Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

Chemical and biological release of 14C‐bound residues from soil treated with 14C‐p,p'‐DDT

Abstract

¹⁴C‐p,p'‐DDT‐bound residues in soil can be released by treatment with concentrated sulphuric acid at ambient temperatures. Within 6 days, about 70% of the bound residues was released. Bound residues released after 9 months incubation with ¹⁴C‐DDT showed the presence of DDT and DDE only while bound residues released after 18 months, contained in addition 13% DDD.

Release of bound ¹⁴C‐residues also occurs readily following inoculation of the soil‐bound residues with fresh soil or with individual microorganisms. Almost complete release of bound residues was observed after incubation for 45 days. The rate of release was rapid during the first two weeks and decreased thereafter. TLC and HPLC analysis showed that the released residues contained DDE (about 80%) and a smaller amount of DDD. The disappearance of DDT from the released residues may be attributed to its microbiological degradation to DDE and DDD, shortly after its release.     

Assessment of DDT and mercury levels in fish and sediments in the Iriri River,Brazil: Distribution and ecological risk

Abstract

In order to assess the risk of exposure of human populations to dichlorodiphenyltrichloroethane (DDT) and mercury, muscles of five fish species were analysed, along with the surface sediment of 14 Iriri River sampling sites. The fish specimens were sacrificed by the spinal section, prior to sex identification, body weight determination and total length. Considering the fish specimens studied, 11% of them showed concentrations of mercury higher than the maximum established by the World Health Organization for safe human consumption. A positive correlation between fish body weight and mercury concentration was observed, besides a positive correlation between the fish size and Hg concentration. Significant differences (P?<?0.05) were found between mean concentrations of DDT and metabolites among species of fish studied. In the Plagioscion squamossissimus species, the highest concentration of total DDT (151.4?ng/g) was found, while in Eugerres Brasilianus species, the lowest. However, the DDT levels in fish muscle of studied species are below the maximum set by FAO-Alimentarius CODEX. In the sediments, total DDT ranged from 11.58?ng/g to 48.4?ng/g, which is associated with the historical DDT use in the Amazon. According to sediment quality guidelines, these levels have a moderate toxic effect in almost all of the studied region.     

Pesticide contaminants in selected species of edible wild mushrooms from the north-eastern part of Poland

ABSTRACT

The aim of this study was to determine the level of chlorinated hydrocarbon residues in selected edible mushrooms from north-eastern Poland. The experiment was carried out on 45 samples consisting of 15 fruiting bodies each of the following species: Boletus edulis, Imleria badia and Cantharellus cibarius. Dried samples were subjected to extraction of lipids with a Soxhlet and a standard procedure—based on the decomposition of lipids by concentrated sulfuric acid and the release of organic insecticides to the hexane layer—was used to determine chlorinated hydrocarbons. The quantitative determination of DDT, DDE, DDD and γ-HCH were conducted using gas chromatography with electron capture detection (GC-ECD). Chlorinated hydrocarbons were found in all tested samples. The contents of these compounds varied between all three species. Mean content of γ-HCH in B. edulis, I. badia and C. cibarius was: 2.60; 4.83; 7.52 µg kg^?1 of lipids, while the content of ΣDDT was: 57.02; 25.20; 127.10 µg kg^?1 of lipids, respectively. These results show that mushrooms from the north-eastern part of Poland can be used as potential bio-indicators of environmental contamination with chlorinated hydrocarbons. Moreover, the studied fungi could still be used as food due to the low levels of analyzed organochlorine compounds.     

Dissipation of chlorpyrifos,oxon, and 3,5,6‐trichloro‐2‐pyridinol in litter and elm forest soil

Abstract

After chlorpyrifos was applied to the basal 1 meter of elm tree trunks for control of elm bark beetles at two different application times and sites, initial chlorpyrifos residues in forest floor litter ranged from 120 to 916 μg/g depending on the application time. Residues dissipated by approximately 99% after 791 d with the DT₅₀ from 3.9 to 59 d and DT₉₀ from 55 to 310 d. The initial residues of chlorpyrifos in elm forest soil varied from 0.8 to 28 μg/g and were 1 to 2 μg/g at 791 d after application. The dissipation half‐lives of chlorpyrifos in fortified soil placed in the field ranged from 116 to 121 d.     

