Distribution of organochlorine pesticides in soils from South Korea

Soil samples were collected from rice growing and industrial areas in South Korea and analysed for organochlorine pesticide content using gas chromatography with electron capture detection. The soils were monitored for the presence of 18 organochlorine pesticides. The main pesticides found were gamma- and delta-hexachlorocyclohexane, heptachlor epoxide and dieldrin. The range of concentrations, for each compound, was respectively, 0.17-0.94, 0.77-2.97, 1.38-48.0 and 0.32-0.49 ng/g soil. The highest values were found in soil obtained from rice fields indicating that, although the use of organochlorine pesticides has been discontinued since 1980, substantial concentrations of residues particularly the oxidised form of heptachlor remain in the soil.     

A survey of organochlorine pesticide residues in cheese samples from three Mexican regions

Organochlorine pesticide residues were determined in cheese samples from three Mexican regions. All samples were found to be contaminated by these residues: p,p'-DDE was present in 100% of the samples. Other pesticides found with high frequencies were HCB, three of the BHC isomers, as well as heptachlor and its epoxide. Also found, although less frequently, were residues of p,p'-DDD, p,p'-DDT, aldrin, dieldrin and endrin. Samples from the region known as Comarca Lagunera had the highest number of pesticides per sample. The highest concentrations of residues were found in cheese samples from the Soconusco and the Comarca Lagunera regions.     

Removal of aldrin, dieldrin, heptachlor, and heptachlor epoxide using activated carbon and/or Pseudomonas fluorescens free cell cultures

Degradation of aldrin (1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5-8-dimethanonaphthalene), heptachlor (1H-1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano indene), dieldrin (1aalpha,2beta,2aalpha,3beta,6beta,6aalpha,7beta,7aalpha)-3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-d-methanonaphtha[2,3-b]oxirene, and heptachlor epoxide (1aalpha, 1bbeta,2alpha,5alpha,5alphabeta,6beta,6aalpha-2,3,4,5,6,7,7-Heptachloro-1a,1b,5,5a,6,6a-hexahydro-2,5-methano-2H-inden[1,2-b]-oxirene) was tested using free cultures of Pseudomonas fluorescens under controlled conditions. Pesticide concentrations were monitored by gas chromatography during 120 h. Percentages of degradation and biodegradation rates (BDR) were calculated. Data showed a trend suggesting a relation between chemical structure and degradability. Degradation kinetics for each pesticide tested showed that the highest degradation rates were found in the first 24 h. Kinetics data were adjusted to an empirical equation in order to predict their behavior, and the correlation coefficients obtained were satisfactory. Gas chromatography/mass spectrometry (GC/MS) analysis of the final extracts allowed the identification of chlordene and monodechlorodieldrin, which have been reported as final metabolite produced in the biodegradation of this kind of compounds. Regarding adsorption of pesticides on activated vegetal carbon, we concluded that removal efficiencies between 95.45 and 97.18% can be reached, depending on the pesticide and the carbon dose applied. The values for K from the Freundlich equation were quite similar for the four pesticides (between 1.0001 and 1.04), whereas the n values were quite different for each pesticide in the following order of affinity: dieldrin > aldrin > heptachlor epoxide > heptachlor. Equilibrium times, very important for scaling up the process, were between 43 min and 1 h, for the heptachlor epoxide and the heptachlor, respectively.     

Removal of Aldrin,Dieldrin, Heptachlor,and Heptachlor Epoxide Using Activated Carbon and/or Pseudomonas fluorescens Free Cell Cultures

