Chlorinated pesticide residues in surface sediments from the River Kaveri, south India

Chlorinated compounds have preferential attraction for organic phases found in sediments. Usage of chlorinated pesticides in agriculture and vector control is more in developing countries. The residue levels of HCH isomers, and DDT, and its metabolites were quantified in surface sediments from the River kaveri and Coleroon in Tamil Nadu state, South India. The concentration of HCH ranged from 4.35 to 158.4 ng g-1 (dry wt.). Among the isomers of HCH, alpha-HCH is predominant followed by beta and gamma-HCH. The levels of DDT varied from 0.69 to 4.85 ng g-1 (dry wt.). Among the DDT compounds, p,p'-DDE quantified more (> 40%) in all the sites. This suggests that p,p'-DDE is a major breakdown (dehydrochlorination) product of DDT in the sediment compartment. Higher concentration of HCH residues reveals its large usage in agriculture. The flux of pesticide residues from land to river including downward flux to sediment is less.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Evaluation of hexachlorocyclohexane contamination from the last lindane production plant operating in India

Purpose

??-Hexachlorocyclohexane (HCH), ??-HCH, and lindane (??-HCH) were listed as persistent organic pollutants by the Stockholm Convention in 2009 and hence must be phased out and their wastes/stockpiles eliminated. At the last operating lindane manufacturing unit, we conducted a preliminary evaluation of HCH contamination levels in soil and water samples collected around the production area and the vicinity of a major dumpsite to inform the design of processes for an appropriate implementation of the Convention.

Methods

Soil and water samples on and around the production site and a major waste dumpsite were measured for HCH levels.

Results

All soil samples taken at the lindane production facility and dumpsite and in their vicinity were contaminated with an isomer pattern characteristic of HCH production waste. At the dumpsite surface samples contained up to 450?g?kg^?1 ?? HCH suggesting that the waste HCH isomers were simply dumped at this location. Ground water in the vicinity and river water was found to be contaminated with 0.2 to 0.4?mg?l^?1 of HCH waste isomers. The total quantity of deposited HCH wastes from the lindane production unit was estimated at between 36,000 and 54,000?t.

Conclusions

The contamination levels in ground and river water suggest significant run-off from the dumped HCH wastes and contamination of drinking water resources. The extent of dumping urgently needs to be assessed regarding the risks to human and ecosystem health. A plan for securing the waste isomers needs to be developed and implemented together with a plan for their final elimination. As part of the assessment, any polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) generated during HCH recycling operations need to be monitored.     

Pesticide residues in cow milk consumed in São Paulo City (Brazil)

Residues of pesticides were surveyed in 132 samples of cow milk collected from bulk transports (38 samples of raw milk) and market (94 samples of pasteurised milk). These samples were analysed by the multiresidue analytical method DFG S19 for pesticide contamination. More than 70 active substances were studied and the identification and quantification were made by gas chromatographic technique. The results showed that 0.76% of samples were contaminated with HCH (alpha isomer) and 10.60% with endosulfan (alpha and beta isomers). Both pesticides, endosulfan and HCH, found in milk samples, indicated their use in agriculture practices, although legislation in Brazil does not permit the use of HCH since 1985 and endosulfan can be used only in a few crops. These compounds should not be present in milk because there are implications on human health. Organophosphorus, carbamates, pyrethroids, herbicides, and fungicides were not detected in cow's milk samples.     

Distribution of hexachlorocyclohexane isomers in soil samples from a small scale industrial area of Lucknow, North India, associated with lindane production

Concentrations of hexachlorocyclohexane isomers (alpha-HCH, beta-HCH, gamma-HCH, and delta-HCH) were studied in soils samples collected from a small scale industrial unit of Lucknow associated with lindane production. All four isomers were detected from ten sites and the total HCH isomers in the analyzed samples varied from 53 to 99mgkg(-1). Cluster analysis was performed to group the soil sites in terms of their HCH contamination level. Low alpha/gamma HCH ratios were found and they indicate recent input of HCH. There is an urgent need for the on-site remediation of these contaminated sites in order to prevent the long-term environmental pollution.     

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.     