Laboratory studies on volatilization and mineralization of 14c‐p,p'‐DDT in soil,release of bound residues and dissipation from solid surfaces

Abstract

In support of field data, laboratory studies were conducted on volatilization, mineralization and binding of ¹⁴C‐p,p'‐DDT in soils at Sao Paulo. Incubation of soil for 6 weeks did not result in volatilized organics or mineralization; with >95% extractable radiocarbon in the form of p,p'‐DDT. Small amounts of bound residues (1.8%) were detected in soil. These data confirm the very slow dissipation of DDT in the field which presumably relates to the acidic pH of soil (4.5–4.8).

Bound ¹⁴C‐residues in soils treated with ¹⁴C‐p,p'‐DDT at Praia Grande and Sao Paulo could be released (5–21%) by sulphuric acid treatment. The released residue had the composition: 69–90% DDT, 7–32% DDD and 0–3% DDE. Incubation of soil bound ¹⁴C‐residues with fresh inoculum for 3 months did not result in release of ¹⁴C.

Dissipation from wooden surfaces was fairly slow. After 20 weeks, 74% of the applied radioactivity could be recovered; 44% hexane‐non‐extractable.     

DETERMINATION OF DDT AND ITS METABOLITES IN CATTLE DIP SOIL AVAILABLE IN AQUEOUS PHASE AFTER REMEDIATION

Soil taken from a former cattle tick dip site in NSW Australia, was remediated with a chemical leaching technology. The pre- and post-remediated soil (20g) was dispersed in water (100mL) and subjected to passive diffusion using polymeric membranes. The remediation reduced tDDT from 1174.3μg/g to 102.9μg/g (ash weight basis), which was further reduced to 43.2μg/g with composting. The membranes accumulated 41.3μg tDDT/g from the dip soil, 49.2μg tDDT/g from the chemically leached soil and 3.1μg tDDT/g from the leached composted soil. The chemical leaching removed over 90% of the tDDT, but released soil bound DDT, which was converted to DDE, while 2.99μg/g was accumulated by the membranes from dip soil, 37.52μg/g was accumulated from remediated soil. Composting, however, almost eliminated the availability for passive diffusion by the membranes from 50 – 60μg/g in remediated soil to 3–3.5μg/g in composted soil. Variability studies of the membranes using eight replicates demonstrated that the accumulation by the membranes was reproducible with an average relative error of 20.3% for p,p'-DDT in soil type two, whilst the lowest average relative error for p,p'-DDE was 4.3%, suggesting that triplicate analyses will achieve acceptable accuracy.     

DDT residues in water, sediment, domestic and indigenous biota from a currently DDT-sprayed area

DDT is used for indoor residual spraying (IRS) in Limpopo Province, northern South Africa to control malaria. Through IRS, DDT may reach the outdoor environment via dust and air and from possible spillages during application. In this area the local people consume domestic chickens, wild fish or birds. Fish from the river catchment and impoundments seem to be the major source of protein intake. Water, sediment and tissue samples from two such fish species, domestic chickens and wild birds (terrestrial and aquatic) from this DDT-sprayed area were analysed for DDT and metabolite residues. The samples contained p,p′-DDT, p,p′-DDD and p,p′-DDE residues, with the latter the most ubiquitous and in the highest concentrations. These findings raise concern that both water and food may be major routes of human exposure to DDT and metabolites, thereby posing possible adverse human health implications to the local communities.     

Residues of legacy organochlorine pesticides and DDT metabolites in highly consumed fish from the polluted Guanabara Bay,Brazil: distribution and assessment of human health risk

Abstract

Organochlorine (OCP) pesticides were determined in samples of sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri), and mullet (Mugil liza) from Guanabara Bay (state of Rio de Janeiro, Brazil). OCP concentrations and fish consumption were linked with acceptable daily intake values in order to assess the human health risk for the Brazilian population. The total concentrations of OCPs (Σ OCP) was 6.6?ng/g f.w., 7.5?ng/g f.w., and 2.8?ng/g f.w. for sardines, corvina, and mullet, respectively. There was a significant difference (P?<?0.05) among the species related to o,p’-DDD and o,p’-DDT concentrations. Both DDT-related compounds were 5 and 76 times more abundant in sardines than in whitemouth croaker and mullet. Newly discovered DDT metabolite, o-Cl-DDMU, was frequently detected in the fish. None of the samples exceeded the maximum limits for acceptable levels of OCP residues. According to the data of average intake of Brazilian population, none of three species exceeded toxicological parameter. The investigated fishes are considered as safe for human consumption in regard to exposure of the studied OCPs. However, fish may be a intake source of OCP metabolites such as o-Cl-DDMU whose toxicity is still unknown.     