Degradation of aldrin (1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5-8-dimethanonaphthalene), heptachlor (1H-1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano indene), dieldrin (1aα,2β,2aα,3β,6β,6aα,7β,7aα)-3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-d-methanonaphtha[2,3-b]oxirene, and heptachlor epoxide (1aα, 1bβ,2α,5α,5αβ,6β,6aα-2,3,4,5,6,7,7-Heptachloro-1a,1b,5,5a,6,6a-hexahydro-2,5-methano-2H-inden[1,2-b]-oxirene) was tested using free cultures of Pseudomonas fluorescens under controlled conditions. Pesticide concentrations were monitored by gas chromatography during 120 h. Percentages of degradation and biodegradation rates (BDR) were calculated. Data showed a trend suggesting a relation between chemical structure and degradability. Degradation kinetics for each pesticide tested showed that the highest degradation rates were found in the first 24 h. Kinetics data were adjusted to an empirical equation in order to predict their behavior, and the correlation coefficients obtained were satisfactory. Gas chromatography/mass spectrometry (GC/MS) analysis of the final extracts allowed the identification of chlordene and monodechlorodieldrin, which have been reported as final metabolite produced in the biodegradation of this kind of compounds. Regarding adsorption of pesticides on activated vegetal carbon, we concluded that removal efficiencies between 95.45 and 97.18% can be reached, depending on the pesticide and the carbon dose applied. The values for K from the Freundlich equation were quite similar for the four pesticides (between 1.0001 and 1.04), whereas the n values were quite different for each pesticide in the following order of affinity: dieldrin > aldrin > heptachlor epoxide > heptachlor. Equilibrium times, very important for scaling up the process, were between 43 min and 1 h, for the heptachlor epoxide and the heptachlor, respectively.     

Patterns of organochlorine pesticide contamination in neotropical migrant passerines in relation to diet and winter habitat

Eleven species of Neotropical migrant passerines collected in Illinois (USA) during May 1996, were analyzed for the presence of organochlorine (OC) pesticides. At least one of five OC pesticide residues was detected in 66 of 72 birds, representing all species examined. The contaminants most frequently detected were p,p'-DDE, dieldrin and heptachlor epoxide, all of which were present in the 10-30 ng/g range. Insectivores had significantly higher levels of these compounds than did non-insectivores, while there was no significant main effect of winter habitat (forest and scrub). Future research on OC pesticide contamination in resident New World passerines may allow more accurate predictions regarding the sources of contamination in Neotropical migrants.     

Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003

In Malaysia, rivers are the main source of public water supplies. This study was conducted from 2002 to 2003 to determine the levels of selected organochlorine and organophosphate pesticides in the Selangor River in Malaysia. Surface water samples have been collected seasonally from nine sites along the river. A liquid-liquid extraction followed by gas chromatography-mass spectrometry technique was used to determine the trace levels of these pesticide residues. The organochlorine pesticides detected were lindane, heptachlor, endosulfan, dieldrin, endosulfan sulfate, o,p'-DDT, p,p'-DDT, o,p'-DDE and p,p'-DDE whereas for organophosphate pesticides, they were chlorpyrifos and diazinon. At the river upstream where a dam is located for public water supply, incidents of pesticide levels exceeding the European Economic Community Directive of water quality standards have occurred. Furthermore, the wetland ecosystems located at the downstream of the river which houses the fireflies community is being threatened by occasional pesticide levels above EPA limits for freshwater aquatic organisms. The occurrence of these residual pesticides in the Selangor River can be attributed to the intense agriculture and urban activity.     

Molecular characterization of conjugative plasmids in pesticide tolerant and multi-resistant bacterial isolates from contaminated alluvial soil

A total of 35 bacteria from contaminated soil (cultivated fields) near pesticide industry from Chinhat, Lucknow, (India) were isolated and tested for their tolerance/resistance to pesticides, heavy metals and antibiotics. Bacterial isolates were identified by 16S rDNA sequencing. Gas Chromatography analysis of the soil samples revealed the presence of lindane at a concentration of 547 ng g⁻¹ and α-endosulfan and β-endosulfan of 422 ng g⁻¹ and 421 ng g⁻¹ respectively. Atomic Absorption Spectrophotometry analysis of the test sample was done and Cr, Zn, Ni, Fe, Cu and Cd were detected at concentrations of 36.2, 42.5, 43.2, 241, 13.3 and 11.20 mg kg⁻¹ respectively. Minimum inhibitory concentrations of all the isolates were determined for pesticides and heavy metals. All the multi-resistant/tolerant bacterial isolates were also tested for the presence of incompatibility (Inc) group IncP, IncN, IncW, IncQ plasmids and for rolling circle plasmids of the pMV158-family by PCR. Total community DNA was extracted from pesticide contaminated soil. PCR amplification of the bacterial isolates and soil DNA revealed the presence of IncP-specific sequences (trfA2 and oriT) which was confirmed by dot blot hybridization with RP4-derived DIG-labelled probes. Plasmids belonging to IncN, IncW and IncQ group were neither detected in the bacterial isolates nor in total soil DNA. The presence of conjugative or mobilizable IncP plasmids in the isolates indicate that these bacteria have gene transfer capacity with implications for dissemination of heavy metal and antibiotic resistance genes. We propose that IncP plasmids are mainly responsible for the spread of multi-resistant bacteria in the contaminated soils.     

