Removal mechanism of endosulfan sorption onto wood charcoal

Endosulfan is among the most widely used pesticides in developing countries and other parts of the world and has been found to contaminate various parts of the environment, including drinking water sources. In an earlier study to find a suitable adsorbent to remove endosulfan, wood charcoal was found to give promising results. In the present study, the process controlling the rate of endosulfan sorption onto wood charcoal and the mechanism of removal were examined using various methodologies. Both film and pore diffusion coefficients were determined, and the linearity of the rate constants of adsorption with initial endosulfan concentrations revealed the process to be controlled by film diffusion. This was supported by the linear fit of the rate constants with the inverse of the diameter of adsorbent particles and the change in adsorption rates with agitation speed. Multiple interruption tests also revealed that endosulfan sorption onto wood charcoal is controlled by film diffusion. The increase in reaction rate constant with temperature and isosteric heat of adsorption in the range of -2.655 to 5.185 kcal/mol implied that the endosulfan removal process was endothermic in nature. The activation energy of 2.33 kcal/mol, which was less than 12 kcal/mol, revealed that the removal mechanism could be attributed to physisorption with a major contribution of van der Waals and electrostatic forces.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76-128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

Validation and application of an analytical method for determining pesticides in the gas phase of ambient air

A method for determining atmospheric concentrations of eight pesticides applied to corn and soybean crops in Mato Grosso state, Brazil is presented. The method involved a XAD-2 resin cartridge coupled to a low volume air pump at 2 L min^?1 over 8 hours. Pesticides were recovered from the resin using sonication with n-hexane:ethyl acetate and determined by GC-MS. Good accuracy (76–128%) and precision (CV < 20%) were obtained for atrazine, chlorpyrifos, alpha- and beta-endosulfan, endosulfan sulfate, flutriafol, malathion, metolachlor and permethrin. Method detection ranged from 9.0 to 17.9 ng m^?3. This method was applied to 61 gas phase samples collected between December 2008 and June 2009. Atrazine and endosulfan were detected both in urban and rural areas indicating the importance of atmospheric dispersion of pesticides in tropical areas. The simple and efficient extraction method and sampling system employed was considered suitable for identifying pesticides in areas of intense agricultural production.     

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.     

Biodegradation of malathion, α- and β-endosulfan by bacterial strains isolated from agricultural soil in Veracruz,Mexico

The objective of this study was to evaluate the capacity of two bacterial strains isolated, cultivated, and purified from agricultural soils of Veracruz, Mexico, for biodegradation and mineralisation of malathion (diethyl 2-(dimethoxyphosphorothioyl) succinate) and α- and β-endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6-9-methano-2,4,3-benzodioxathiepine-3-oxide). The isolated bacterial strains were identified using biochemical and morphological characterization and the analysis of their 16S rDNA gene, as Enterobacter cloacae strain PMM16 (E1) and E. amnigenus strain XGL214 (M1). The E1 strain was able to degrade endosulfan, whereas the M1 strain was capable of degrading both pesticides. The E1 strain degraded 71.32% of α-endosulfan and 100% of β-endosulfan within 24 days. The absence of metabolites, such as endosulfan sulfate, endosulfan lactone, or endosulfan diol, would suggest degradation of endosulfan isomers through non-oxidative pathways. Malathion was completely eliminated by the M1 strain. The major metabolite was butanedioic acid. There was a time-dependent increase in bacterial biomass, typical of bacterial growth, correlated with the decrease in pesticide concentration. The CO₂ production also increased significantly with the addition of pesticides to the bacterial growth media, demonstrating that, under aerobic conditions, the bacteria utilized endosulfan and malathion as a carbon source. Here, two bacterial strains are shown to metabolize two toxic pesticides into non-toxic intermediates.     

Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

Residues of organochlorinated pesticides in soils from the Czech Republic

National POPs inventories carried out currently in many countries as a part of the implementation of Stockholm Convention revealed the need for detailed information about a distribution of pollutants in various regions. Screening for the residues of selected organochlorinated pesticides (chlordane, heptachlor, dieldrin, aldrin, endrin, isodrin, endosulfan I, endosulfan II, methoxychlor, mirex) in soil and biotic samples from the Czech Republic was performed. Although these pesticides have never been used in large quantities in this region, results indicate that their residues still persist in the top layer soils more than 20 years after they have been banned. The fact that their soil concentrations in the mountains are generally higher than those in agricultural areas, and detection of the traces of pesticides that have never been used in this region suggest on their occurrence in soils due to the atmospheric redistribution rather than as a result of direct application.     