Fate of parathion in soil under sub‐tropical field conditions

Abstract

Persistence, metabolism and binding of ¹⁴C‐parathion in alkaline sandy loam soil under sub‐tropical conditions of Delhi were studied for 545 days. After 3 days of treatment, ¹⁴C‐residues declined to 41% of the amount applied. The dissipation curve was biphasic; an initial rapid phase (up to 7 days) followed by slow dissipation. The half life of dissipation was only 3.36 days for the first phase and 84 days for the slow phase. The overall half life was 64.5 days. The total residues at zero‐time were 10.65 μg/g dry soil and were almost totally extractable. The extracts consisted of parathion, 4‐aminophenol, 4‐nitrophenol and paraoxon. The bound residues gradually increased and accounted for the total residue at the end of one year (0.7 μg/g).     

Procedure for the determination of 2,4‐D and dicamba in inhalation,dermal, hand‐wash,and urine samples from spray applicators

Abstract

Analytical procedures for the simultaneous determination of residues of 2,4‐D and dicamba from polyurethane foam plug air samplers, ethylene glycol impregnated glass‐fiber filter paper dermal samplers, 1% sodium bicarbonate hand wash solution, and urine are presented. Residues were derivatized with diazomethane and quantitated using electron capture gas chromatography. Recoveries were greater than 80% at the limit of detection in all substrates. The limits of detection for both herbicides were 0.1 μg/foam plug and 0.5 μg/filter paper, and in the urine, 1.7 μg/100 mL and 5.0 μg/100 mL for dicamba and 2,4‐D, respectively.     

Fate of DDT and parathion in grapes processed into Arak,an alcoholic beverage

Abstract

Arak, the national alcoholic drink in Lebanon, was prepared from grapes to which either DDT or parathion had been added. Samples of the nine fractions produced from the fermentation and distillation steps were analyzed for DDT and parathion and their respective metabolites.

DDT degraded to DDD during the fermentation step resulting in a sharp decrease in DDT level. The two distillation steps contributed to a further decrease in the DDT level so that the final product contained less than 2% of the amount found in the fresh grape juice. Although the concentration of DDD increased sharply during fermentation, it also decreased to a negligible level during the subsequent distillation procedure.

Parathion was more stable than DDT during the fermentation and first distillation steps. However, the second distillation process caused a share decline in its level and the Arak contained only about 6% of the residues present in the fresh juice, paranitrophenol being the only metabolite detected.     

Screening pesticides for their ability to damage bacterial DNA

Abstract

Twenty‐six pesticides and pesticide degradation products were screened (125 μg ‐ 2000 μg) for their ability to induce unrepairable damage to bacterial DNA. Three repair test systems were utilized in this study, the Salmonella typhimurium (TA1538/TA1978), the E. coli K‐12 (Pol A₁ ⁺/Pol^‐ ₁) and the E. coli WP₂ (WP₂, WP₂ uvrA, WP67, CM611 and CM571). Aldicarb (1000 μg), benomyl (250 μg), 2‐aminobenzimidazole (2000 μg), captan (125 μg), fenazalor (500 μg), 5,6‐dichloro‐2‐trifluoromethylbenzimida‐zole (NC‐2983) (250 μg), isothymol (250 μg), maleic hydrazide(1000 μg), pentachloronitrobenzene (1000 μg) were DNA‐damaglng to one or more bacterial test systems. Isothymol and NC‐2983 affected all three test systems. Chlorinated hydrocarbon insec ticides, some being recognized as carcinogens, did not: produce a zone of inhibition in any of the tester strains possibly due to their poor solubility and diffusion in the agar overlay. It was concluded that these tests can be performed along with bacterial reversion tests to complement each other as short‐term screening tests for potential carcinogens and mutagens.     