Investigation of pesticide residues in water,sediments and fish samples from Tapi River,India as a case study and its forensic significance

Abstract

This research is a case study on detection of pesticides in river water, sediment as well as fish samples from Tapi River, among the major rivers of Gujarat, India. To investigate the misuse, concentration level and occurrence patterns of persistent pesticides, samples were collected from the river. Chlorpyrifos, methyl parathion, hexachlorocyclohexane (HCH), dichloro diphenyl trichloroethane (DDT) and endosulfan were analyzed by gas chromatography technique with flame ionization detector (FID). Scanty reports are available, but after 1999, no such data are reported as some of these pesticides have been banned. Although these pesticides are still in use which we observed from the obtained results. In this river, the amount of endosulfan, chlorpyrifos, and methyl parathion was observed in surface water with concentrations of 37.56?µg/L, 0.86?µg/L and 0.43?µg/L, respectively. Endosulfan, DDT and methyl parathion detected in sediment were 38.38?ng/g, 0.65?ng/g and 0.77?ng/g, respectively. In fish samples, levels of endosulfan, chlorpyrifos, and methyl parathion detected were 101.28, 0.392, and 3.49?ng/g correspondingly. Results showed that highly toxic pesticides are still being used in the surrounding area, and there is an urgent need for enforcement of rules to control the production and application of such pesticides.     

Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.     

Residues of organochlorine pesticides in Hong Kong soils

It was short of research on the organochlorine pesticides (OCPs) residues in the soils of Hong Kong. Sixty-six representative soil samples were collected from the 46 sites covering five types of land uses in Hong Kong. Hexachlorohexanes (HCH) and 7 Stockholm Convention OCPs were analyzed by gas chromatograph (GC) equipped with a Nickel 63 electronic capture detector (muECD). The results presented that HCH and 5 Stockholm Convention pesticides were detected in Hong Kong soils although the detectable ratio varies to a great extent. The concentration sequence of the five detectable OCPs was HCH > dichlorodiphenyltrichloroethane (DDT) > hexachlorobenzene (HCB) approximately = Endrin > alpha-endosulfan. Among the OCPs and their homologues or isomers, beta-HCH and p,p'-DDE were the two predominant substances according to the concentrations and detectable ratios, concentrations of which in soils were averagely 6.12 microg kg(-1) and 0.41 microg kg(-1) respectively. Soil horizon samples of 0-10 cm, 10-30 cm and >30 cm depth were selected from nine soil profiles to demonstrate the depth distributions of DDT and HCH in soil profiles. Concentrations of HCH tended to increase gradually from the topsoil to bottom layer while the lowest concentration of DDT is usually found in the subsoil (10-30 cm) in most sampling sites. In addition, close correlations of pH(KCl) and total organic carbon (TOC) with HCH indicated an effect on the residues of HCH caused by these two soils properties, but such relationships were not found with DDT or other OCPs.     

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain)

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC–ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers β-HCH and -HCH in all samples whereas δ-HCH and γ-HCH were at lower levels. Some other pesticides such as p,p′-DDT, p,p′-DDD and p,p′-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC–MS.     

Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua

The hydrographic basin of the Atoya river, located in the Department of Chinandega, one of the main cotton producing regions in Nicaragua, is intensively contaminated by pesticides. Samples of river waters and sediments, as well as strategically selected wells have been analyzed to study variations in the concentrations of organochlorine and organophosphorus pesticide residues between the dry season (November-April) and the rainy season (May-June). Generally, higher concentrations of pesticides have been detected in the river waters and sediments in the dry season. DDT, DDD, DDE compounds and toxaphene are the most frequent organochlorine residues found in the water and sediment samples, while endrin, aldrin, dieldrin and lindane are mainly found in the waters of rivers and wells. Organophosphorus compounds were rarely detected. However, residues of ethion, methyl-parathion and ethyl-parathion were found in high concentrations in some river and well water samples. Generally, organochlorine compounds tend to accumulate in the fine grain-size fractions, rich in organic matter, except DDE, which concentrates basically in the coarse grain-size fractions.     

Occurrence and distribution of hexachlorocyclohexane isomers in vegetation samples from a contaminated area

The occurrence and distribution of four major hexachlorocyclohexane (HCH) isomers (alpha-, beta-, gamma- and delta-) were studied in vegetation samples of a highly contaminated area close to a small-scale industrial belt in Lucknow (North India). Eight species of plants were collected at different points of the contaminated area and different parts of the plants were separated in order to study the difference in uptake and accumulation. The samples were extracted by matrix solid-phase dispersion (MSPD) extraction and finally determined by a gas-chromatograph equipped with (63)Ni electron capture detector (ECD). HCH isomers were present in almost all samples and the concentration of total HCH in the plant sample analyzed varied between 13 and 44 mg kg(-1), being the main isomer of beta-HCH (8-22 mg kg(-1)). Lindane (gamma-HCH) was present in all samples (1-9 mg kg(-1)). Solanum torvum Sw., and Erianthus munja shows the highest and lowest capacity for accumulation of HCH, respectively with a significant difference at p<0.01 level. The highest concentration of HCH residue in root samples indicates the most likely mechanism of HCH accumulation in these plants was sorption of soil HCH on roots. Solanum torvum Sw., and Withania somnifera (L.) Dunal could accumulate considerable levels of HCH isomers (44 and 34 mg kg(-1), respectively). The results reflect the importance of plants in monitoring purposes and their potential for phytoremediation of HCH contaminated soils.     