Pesticides in precipitation in the Gdańsk region (Poland)

Selected organonitrogen, organophosphorus and organochlorine pesticides have been determined in precipitation samples collected at 10 sites in the Gdańsk region (northern Poland) over a period of one year (1998). Compounds which were detected most often included simazine (0.11-5.80 ng/l), fenitrothion (0.1-2.10 ng/l), chlorfenvinfos (0.1-1.30 ng/l), gamma-HCH (0.012-5.06 ng/l), heptachlor epoxide (0.05-3.28 ng/l) and aldrin (0.02-3.28 ng/l). The pesticide concentrations in precipitation samples revealed seasonal fluctuations, with higher concentrations observed during the application periods (June and July). The concentrations observed were also affected by the inflow of polluted air masses from the southwest. The total pesticide concentration in the precipitation samples was strongly related to the abundance of green areas in the vicinity of the sampling sites. A weak correlation was also found between the total concentration of organonitrogen and organophosphorus pesticides, and the total concentration of organochlorine pesticides in the samples collected.     

An eleven-year study of chlorinated hydrocarbon insecticide residues in bovine fat in Illinois, 1972-1982

Bovine fat samples in Illinois were monitored for residues of chlorinated hydrocarbon insecticides from 1972 through 1982. The percentage of fat samples that were contaminated with all chlorinated hydrocarbons decreased during the 11-year study. The percentage of samples contaminated with DDT and its analogs decreased most markedly from 82.4% in 1972 to 2.1% in 1982. The percentage of samples contaminated with aldrin/dieldrin and heptachlor/heptachlor epoxide began to decline in 1980 and continued to decrease through 1982.     

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.     

A preliminary investigation of persistent organic pollutants in ambient air in Hong Kong

Air samples were collected for characterisation of PCDD/Fs and other persistent organic pollutants (POPs) such as aldrin, alpha-HCH, beta-HCH, delta-HCH, gamma-HCH, o,p'-DDT, p,p'-DDT, o,p'-DDE, p,p'-DDE, o,p'-DDD, p,p'-DDD, dieldrin, endrin, endosulfan I and II, heptachlor, heptachlor epoxide and hexachlorobenzene during the winter of 2000/2001 at the weather station of the Hong Kong Observatory at Tai Mo Shan (TMS), which is the highest point (approximately 957 m) in Hong Kong, besides the routine monitoring of PCDD/Fs and 200 other toxic air pollutants (TAPs) at two urban TAPs stations at Tsuen Wan and Central & Western. Concentrations of the pollutants detected at TMS station were evaluated and compared to those recorded at the urban stations. Though pesticides including alpha-HCH, hexachlorobenzene, DDT, DDE, heptachlor, and endosulfan I were detected, these pesticides were found at relatively low concentrations of about 0.02-0.23 ng/m3 and should not have any significant health effects. Concentrations of some of the monitored POPs were found to be higher whilst most of the monitored TAPs were at comparable levels to those measured at the urban stations during the same period. According to the Stockholm Convention on POPs (May 2001), the 12 chemicals labelled by the United Nations as the most dangerous are: aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, mirex, toxaphene, hexachlorobenzene, PCBs and dibenzo-p-dioxins/dibenzofurans (PCDDs)/(PCDFs). Given that there has not been any large scale use of organo-chlorine pesticides recorded since the decline of local farming activities in recent years, the results of the present study again show that pesticides and POPs such as PCDDs/PCDFs are ubiquitous environmental contaminants present in the atmosphere of Hong Kong. The findings also indicate that organo-chlorine pesticides and PCDDs/PCDFs are among the most prevalent chlorinated semi-volatile pollutants present in Hong Kong. Results obtained in the present study suggest that selected pesticides may be used as tracers for transport of pollutants for regional air quality study.     