Studies on the dissipation of 14C‐DDT from water and solid surfaces

Abstract

Dissipation of ¹⁴C‐p,p'‐DDT from water was studied for 180 days under outdoor conditions. DDT dissipated rapidly with overall half‐life of 53 days. The main degradation products were p,p'‐DDE and p,p'‐DDD. A portion of ¹⁴C‐residues was found in the sediment plus biomass (pellet) and on the inner surface of the glass container. This amounted to 7.2 and 6.7% of the initially added radioactivity, respectively. After 6 months, bound¹⁴C was more as compared to extractable ¹⁴C and p,p'‐DDD was the major metabolite of p,p'‐DDT in the extractable fraction. DDT dissipated from clay plates under indoor conditions with an overall half‐life of 160 days.     

Organochlorine pollutants in human blood and their relation with age, gender and habitat from North-east India

Organochlorine pesticides (OCPs) have been beneficial to man and environment but their inadvertent use has caused considerable harm to human health. Despite the proliferation of different types of pesticides, organochlorines such as HCH and DDT still account for two third of the total consumption in India because of their low cost and versatility in action again various pests. Since, Assam, a state in North-eastern part of India is an endemic area with perennial transmission where mosquito borne diseases are serious health problems; these pesticides are still being used in huge quantities in vector control as well as in agriculture. A total of 331 human blood samples were collected from district Nagaon and Dibrugarh of Assam to determine the residue levels of DDT and HCH in human blood. The concentrations of selected persistent organochlorine pollutants were measured with gas chromatography-electron capture detector. The results demonstrated that the mean levels of total DDT and HCH were 743 μg L(-1) and 627 μg L(-1) for district Nagaon while 417 μg L(-1) and 348 μg L(-1) for district Dibrugarh. The difference of total HCH and total DDT between these two districts was found to be highly significant (P<0.0001). Among DDT metabolites, the same trend was observed for both the districts as p,p-DDT was the principal component contributed 41% for Nagaon and 58% for Dibrugarh. In case of HCH residues, for Nagaon, β-HCH was the predominant contaminant comprised more than 34% while for Dibrugarh, it was α-HCH that was contributing 43% of total HCH concentration.     

The sorptive capacity of an aquatic macrophyte for the pesticide aminocarb

Abstract

Ceratophyllum demersum exposed to a constant 1 μg/rnl aminocarb exhibited a large capacity for the sorption of the pesticide, up to 400 μg/g fresh weight in the dark and 1000 μg/g fresh weight in the light. Smaller, actively growing sprigs sorbed 5 times more pesticide per gm fresh weight than larger, older sprigs, although total uptake per plant was greater in the larger plants. Membrane conformation and integrity appear to be important factors in determining the capacity of this aquatic plant for pesticide sorption.     

Bioavailability and dissipation of fluridone under controlled conditions

Abstract

Bioavailability of fluridone, l‐methyl‐3‐phenyl‐5‐[3‐(trifluoromethyl) phenyl]‐4(1H)‐pyridinone, as affected by soil temperature, soil moisture regime, and duration of incubation was investigated in three soil types by grain sorghum (Sorghum bicolor [L.] Moench cv. Abu Sabien) chlorophyll bioassay. Initial loss of fluridone was rapid and dissipation followed first‐order kinetics under most of the incubation treatments investigated. Soil moisture, in general, had a greater impact than soil temperature on dissipation of fluridone. The herbicide dissipated faster at the fluctuating room temperature (18–24°C) than at the constant 10°C in Sonning sandy clay loam (O.M. = 1.2%) and Erl Wood sandy loam (O.M. = 2.5%) but not in Shropshire loamy peat (O.M. = 33%). In the two mineral soils, bioassay‐detectable residues from an initial rate of 1.00 μg/g were least (0.00 ‐ 0.10 μg/g) at 1/2 field capacity (FC) and greatest (0.16 ‐ 0.37 μg/g) at 1/4 FC, 400 days after treatment. At 10°C, the DT₅₀ values (days) at 1/4 FC and 1/2 FC were, respectively, 147 ± 16 and 69 ± 6 for Erl Wood soil, and 257 ± 28 and 51 ± 12 for Sonning soil. In Shropshire soil, concentrations of bioavailable fluridone were least at each bioassay date when soil moisture was maintained at FC, at both temperatures of incubation. At 10°C, herbicide concentrations in the organic soil from an initial rate of 10.00 μg/g were 0.95 and 4.69 μg/g, respectively, at FC and 1/4 FC.     

