Distribution and fate of organochlorine pesticide residues in sediments from the selected rivers in Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from selected rivers in Taiwan was investigated to evaluate the pollution potentials and hazard in river sediments. Da-han River and Erh-jen River were selected as the target rivers due to their serious pollution. A total of 40 surface sediment samples were collected at five sampling stations along the rivers. Results showed that the concentrations of various pesticides in sediments were in the range of 0.57-14.1 ng/g for sigmaHCH, 0.05-0.15 ng/g for aldrin, 0.12-5.8 ng/g for dieldrin, 0.22-0.64 for endrin, 0.24-6.37 ng/g for endosulfan and 0.21-8.81 ng/g for EDDT (p,p'-DDD, p,p'-DDE, p,p'-DDT). Among the OCPs, sigmaHCH, endosulfan and sigmaDDT were the most dominant compounds in the river sediments. Endosulfan sulfate was the most frequent detected compound in the sediments from the selected rivers. Also, sigmaDDT, dieldrin and beta-HCH were in abundance. Different contamination patterns between the selected river sediments were also observed. Da-han River was mainly contaminated with endosulfan sulfate and sigmaDDT. Whereas the main pesticides in Erh-jen River were beta-HCH and sigmaDDT. Among the cyclodiene compounds, dieldrin was in abundance in most of the sediments. Moreover, the frequencies of detection of the metabolites were higher than those of parent compounds, depicting that the sediments have contaminated for a long time. The results obtained in this study showed that there still exist a variety of OCP residues in the river sediments in Taiwan.     

Degradation of aldrin and endosulfan in rotary drum and windrow composting

Removal efficiencies, kinetics and degradation pathways of aldrin, endosulfan α and endosulfan β in vegetable waste were evaluated during rotary drum and conventional windrow composting. The highest percentage removal of aldrin, endosulfan α and endosulfan β in rotary drum composting was 86.8, 83.3 and 85.3% respectively, whereas in windrow composting, it was 66.6%, 77.7% and 67.2% respectively. The rate constant of degradation of aldrin, endosulfan α and endosulfan β during rotary drum composting ranged from 0.410–0.778, 0.057–0.076 and 0.009–0.061 day^?1 respectively. The pathways of degradation of these pesticides in composting process were proposed. Metabolites dieldrin and 1 hydroxychlorodene formed during composting of aldrin in the vegetable waste indicated the occurrence of epoxidation reaction and oxidation of bridge carbon of aldrin containing the methylene group. Formation of chloroendic acid and chloroendic anhydride during composting of endosulfan containing vegetable waste support the occurrence of endosulfan sulfate and dehydration reaction respectively.     

Organochlorine pesticides in the surface waters of Northern Greece

A survey undertaken in Northern Greece has shown that organochlorine pesticides are present in the surface waters. Surface water samples have been collected seasonally from four rivers and five lakes for a period of two years. Solid-phase extraction followed by gas chromatographic techniques with electron capture detection was used for the determination of the compounds. The most commonly encountered organochlorine pesticides in surface waters were the isomers of hexachlorocyclohexane, aldrin, dieldrin and endosulfan sulfate. In some cases the concentrations detected were higher than the qualitative target levels set by the European Union, especially for hexachlorocyclohexane and aldrin. The occurrence of these compounds in Greek surface waters can be attributed to intense agricultural activity as well as to transboundary pollution.     

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.     

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.     

Enrichment and isolation of endosulfan-degrading microorganism from tropical acid soil

Endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,3,4-benzo-dioxathiepin-3-oxide) is a cyclodiene organochlorine currently used as an insecticide all over the world and its residues are posing a serious environmental threat. This study reports the enrichment and isolation of a microbial culture capable of degrading endosulfan with minimal production of endosulfan sulfate, the toxic metabolite of endosulfan, from tropical acid soil. Enrichment was achieved by using the insecticide as sole sulfur source. The enriched microbial culture, SKL-1, later identified as Pseudomonas aeruginosa, degraded up to 50.25 and 69.77 % of α and β endosulfan, respectively in 20 days. Percentage of bioformation of endosulfan sulfate to total formation was 2.12% by the 20th day of incubation. Degradation of the insecticide was concomitant with bacterial growth reaching up to an optical density of 600 nm (OD600) 2.34 and aryl sulfatase activity of the broth reaching up to 23.93 μg pNP/mL/hr. The results of this study suggest that this novel strain is a valuable source of potent endosulfan–degrading enzymes for use in enzymatic bioremediation. Further, the increase in aryl sulfatase activity of the broth with the increase in degradation of endosulfan suggests the probable involvement of the enzyme in the transformation of endosulfan to its metabolites.     

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.     