Pesticide pollution remains severe after cleanup of a stockpile of obsolete pesticides at Vikuge, Tanzania

High levels of DDT residues and hexachlorocyclohexanes (HCHs) were found in soil, well water, and surface water around a collapsed pesticide storage shed at Vikuge Farm, Tanzania. Residues of DDT and HCHs were found at three soil depths down to 50 cm. Surface soil samples contained up to 28% total DDT and 6% total HCH residues. Water samples had concentrations of up to 30 microg L(-1) of organochlorine pesticides. Other compounds detected were aldrin, azinphos-methyl, carbosulfan, gamma-chlordane, chlorprofam, heptachlor, hexazinone, metamitron, metazachlor, pendimethalin, and thiabendazole. Although the visible remains of pesticides have been removed, the remaining soil is itself hazardous waste and poses a risk to the environment and the inhabitants of the surrounding villages. These findings show the necessity to follow up the environmental situation at former storage sites of obsolete stocks of pesticides, and that the environmental problems are not necessarily solved by removing the visible remains.     

Seasonal variation of persistent organochlorine insecticide residues in Vellar River waters in Tamil Nadu, South India

Water samples collected from Vellar river and Pichavaran mangroves at Porto Novo (11 degrees 29' N, 79 degrees 46' E), Tamil Nadu State, South India, from December 1987 to January 1989 were analyzed to determine the seasonal variation of the levels of organochlorine insecticides such as HCH (BHC) and DDT. Both these insecticides showed higher levels from October to February, although this trend was more pronounced in HCH than DDT, reflecting the application of technical HCH largely and probably small quantities of DDT during the flowering season of rice. The alpha-HCH was detected as a dominant isomer for all seasons monitored followed by beta-HCH. Among DDT compounds, p,p'-DDT was the highest in river water except in the dry season when p,p'-DDD showed a higher percentage. On the other hand, in mangroves p,p'-DDE was highest during the wet season and p,p'-DDD during the dry season. Air-water partitioning data of HCH isomers and DDT compounds in Vellar river revealed that these chemicals tend to be in the water phase. These observations may aid in understanding the role of a tropical paddy area on the behavior and fate of man-made chemicals in view of worldwide contamination.     

Organo-chlorine pesticide (DDT and HCH) residues in the Taihu Lake Region and its movement in soil-water system I. Field survey of DDT and HCH residues in ecosystem of the region

The use of organo-chlorine (DDT and HCH) has been banned in China for 20 years. A field survey was carried out during 1999-2000 in the Taihu Lake Region. Organo-chlorine pesticide (OCP) residues in soil, water, fish and sediment samples were investigated. DDT was detected in 5 out of 10 samples with concentration ranging from 0.3 to 5.3 microg/kg in the surface (0-15 cm) layer, 6 out of 10 with 0.5 to 4.0 microg/kg in the subsoil layer (16-30 cm), and 4 of 10 with 0 to 2.7 microg/ kg in the deep soil layer (31-50 cm). Results for HCH residues in soil samples were similar to those of DDT. These results indicate that OCP residues in 0-50 cm profile had been leached out or degraded to safe level. In river water DDT was detected in 10 out of 13 samples ranging from 0.2 to 9.3 microg/l, with an average of 1.0 microg/l. While HCH was detected in 12 out of 13 samples ranging from 0.02 to 36.1 microg/l, with an average 5.6 microg/l. DDT residues in sediment ranged from 0.1 to 8.8 microg/kg, while HCH ranged from 0.3 to 66.5 microg/kg. DDT residues in fish body ranged from 3.7 to 23.5 microg/kg and HCH ranged from 3.7 to 132 microg/kg. These results demonstrate an accumulation through food chain (from soil-water-sediment-microbes-crop-fish-... etc.), also that HCH residues are generally more persistent than DDT residues. However, all these data are well below than the state warning standard limit.     