An eleven‐year study of chlorinated hydrocarbon insecticide residues in bovine fat in illinois, 1972–1982

Abstract

Bovine fat samples in Illinois were monitored for residues of chlorinated hydrocarbon insecticides from 1972 through 1982. The percentage of fat samples that were contaminated with all chlorinated hydrocarbons decreased during the 11‐year study. The percentage of samples contaminated with DDT and its analogs decreased most markedly from 82.4% in 1972 to 2.1% in 1982. The percentage of samples contaminated with aldrin/dieldrin and heptachlor/heptachlor epoxide began to decline in 1980 and continued to decrease through 1982.     

Translocation of aged cyclodiene insecticide residues from soil into forage crops and pastures at various growth stages under field conditions.

Field trials were conducted to measure translocation of pesticides by summer and winter forage/pasture species from soil containing aged residues of heptachlor and, to a lesser extent, dieldrin. Substantial amounts of heptachlor epoxide, and lesser amounts of gamma-chlordane were translocated to plants from contaminated soil. Residue levels varied with crop species and stage of plant development. In summer crops residues were higher in soybean > cowpeas > lab-lab > Sorghum > millet > sweet saccaline at the grazing and mature stages. Compared to glasshouse studies undertaken previously, residues in crops grown under field conditions were much lower. This apparently reflects the lower soil moisture levels and the reduced rates of translocation. Heptachlor residues in winter crops were highest in Saia oats > Berseem clover > Haifa clover > Cassia oats > Tetila ryegrass > Schooner barley > Shaftal clover > Hunter river lucerne at the grazing stage. There were no detectable levels in barley and oats at the mature stage. No dieldrin residues were translocated into the various crop species.     

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.     

Residues of organochlorine pesticides in Alabama soils

A survey was made of 36 Alabama agricultural soils to assess residues of formerly used organochlorine pesticides. Compounds determined comprised alpha- and gamma-hexachlorocyclohexane, heptachlor, heptachlor-exo-epoxide, trans- and cis-chlordane, trans-nonachlor, dieldrin, toxaphene, DDT and DDE. Concentrations varied by several orders of magnitude among farms and appeared to be log-normally distributed. Highest concentrations (ng g(-1) dry soil, arithmetic means) were found for toxaphene (285+/-390) and DDTs (p,p'-DDE, 22.7+/-21.4; p,p'-DDT, 24.6+/-30.5; o,p'-DDT, 4.00+/-5.86; p,p'-DDD, 2.40+/-2.41) which were once heavily used in the southern USA. Pesticide residues were not proportional to soil organic carbon content indicating that residue concentrations were a reflection of pesticide application history and dissipation rates rather than air-soil equilibrium. Mean ratios of DDT/DDE in six regions of the state ranged from 0.39 to 1.5, and compound ratios for chlordanes and toxaphene were different from those in the technical mixtures.     

Biodegradation of heptachlor and heptachlor epoxide-contaminated soils by white-rot fungal inocula

The ability of certain white-rot fungi (WRF) inocula to transform heptachlor and heptachlor epoxide and its application in artificially contaminated soil were investigated. Fungal inoculum of Pleurotus ostreatus eliminated approximately 89 % of heptachlor after 28 days of incubation, and chlordene was detected as the primary metabolite. The fungal inoculum of Pleurotus ostreatus had the highest ability to degrade heptachlor epoxide; approximately 32 % were degraded after 28 days of incubation, and heptachlor diol was detected as the metabolite product. Because Pleurotus ostreatus transformed heptachlor into a less toxic metabolite and could also effectively degrade heptachlor epoxide, it was then selected to be applied to artificially contaminated soil. The spent mushroom waste (SMW) of Pleurotus ostreatus degraded heptachlor and heptachlor epoxide by approximately 91 and 26 %, respectively, over 28 days. This finding indicated that Pleurotus ostreatus SMW could be used to bioremediate heptachlor- and heptachlor epoxide-contaminated environments.     