Dissipation, half-lives, and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre(-1). Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T(1/2) = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T(1/2) = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

Dissipation,half-lives,and mass spectrometric identification of endosulfan isomers and the sulfate metabolite on three field-grown vegetables

Endosulfan 3 EC, a mixture of α- and β-stereo isomers, was sprayed on field-grown pepper, melon, and sweet potato plants at the recommended rate of 0.44 kg A.I. acre^?1. Plant tissue samples (leaves, fruits, or edible roots) were collected 1 h to 30 days following spraying and analyzed for endosulfan isomers (α- and β-isomers). Analysis of samples was accomplished using a gas chromatograph (GC) equipped with a mass detector in total ion mode. The results indicated the formation of endosulfan sulfate as the major metabolite of endosulfan sulfite and the relatively higher persistence of the β-isomers as compared to the α-isomer. The initial total residues (α- and β-isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper and melon fruits, the α-isomer, which is the more toxic to mammals, dissipated faster (T_1/2 = 1.22 and 0.95 d, respectively) than the less toxic β-isomer (T_1/2 = 3.0 and 2.5 d, respectively). These results confirm the greater loss of the α-isomer compared to the β-isomer, which can ultimately impact endosulfan dissipation in the environment. Additionally, the higher initial residues of endosulfan on pepper and sweet potato leaves should be considered of great importance for timing field operations and the safe entry of harvesters due to the high mammalian toxicity of endosulfan.     

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.     

Biodegradation of alpha and beta endosulfan in soil as influenced by application of different organic materials

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of alpha and beta endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg(-1). The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for alpha and beta endosulfan isomers by gas chromatography. The results indicated that the half-life (T(1/2)) of alpha-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T(1/2) of beta-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T(1/2) was about 115 days for the other three treatments.     

The fate of endosulfan in water

Although the use of endosulfan to control cotton pests has declined, this insecticide still has widespread application in agriculture and can contaminate riverine systems as runoff from soil or by aerial deposition. The degradation of endosulfan in pure water at different pH values of 5, 7 and 9 and in river water from the Namoi and the Hawkesbury rivers of New South Wales (NSW), Australia, was studied in the laboratory. Endosulfan transformation into endosulfan sulfate in river water using artificial mesocosms was also investigated. The results show endosulfan is stable at pH 5, with increasing rates of disappearance at pH 7 and pH 9 by chemical hydrolysis. Incubation of endosulfan with river water at pH 8.3 resulted in the disappearance of endosulfan and the formation of endosulfan diol due to the alkaline pH as well as formation of endosulfan sulfate. Although the degradation of endosulfan by Anabaena, a blue-green alga, did not result in the transformation of endosulfan to endosulfan sulfate, we conclude that other microorganisms catalyzed the formation of the sulfate. Significant conversions of endosulfan into endosulfan sulfate were also reported from associated field studies using artificial mesocoms containing irrigation water from rivers inhabitated by micro-macro fauna. From these results, we conclude that the presence of endosulfan sulfate in river water cannot be used to distinguish contamination by runoff from soil from contamination by aerial drift or redeposition.     

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 Endosulfan in Water

Although the use of endosulfan to control cotton pests has declined, this insecticide still has widespread application in agriculture and can contaminate riverine systems as runoff from soil or by aerial deposition. The degradation of endosulfan in pure water at different pH values of 5, 7 and 9 and in river water from the Namoi and the Hawkesbury rivers of New South Wales (NSW), Australia, was studied in the laboratory. Endosulfan transformation into endosulfan sulfate in river water using artificial mesocosms was also investigated. The results show endosulfan is stable at pH 5, with increasing rates of disappearance at pH 7 and pH 9 by chemical hydrolysis. Incubation of endosulfan with river water at pH 8.3 resulted in the disappearance of endosulfan and the formation of endosulfan diol due to the alkaline pH as well as formation of endosulfan sulfate. Although the degradation of endosulfan by Anabaena, a blue-green alga, did not result in the transformation of endosulfan to endosulfan sulfate, we conclude that other microorganisms catalyzed the formation of the sulfate. Significant conversions of endosulfan into endosulfan sulfate were also reported from associated field studies using artificial mesocoms containing irrigation water from rivers inhabitated by micro-macro fauna. From these results, we conclude that the presence of endosulfan sulfate in river water cannot be used to distinguish contamination by runoff from soil from contamination by aerial drift or redeposition.     