Bioefficacy of Iprodione Against Two Desapers,its Compatibility with T. harzianum and Residues on Cabbage Crop

Iprodione (3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide) bio-assayed against fungi Alternaria brassicicola and Sclerotinia sclerotiorum was found to be highly effective for inhibiting these desapers. Inhibition of A. brassicicola was 100% up to the dose of 75 ppm and for S. sclerotiorum there was 50% inhibition for the same concentration. Formulation of the pesticide was applied @ 500 and 1000 g. a.i./ha on the cabbage crop grown in the fields. Residues in the edible sample of cabbage were analyzed by gas choromatography for the fungicide and its metabolites. The dissipation of residues of the fungicide and its bio-efficacy against two fungi are presented. It dissipated from 3.72 to 0.072 μg/g on cabbage head by 15 days after treatment. The EC₅₀ values of iprodione were found to be 11.5 ppm and 79.4 ppm for A. brassicicola and S. sclerotiorum, respectively. Half-life of iprodione was found to be 3 days for both cabbage head and leaves. The compatibility of the fungicide with a bio agent, T. harzianum was also studied and these two were not found to be compatible.     

The critical levels and the maximum metal uptake for wheat and rice plants when applying metal oxides to soil

Abstract

Wheat is more sensitivity to CdO and ZnO compared with rice plant. The yield of wheat decreased by 30% in the presence of 30 ppm Cd, but that of rice plants by only 8%. The critical levels of meal uptake by wheat and rice plants for applying metal oxides to soil (CdO, ZnO, PbO) were determined. The highest concentration obtained for wheat grain was 141 μg/g Cd at the Cd 10,000 ppm in soil. This value is higher the value of 4.97 μg/g for unpolished rice and higher than any other we have seen in the reports for treatment with CdO. Also, as concentration of more than 1.0 μg/g Cd in wheat was obsertced at 5 ppm Cd, while similar concentrations for rice plants were observed at 30 ppm Cd in soil.     

Toxicity of the Mosquito Control Pesticide Scourge® to Adult and Larval Grass Shrimp (Palaemonetes pugio)

Abstract

This study investigated the toxicity of various concentrations of technical resmethrin and Scourge® on adult and larval Palaemonetes pugio, a common grass shrimp species. Two types of tests were conducted for each of the resmethrin formulations using adult and larval grass shrimp life stages, a 96-h static renewal aqueous test without sediment, and a 24-h static nonrenewal aqueous test with sediment. For resmethrin, the 96-h aqueous LC₅₀ value for adult shrimp was 0.53 μg/L (95% confidence interval (CI): 0.46–0.60 μg/L), and for larval shrimp was 0.35 μg/L (95% CI: 0.28–0.42 μg/L). In the presence of sediment, technical resmethrin produced a 24-h LC₅₀ value for adult shrimp of 5.44 μg/L (95% CI: 4.52–6.55 μg/L), and for larval shrimp of 2.15 μg/L (95% CI: 1.35–3.43 μg/L). For Scourge®, the 96-h aqueous LC₅₀ for adult shrimp was 2.08 μg/L (95% CI: 1.70–2.54 μg/L), and for larval shrimp was 0.36 μg/L (95% CI: 0.24–0.55 μg/L). The 24-h sediment test yielded an LC₅₀ value of 16.12 μg/L (95% CI: 14.79–17.57 μg/L) for adult shrimp, and 14.16 μg/L (95% CI: 12.21–16.43 μg/L) for larvae. Adjusted LC₅₀ values to reflect the 18% resmethrin concentration in Scourge® are 0.37 μg/L (adult), 0.07 μg/L (larvae) for the 96-h aqueous test, and 2.90 μg/L (adult), 2.6 μg/L (larvae) for the 24-h sediment test. Larval grass shrimp were more sensitive to technical resmethrin and Scourge® than the adult life stage. The results also demonstrate that synergized resmethrin is more toxic to P. pugio than the nonsynergized form, and that the presence of sediment decreases the toxicity of both resmethrin and Scourge®