Biological treatment of a synthetic gold milling effluent

This paper reports on biological sludge acclimatisation and the results concerning the removal of free cyanide, thiocyanate and metallocyanides (copper, iron and zinc) from a synthetic gold milling effluent. The experiments were carried out in a continuous bench-scale bioreactor, and the experimental set-up consisted of two identical units, one of which served as control. The acclimatisation of the biomass was based on a stepwise procedure, in which the proportion of synthetic solution in the influent was gradually increased. The reactors were fed with a mixture of synthetic effluent and sewage, and the treatment efficiency was evaluated through the monitoring of the following parameters: chemical oxygen demand (COD), free cyanide, thiocyanate, copper, iron and zinc concentrations. A well adapted microbial consortium was obtained at the end of the acclimatisation period, which was able to remove more than 95% of free cyanide, thiocyanate, copper and zinc, originally found in the influent. These removal efficiencies were obtained when the reactor was operated with a hydraulic retention time (HRT) of about 8 h. The performance results of experiments carried out with lower HRT (5 h) and higher dissolved oxygen (DO) concentration (6.5 mg litre(-1)) are also presented and discussed in this study.     

Perspectives of using fungi as bioresource for bioremediation of pesticides in the environment: a critical review

Pesticides are used for controlling the development of various pests in agricultural crops worldwide. Despite their agricultural benefits, pesticides are often considered a serious threat to the environment because of their persistent nature and the anomalies they create. Hence removal of such pesticides from the environment is a topic of interest for the researchers nowadays. During the recent years, use of biological resources to degrade or remove pesticides has emerged as a powerful tool for their in situ degradation and remediation. Fungi are among such bioresources that have been widely characterized and applied for biodegradation and bioremediation of pesticides. This review article presents the perspectives of using fungi for biodegradation and bioremediation of pesticides in liquid and soil media. This review clearly indicates that fungal isolates are an effective bioresource to degrade different pesticides including lindane, methamidophos, endosulfan, chlorpyrifos, atrazine, cypermethrin, dieldrin, methyl parathion, heptachlor, etc. However, rate of fungal degradation of pesticides depends on soil moisture content, nutrient availability, pH, temperature, oxygen level, etc. Fungal strains were found to harbor different processes including hydroxylation, demethylation, dechlorination, dioxygenation, esterification, dehydrochlorination, oxidation, etc during the biodegradation of different pesticides having varying functional groups. Moreover, the biodegradation of different pesticides was found to be mediated by involvement of different enzymes including laccase, hydrolase, peroxidase, esterase, dehydrogenase, manganese peroxidase, lignin peroxidase, etc. The recent advances in understanding the fungal biodegradation of pesticides focusing on the processes, pathways, genes/enzymes and factors affecting the biodegradation have also been presented in this review article.     

Removal of hydrocarbon from refinery tank bottom sludge employing microbial culture

Accumulation of oily sludge is becoming a serious environmental threat, and there has not been much work reported for the removal of hydrocarbon from refinery tank bottom sludge. Effort has been made in this study to investigate the removal of hydrocarbon from refinery sludge by isolated biosurfactant-producing Pseudomonas aeruginosa RS29 strain and explore the biosurfactant for its composition and stability. Laboratory investigation was carried out with this strain to observe its efficacy of removing hydrocarbon from refinery sludge employing whole bacterial culture and culture supernatant to various concentrations of sand–sludge mixture. Removal of hydrocarbon was recorded after 20 days. Analysis of the produced biosurfactant was carried out to get the idea about its stability and composition. The strain could remove up to 85?±?3 and 55?±?4.5 % of hydrocarbon from refinery sludge when whole bacterial culture and culture supernatant were used, respectively. Maximum surface tension reduction (26.3 mN m^?1) was achieved with the strain in just 24 h of time. Emulsification index (E24) was recorded as 100 and 80 % with crude oil and n-hexadecane, respectively. The biosurfactant was confirmed as rhamnolipid containing C₈ and C₁₀ fatty acid components and having more mono-rhamnolipid congeners than the di-rhamnolipid ones. The biosurfactant was stable up to 121 °C, pH 2–10, and up to a salinity value of 2–10 % w/v. To our knowledge, this is the first report showing the potentiality of a native strain from the northeast region of India for the efficient removal of hydrocarbon from refinery sludge.     