Residues of organochlorine pesticides in near shore waters of LaiZhou Bay and JiaoZhou Bay, Shandong Peninsula, China

The extent of organochlorine pesticides (OCPs) contamination in coastal waters around LaiZhou Bay and JiaoZhou Bay in Shandong Peninsula, northern China, was investigated. The areas around the two bays are both densely populated, thrive with intensive agriculture and industrial activities. Multi-techniques including GC-MS, GC-muECD coupled with chemical peak confirmation and strict QC procedures were used for the quantitative determination of 15 OCPs including alpha, beta, gamma and delta isomers of hexachlorocyclohexane (HCH), pentachloronitrobenzene (PCNB), heptachlor, aldrin, endosulfan, p,p'-DDE, dieldrin, endrin, p,p'-DDD, o,p'-DDT, p,p'-DDT and methoxychlor. The survey results show that contaminations by OCP residues remain widespread in the areas, but the averaged concentration levels are all below the regulatory limits, e.g., CMC limits (acute criterion values) specified in US Environmental Protection Agency (USEPA) and China national standards. Average concentration of OCPs in water samples were from undetectable to 3.8 ng l(-1) in LaiZhou Bay and from 0.1 to 3.9 ng l(-1) in JiaoZhou Bay, respectively. A comparison between the current and historical data shows a rapidly decreasing trend of OCPs over the past twenty years in the study areas.     

Biodegradation of α and β Endosulfan in Soil as Influenced by Application of Different Organic Materials

Abstract

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of α and β endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg^?1. The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for α and β endosulfan isomers by gas chromatography. The results indicated that the half-life (T _½) of α-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T _½ of β-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T _½ was about 115 days for the other three treatments.     

Determination of organochlorine pesticide residue in sediment and water from the Densu river basin, Ghana

The distribution of organochlorine pesticides in the aquatic ecosystem from the Densu river revealed varying levels of concentration in water and the sediment samples. Three locations were sampled along the river to evaluate the levels of organochlorine pesticide residue in the river. Sediment and surface water samples were extracted by soxhlet and liquid-liquid extraction respectively and analyzed using Gas Chromatograph coupled with electron capture detector. The detectable organochlorine pesticides were gamma-hexachlorocyclohexane (HCH), delta-hexachlorocyclohexane, heptachlor, aldrin and dieldrin. The other pesticides that were investigated are gamma-chlordane, alpha endosulfan, endosulfan sulfate, p,p′-DDT and its metabolite p,p′-DDE, methoxychlor, endrin and its metabolite endrin aldehyde and endrin ketone. The order of increasing frequency of detection of samples was higher in sediment than water. In sediment, the mean concentration ranged from 0.030 μg kg⁻¹ dry weight (endrin) to 10.98 μg kg⁻¹ dry weight (aldrin). The highest detected concentration of organochlorine in water was endosulfan sulfate with mean concentration of 0.185 μg L⁻¹. Analysis of variance indicated significant differences for most organochlorine pesticide residue in the sediment sampled from the various locations. Some of the levels of organochlorine pesticides detected in water were relatively high compared to guideline values set by World Health Organization and Australia and thus could be harmful if the trend is not checked.     

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.     

Concentration of organochlorine pesticides in wine corks

Wine corks were extracted and analyzed for 23 organochlorine pesticides, including alpha-, beta-, and gamma-hexachlorocyclohexanes (HCH), hexachlorobenzene, DDT, DDE and DDD, chlordane, endosulfan, dieldrin, aldrin, and endrin. This was done to investigate the occurrence, concentrations, composition profiles, and possible sources of organochlorine contamination. All groups of compounds were detected in every sample investigated, with the exception of aldrin and endrin. The total concentrations of organochlorine compounds in all samples ranged from 75-120 ng/g lipid, and for most compounds, the concentrations of organochlorines in cork were consistent with published data for other plant tissues. Differences in the relative abundances of the various classes of organochlorine pesticides were substantial and were probably due to differences in the pesticide usage practices of the various regions in which the cork producing trees were grown.     

Quantification of low levels of organochlorine pesticides using small volumes (<or=100 microl) of plasma of wild birds through gas chromatography negative chemical ionization mass spectrometry

A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100 microl from wild birds. The method detection limits ranged from 0.012 to 0.102 pg/microl and the method reporting limit from 0.036 to 0.307 pg/microl for alpha, gamma, beta and delta-hexachlorocyclohexane (HCH), heptachlor, aldrin, heptachlor epoxide, endosulfan I, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), dieldrin, endrin, endosulfan-II, endrin-aldehyde and endosulfan-sulfate. Pesticide levels in small serum samples from individual Falco sparverius, Sturnella neglecta, Mimus polyglottos and Columbina passerina were quantified. Concentrations ranged from not detected (n/d) to 204.9 pg/microl for some OC pesticides. All levels in the food web in and around cultivated areas showed the presence of pesticides notwithstanding the small areas for agriculture existing in the desert of Baja California peninsula.