Detection of residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region of San Luis Potosi,Mexico

Organochlorine pesticides were intensively used in Mexico from 1950 until their ban and restriction in 1991. However, the presence of these compounds is commonly reported in many regions of the country. The aim of the present study was to identify and quantify residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region, San Luis Potosi state, which has been identified as possibly polluted by pesticides. Composed samples from 24 zones covering an area of approximately 5,440 ha were analyzed. The most frequently found pesticides were p,p´-DDT followed by ,p,p´-DDE, heptachlor, endosulfan and γ-HCH whose frequency rates were 100, 91, 83 and 54%, respectively. The concentration of p,p´-DDT in the crops grown in these soils was in the following order: chili > maize > tomato > alfalfa. The results obtained in this study show that p,p´-DDT values are lower or similar to those found in other agricultural regions of Mexico. Methyl and ethyl parathion were the most frequent organophosphate pesticide detected in 100% and 62.5% of the samples with average concentrations of 25.20 and 47.48 μg kg^–1, respectively. More research is needed to establish the background levels of pesticides in agricultural soils and their potential ecological and human health effects in this region.     

The health risk assessment of organochlorine pesticides in smoked fish products available in Szczecin,Poland

The aim of this study was to determine the concentration of organochlorine pesticides [HCH and isomers (α, β, γ), aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide and DDT and its metabolites (op’-DDD, pp’-DDD, op’-DDT, pp’-DDE, pp’-DDT] in smoked fish. Analysis was made of 12 typical smoked fish products that are the most popular among customers from the city of Szczecin, Poland. Pesticide residues were found in all samples of smoked fish. The smoked sprat and cold-smoked Baltic salmon were the most contaminated smoked fish products in terms of chlorine pesticides. The sum of DDT metabolites ranged from 1.48 (smoked mackerel) to 35.53 ng/g wet weight (smoked sprat), with the lowest concentrations found for op’-DDT and the highest for pp’-DDE. The level of heptachlor epoxide isomer B was low and ranged from 0.06 ± 0.01 (smoked eel) to 0.27 ± 0.07 ng/g w.w. (smoked sprat). The content of heptachlor was 0.48–1.99 ng/g w.w. Concentration of endrin was higher compared to other pesticides, ranged from 1.50 (cold-smoked salmon fillet) to 16.84 ng/g w.w (hot-smoked warehou). The contamination of smoked products was significantly low and poses no risk to the health of consumers provided that they eat a diverse diet. The concentration of organochlorine pesticides in the analysed products was below the standards accepted in European countries.     

Hair as a marker for pesticides exposure

Rats were orally treated with mixtures of chlorinated pesticides. Hair was collected and analyzed for pesticide residues over a period of up to four weeks. Quantitative and qualitative analysis of the recovered pesticides in hair were determined using gas chromatography with electron capture detector. Results suggest that hair can be used as a biomarker for the monitoring of organochlorinated pesticide residues at low parts per billion levels. Chlorinated pesticides were also detected in human hair of environmentally exposed and occupationally exposed individuals, which indicates that hair can be used for monitoring pesticides exposure.     

Levels and seasonal variations of organochlorine pesticides in urban and rural background air of southern Ghana

Urban, suburban and rural background air samples were collected in southern Ghana in 2008 employing polyurethane foam disc passive air samplers (PAS). PAS were analysed for organochlorine pesticides (OCPs), namely hexachlorocyclohexanes (α-, β-, γ- and δ-hexachlorocyclohexane), dichlorodiphenyltrichloroethane including metabolites (o,p'- and p,p'-DDT, DDE and DDD), hexachlorobenzene, pentachlorobenzene, aldrin, dieldrin, endrins (endrin, endrin aldehyde and endrin ketone), isodrin, heptachlors (heptachlor, heptachlor epoxide A and heptachlor epoxide B), chlordanes (α-, β-chlordane, oxychlordane and trans-nonachlor), endosulfans (α- and β-endosulfan and endosulfan sulphate), methoxychlor and mirex using a gas chromatograph coupled to a mass spectrometer. The levels of OCPs ranged for the individual pesticides from below limit of quantification to 750 pg m(-3) (for α-endosulfan), and current agricultural application seemed to be the main primary source of most abundant pesticides. Re-volatilization of previously used pesticides from contaminated soils could not be ruled out either as potential secondary source of contamination, especially in warm and dry seasons and periods of intensive agricultural activities. Higher atmospheric concentrations were observed in November and December during the dry season compared to lower concentrations observed in June, July and August when the country experiences heavy rains. The highest seasonal variation was observed for currently used pesticides as α-endosulfan. A p,p'-DDT/p,p'-DDE ratio suggested recent inputs of fresh technical DDT.