in giving better result, as Endosulfan was not considerably volatile. It could achieve a removal efficiency of 1.4-2%. Hydrolysis resulted in 28.4% and 17.9% removal of Endosulfan in acidic and alkaline media, respectively. Viable cell bacteria (aerobic) without prior acclimatization showed efficiency of 89.7% and after prior acclimatisation showed 96% removal efficiency. Sorption by the acclimatized biomass was found a suitable method for the removal of Endosulfan at a concentration of 24 mg/l.     

Kinetics of endosulfan sorption on to wood charcoal

Abstract

A part of the research work conducted to evaluate the efficiency of a locally available low cost wood charcoal in removing endosulfan, an organochlorine insecticide, has been presented here in this paper. In the batch experiments conducted at 1 mg/I initial concentration of endosulfan, it was found that wood charcoal could remove endosulfan from water up to 95%. Kinetic profiles were developed for various conditions and they followed second order kinetic reactions. Adsorption equilibrium time was determined by two different approaches namely rough estimate and 2% slope criteria. The equilibrium time was found to be 5 hrs. Forward, reverse, and overall reaction rate constants were determined by approximating the kinetic data to the first order reversible kinetic model. Rate constants increased with increasing initial concentration of endosulfan. Rate limiting process was determined by using kinetics data and further confirmed by the multiple interruption test. Pore and film diffusion coefficients were determined from the half time equations. Film diffusion appeared to be the rate limiting which was further supported by the multiple interruption test.     

Removal of endosulfan using aerobic mixed bacterial culture

With the increasing use of pesticides in modern agriculture, increased evidence of their disastrous effects on the environment has been noticed. Pesticides applied in various modes and places contaminate various parts of the environment, including groundwater sources. As pesticide problems are greater in the rural areas, the authors have developed a successful low-cost technology for rural areas with wood charcoal treated with nitric acid. As pesticides are classified as hazardous waste, the sludge resulting from their treatment has to be disposed off safely. This paper describes the removal of pesticides at a higher concentration of 24 mg/l, using a mixed culture of aerobic bacteria, and also a study of the inhibiting action of endosulfan on bacterial cells. It was found that bacteria without acclimatisation could remove 89.7% of endosulfan, and with prior acclimatisation the efficiency was 96%. It was found that removal in the initial phase is because of the hydrophobic nature of endosulfan and its affinity to sediments. The adsorbed endosulfan subsequently undergoes biotransformation, which has been confirmed by monitoring endosulfan concentrations in the bacterial sludge. Transformation was found to be significant in the acclimatised culture system. The fluctuation in bacterial performance was greater at lower concentrations of endosulfan, and overall inhibition was greater at higher concentrations.