Assessing spatial distribution,sources, and human health risk of organochlorine pesticide residues in the soils of arid and semiarid areas of northwest China

Thirty-two topsoil samples were collected to analyze the residue levels of organochlorine pesticides (OCPs) in topsoil of arid and semiarid areas of northwest China in 2011. Results showed that DDTs were the dominant contaminants with a mean concentration of 12.52 ng/g. The spatial distribution characteristics indicated that α-hexachlorocyclohexanes (HCHs) were mainly used in rural sites, whereas hexachlorobenzene (HCB) and endosulfan were detected mostly in urban areas. DDTs, heptachlor, and chlordane were found almost equally in both urban and rural areas. Source identification revealed that the current levels of HCHs in soils were attributable to the residues from their historical use and fresh usage of lindane (γ-HCH). DDTs were mainly from historical use and fresh usage of dicofol, and HCB was emitted from the chemical industry. It was also found that the current soil levels of heptachlor were mainly from its historical usage, endosulfan from fresh input, and chlordane from long-range atmospheric transport, respectively. The noncarcinogenic health risk assessment with a model was also conducted using USEPA standards for adults and children. Results indicated that health risk under nondietary exposure to OCPs decreased in the sequence of ΣDDT?>?ΣHCH?>?HCB?>?Σheptachlor?>?Σendosulfan?>?Σchlordane. According to the reference dose from the USEPA, the health risk under nondietary exposure to OCPs in the soil samples was at a relatively safe level.     

Anammox enrichment from different conventional sludges

Three sets of sequencing batch reactor (SBR) were used for Anammox enrichment from conventional sludges including upflow anaerobic sludge blanket, activated sludge, and anaerobic digestion sludge. After four months of operation, the Anammox activity occurred in all reactors allowing continuous removal of ammonium and nitrite. The morphology of the cultivated Anammox sludge was observed using scanning electron microscope. The photographs showed that the obtained culture was mostly spherical in shape, presumably Anammox culture. There were also filamentous-like bacteria co-existing in the system. Fluorescence in situ hybridization (FISH) analysis using 16S rRNA targeting oligonucleotide probes PLA46 and Amx820 showed that the dominant population developed in all SBRs was hybridized with both PLA46 and Amx820 gene probes. It means that the cultivated biomass in all SBRs was classified in the group of Planctomycetales bacteria with respect to the anaerobic ammonium-oxidizing bacteria, Candidatus Brocadia anammoxidans and Candidatus Kuenenia stuttgartiensis. Numerous time sequences were tested in this experiment. The shortest workable reaction time was found in the range from 5 to 7 h. Good quiescence of sludge was obtained at 30 min of settle period followed by a discharge period of 15 min. A long-term performance showed a near perfect removal of nitrite based on the influent NO2(-)-N concentration of 50-70 mg l(-1). The maximum ammonia removal efficiency was 80% with the influent NH4(+)-N concentration of 40-60 mg l(-1). It is, therefore, concluded that Anammox cultivation from conventional sludges was highly possible under control environment within four months.     

Biodegradation of lindane, methyl parathion and carbofuran by various enriched bacterial isolates

In the present study, lindane (1,2,3,4,5,6-hexachlorocyclohexane), methyl parathion (O-dimethylO-(4-nitro-phenyl) phosphorothioate) and carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate) degradation potential of different enriched bacterial cultures were evaluated under various environmental conditions. Enriched cultures behaved differently with different pesticides. Degradation was more in a facultative anaerobic condition as compared to that in aerobic condition. A specific pesticide enriched culture showed maximum degradation of that pesticide irrespective of pesticides and environmental conditions. Lindane and endosulfan enriched cultures behaved almost similarly. Degradation of lindane by lindane enriched cultures was 75 +/- 3% in aerobic co-metabolic process whereas 78 +/- 5% of lindane degradation occurred in anaerobic co-metabolic process. Degradation of methyl parathion by methyl parathion enriched culture was 87 +/- 1% in facultative anaerobic condition. In almost all the cases, many intermediate metabolites were observed. However, many of these metabolites disappeared after 4-6 weeks of incubation. Mixed pesticide-enriched culture degraded all the three pesticides more effectively as compared to specific pesticide- enriched cultures. It can be inferred from the results that a bacterial consortium enriched with a mixture of all the possible pesticides that are present in the site seems to be a better option for the effective bioremediation of multi-pesticide contaminated site.     

Removal of heavy metals from anaerobically digested sewage sludge by isolated indigenous iron-oxidizing bacteria

The removal of heavy metals (Cr, Cu, Zn, Ni and Pb) from anaerobically digested sludge from the Yuen Long wastewater treatment plant, Hong Kong, has been studied in a batch system using isolated indigenous iron-oxidizing bacteria. The inoculation of indigenous iron-oxidizing bacteria and the addition of FeSO4 accelerated the solubilization of Cr, Cu, Zn, Ni and Pb from the sludge. pH of the sludge decreased with an increase in Fe2+ concentrations and reached a low pH of 2-2.5 for treatments receiving both bacterial inoculation and FeSO4. After 16 days of bioleaching, the following heavy metal removal efficiencies were obtained: Cr 55.3%, Cu 91.5%, Zn 83.3%, Ni 54.4%, and Pb 16.2%. In contrast, only 2.6% of Cr, 42.9% of Cu, 72.1% of Zn, 22.8% of Ni and 0.56% of Pb were extracted from the control without the bacterial inoculation and addition of FeSO4. The residual heavy metal content in the leached sludge was acceptable for unrestricted use for agriculture. The experimental results confirmed the effectiveness of using the isolated iron-oxidizing bacteria for the removal of heavy metals from sewage sludge.     