Classification and ordination of DDT and HCH in soil samples from the Guanting Reservoir, China

Organochlorine pesticides (OCPs) have been a major environmental issue, drawing much scientific and public attention due to their bioaccumulation potential, persistence and toxicity. Soil samples from three villages around the Guanting Reservoir, one of Beijing's five major water systems located to the northwest of the city, were collected in 2003 and analyzed to determine DDT and HCH-concentrations. The samples were also analyzed for soil texture, pH, and concentrations of total carbon, nitrogen and phosphorus to investigate their possible relationship to current OCP-concentrations. Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) were used to study the distribution and contamination levels of OCPs within the study area. Classification splits were made to divide the 30 samples into three groups. The first group contained samples in soils from village C; the second group contained all of the samples in village B and most of the samples in village A; and the third group contained just three samples from village A, and the three samples had a relatively high concentration of OCPs. Ordination plots of the first two axes from PCA (cumulative percentage 80.91%) were constructed to explore the HCH and DDT-distribution patterns as well as the degradation ratios between the parent substances and their isomers.     

Chlorinated hydrocarbons in coastal bottom sediments of the Japan Sea

Data on distribution of chlorinated hydrocarbons in coastal bottom sediments of different areas of the Japan Sea are presented. Results obtained during the autumn 1994 expedition in Peter-the-Great Bay were compared with the data of previous surveys in the D.P.R. Korea coastal zone and Tatarsky Strait (Sakhalin Island). Concentrations of DDT metabolites and HCH isomers appear to be related mainly to pesticide usage in agriculture. Mean concentrations of total DDTs decreased from 12.5 ng g(-1) in the D.P.R.K. coastal zone to 2.2 ng g(-1) at Sakhalin Island shelf, whereas total HCH concentrations decreased from 3.4 to 0.4 ng g(-1). Differences in chemical composition of pesticides used in the D.P.R.K. and Russia were evident. The importance of further monitoring of persistent organochlorines in bottom sediments and the need for regulation of wastewater discharges is stressed.     

Sources of phenolic compounds in two catchments of southern Portugal - effect of season, land use and soil type

Water quality monitoring in reservoirs used for human water consumption, carried out by the Alentejo Regional Authorities of the Environment (south Portugal), revealed seasonal peaks of phenolic compounds above the water-quality legislation. The main objectives of this work were to identify the main phenolic compounds present in water and soil leachates, and to determine the sources of the seasonal concentrations of phenolic compounds in two catchments with different land use patterns: Roxo and Santa Clara catchments. The main phenolic compound detected was 2,4-dinitrophenol (2,4-DNP), both in stream water and soil leachates, with concentrations higher in Roxo catchment. Roxo catchment represents a larger agricultural area than Santa Clara, and it is likely that the origin of the 2,4-DNP is associated with the use of pesticides. A peak of 2,4-DNP concentrations was observed in stream water of both catchments during February, when farmers plough their fields and apply pesticides. The 2,4-DNP peak was probably caused by a precipitation event shortly after the application of pesticides, increasing their transfer from land surfaces to adjacent streams. The leaching behaviour of 2,4-DNP was strongly dependent on the type of soil and pH. In soils with high clay content and low pH, 2,4-DNP was easily adsorbed, and its runoff from the soil to adjacent streams was reduced. Ribeira de Santa Vitória, from Roxo catchment, was the only stream showing a high abundance of vegetation, and the lowest concentrations of 2,4-DNP in water. Plants may play a role in removing contaminants from stream water.     

The levels and distribution of organochlorine pesticides (OCPs) in sediments from the Haihe River, China

The levels and distribution patterns of the selected organochlorine pesticides (OCPs=p,p'-DDT, o,p'-DDT, p,p'-DDE, p,p'-DDD, alpha-, beta-, gamma- and delta-HCH) in surficial sediments from the Haihe River and Dagu Drainage River of Tianjin were investigated by means of gas chromatography coupled with micro-electronic capture detector (GC-microECD). Concentrations of OCPs in the sediments from the Haihe River ranged from 1.88 to 18.76ng g(-1) (mean 7.33ng g(-1)) for sum HCH, 0.32-80.18ng g(-1) (mean 15.94ng g(-1)) for sum DDT. Compared with the Haihe River, the Dagu Drainage River was much more contaminated by HCHs and DDTs, wherein sum HCH ranged from 33.24 to 141.03ng g(-1) (mean 87.74ng g(-1)) and sum DDT ranged from 3.60 to 83.49ng g(-1) with a mean value of 35.52ng g(-1). The concentration distribution of sum DDT and sum HCH was different indicated their different contamination sources. Composition analyses indicated that a recent usage or discharge of HCH and DDT into the Dagu Drainage River.