Acclimatisation to nitrilotriacetic and in the activated sludge process

The period of acclimatisation prior to the biodegradation of nitrilotriacetic acid in an activated sludge pilot plant was studied in a series of experiments. The effects of low and high influent heavy metals concentrations upon acclimatisation are reported.     

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.     

好氧颗粒污泥处理高浓度氨氮废水的研究

在不同接种源污泥颗粒化过程中污泥理化性状对比研究的基础上,采用成熟好氧颗粒污泥处理高浓度氨氮废水,对其脱氮行为以及不同C/N条件下好氧颗粒污泥微生物的比耗氧速率、好氧颗粒污泥对氨氮的比降解速率随时间的变化等进行了研究.实验结果表明,在进水氨氮质量浓度较高(480 mg/L)、温度30℃左右的条件下,稳定运行15 d,氨氮的去除率维持在85%左右;进水氨氮的浓度越高,随着微生物对环境的逐渐适应,硝化菌的活性也逐步增加;随着进水氨氮浓度的提高,好氧颗粒污泥对氨氮的比降解速率也逐渐上升.     

Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa

This study assesses the risk of current-use pesticides in a temporarily open estuary in South Africa by developing probabilistic risk estimates. Particle-associated pesticides (chlorpyrifos, prothiofos, cypermethrin, fenvalerate, endosulfan and p,p-DDE) and physicochemical parameters (salinity, temperature, flow, and total organic content (TOC)) were measured in the Lourens River estuary (Western Cape) twice a month over a period of two years and equilibrium partitioning theory was applied to calculate concentrations of pesticides in the water. The 90th percentile concentrations of pesticides associated to suspended particles and the calculated concentrations in water were 34.0microg kg(-1) and 0.15microg l(-1) for prothiofos, 19.6microg kg(-1) and 0.45microg l(-1) for chlorpyrifos and 18.6microg kg(-1) and 0.16microg l(-1) for endosulfan. Highest average concentrations were found around the summer season due to higher application rates and as a result of the low flow during this season. Species sensitivity distribution indicated a 1.5-2.8 times higher toxicity (hazardous concentration HC5) for marine organisms compared to freshwater organisms. The calculated concentrations in the water exceeded all threshold values suggested by international water guidelines. Chlorpyrifos and endosulfan posed the highest acute risk to the Lourens River estuary. No sufficient toxicity data and threshold values were found for prothiofos.     

Model development and application for surfactant biodegradation in an acclimatising activated sludge system

A model for the biodegradation of non-ionic surfactants in an activated sludge system during acclimatisation was developed, based on respirometric and titrimetric experimental data. The data were obtained in a sequencing batch reactor (SBR) using a non-ionic surfactant as sole carbon source and sludge previously acclimatised to a different surfactant. The model was successfully applied to successive SBR-cycles of sludge acclimatisation processes subjected to two ethoxylated surfactants. The model was validated using the corresponding total organic carbon data. The evolution of the model parameters along the acclimatisation process was examined. An acclimatisation model was developed using the evolution of two of these parameters (affinity constant and inhibition constant), supported by two independently calculated acclimatisation indicators. This acclimatisation model was then applied to determine an optimal surfactant concentration sequence to feed non-acclimatised sludge during a period of 41 days, in order to induce pre-acclimatisation to this surfactant before it replaces another one in the wastewater. The model was also useful in the economical assessment of this and alternative procedures to cope with frequent changes in activated sludge feed composition.     

The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels

This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides. Rivers were found to be more polluted than lakes. The detected concentrations of most pesticides follow a seasonal variation, with maximum values occurring during the late spring and summer period followed by a decrease during winter. Nationwide, in many cases the reported concentrations ranged in low ppb levels. However, elevated concentrations were recorded in areas of high pesticide use and intense agricultural practices. Generally, similar trends and levels of pesticides were found in Greek rivers compared to pesticide contamination in other European rivers. Monitoring of the Greek water resources for pesticide residues must continue, especially in agricultural regions, because the nationwide patterns of pesticide use are constantly changing. Moreover, emphasis should be placed on degradation products not sufficiently studied so far.