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Handwipe sampling and analysis procedure for the measurement of dermal contact with pesticides.

A handwipe sampling and analysis procedure was developed for the measurement of dermal contact to pesticides. This procedure utilizes cellulose dressing sponges wetted with 2-propanol. A two-step wiping procedure is described that ensures that the entire hand is sampled. Removal efficiency experiments show that dry residues of the pesticides chlorpyrifos and pyrethrin I are quantitatively removed from hands immediately following contact. Results suggest that the procedure may remove pesticide residues that are deeply embedded in the skin and not removed by soap-and-water washing. Extraction efficiency studies for 29 other pesticides show that the proposed extraction method may be applicable for a wide range of pesticides including phenoxy-acid herbicides. Field testing of the procedure indicates that it is easily implemented by sampling personnel and readily accepted by children.

Child↗

Multiresidue method using SPME for the determination of various pesticides with different volatility in confined atmospheres.

An analytical method is described for assessing the vapour concentration of 11 pesticides (bioallethrin, chlorpyriphos methyl, folpet, malathion, procymidone, quintozene, chlorothalonil, fonofos, penconazole and trimethacarb) in confined atmospheres (e.g. a greenhouse after pesticide application). This study is a successful extension of a method previously developed by the authors for dichlorvos to much less volatile pesticides. Sampling was performed by using polydimethylsiloxane-solid phase micro-extraction (PDMS-SPME) fibres immersed in a 250-mL sampling flask through which air samples were dynamically pumped from the analysed atmosphere. After a 40-min sampling duration, samples were analysed by GC/MS. Calibration was performed from a vapour-saturated air sample. The linearity of the observed signal versus pesticide concentration in the vapour phase was proved from spiked liquid samples whose headspace concentrations were measured by using the proposed method. This procedure gave calibration curves with regression coefficients ( R(2)) greater than 0.98, and the repeatability of these measurements was found with RSDs of 1.9-7.6%. As a field application test, this analysis procedure was used for the determination of gaseous procymidone concentrations as a function of time in the atmosphere of an experimental 8-m(2) and 20-m(3) greenhouse. The pesticide was sprayed according to real cultivation conditions, and measurements were made for 80 h after application (8 measurements). The observed concentrations found ranged from 200 to 500 micro g m(-3), thus indicating the level of contamination of the air breathed by people in such working conditions.

Journal Article↗

Identification of bacteria isolated from an oligotrophic lake with pesticide removal capacities.

We studied the growth and capacities for pesticides removal of bacterial strains isolated from the Laguna Grande, an oligotrophic lake at the South of Spain (Archidona, Málaga). Strains were isolated from water samples amended with 10 and 50 microg/ml of nine pesticides: organochlorinated insecticides (aldrin and lindane), organophosphorous insecticides (dimetoate, methyl-parathion and methidation), s-triazine herbicides (simazine and atrazine), fungicide (captan) and diflubenzuron (1-(-4-chlorophenyl)-3-(2,6-difluorobenzoyl urea), a chitinase inhibitor. The majority of the strains belonged to the genera Pseudomonas and Aeromonas and only 9% of the total of strains were Gram positive. From all the strains isolated, only 22 showed a wide growth range in all the pesticides tested and 4 of them were chosen for pesticide removal studies. The genetic identification of these strains showed their affiliation to Pseudomonas pseudoalcaligenes, Micrococcus luteus, Bacillus sp. and Exiguobacterium aurantiacum. These last two strains were those that showed the highest pesticide removal capacities and a high bacterial growth.

Aeromonas↗

Mutagenic and carcinogenic pesticides used in the agricultural environment of Gaza Strip.

More than 100 metric tons of formulated pesticides (about 75 pesticides) are used annually in Gaza Strip. It was found that 19 of these pesticides, that have been used, are internationally suspended, cancelled and banned pesticides. About 1100 cases of cancer have been registered in Gaza Strip (1979-1983). The distribution of cancer types among those patients are lymphoma and hematological malignancy, breast, head and neck, gastrointestinal malignancy, reproductive system, urinary system, soft tissue tumors, brain tumors and others. Consequently, the introduction and heavy use of pesticides and other toxic substances in the Gaza Strip environment is suspected to correlate with the growing incidence of cancer and other abnormalities in the nation. Precise determination of the effects of chronic exposure is, therefore, urgently needed.

Agriculture↗

Induction of prophage lambda by chlorinated pesticides.

Chlorinated organics represent an important class of environmental carcinogens. However, only a small percentage of the carcinogens of this chemical class are genotoxic in prokaryotic bioassays such as the Salmonella assay. In an effort to identify a short-term assay sensitive to chlorinated carcinogens, we have tested a group of chlorinated pesticides, most of which are carcinogenic in rodents, in a prophage-induction assay developed by Rossman et al. (1984). The Microscreen phage-induction assay is a rapid, inexpensive, miniaturized system that uses the induction of prophage lambda in Escherichia coli as an indicator of genetic damage. It has been used successfully to screen complex environmental samples for genotoxicants and has detected carcinogenic metals that are refractory in the Salmonella assay. The pesticides tested were malathion, monuron, p,p'-DDT, mirex, lindane, nitrofen, chlordane, toxaphene, captan, and dichlorvos. All but the first 4 induced prophage. The remaining pesticides were ranked as follows according to induction potency in the presence of S9: captan greater than dichlorvos greater than toxaphene greater than lindane greater than nitrofen greater than chlordane. Rankings were similar in the absence of S9. Of these 6 pesticides, only nitrofen required S9 to induce prophage. Comparisons with mutagenesis data in Salmonella indicated that the Microscreen assay detected as genotoxic each of the pesticides that were mutagenic in Salmonella; moreover, it detected 2 additional carcinogens (chlordane and lindane) that were not mutagenic in the Salmonella assay. The possible use of the Microscreen phage-induction assay to detect chlorinated organics is discussed.

Animals↗

Pesticide residues in freshwater and marine zooplankton: a review.

A review of the scientific literature on pesticide residues in freshwater and marine zooplankton indicates that despite the great number of pesticides in current use, only residues of the persistent organochlorine insecticides, many of which have been restricted or removed from general use in North America, have been determined. Much of this information is outdated. In addition, with the exception of the Great Lakes on which limited information is available, reports on residues in freshwater zooplankton are rare. Information on residues of the newer, less persistent but heavily used pesticides is lacking. As an alternative to field sampling and chemical analysis of endemic populations of zooplankton, scientists have modeled the bioaccumulation of pesticides in zooplankton using either laboratory microcosms or mathematical equations. However, the extent and importance of trophic transfer to higher food levels through this intermediary group of organisms is still controversial. In addition, the relationship between accumulation of pesticides and toxicity to zooplankton remains unresolved.

Journal Article↗

Organic compounds adsorption onto activated carbon: the effect of association between dissolved humic substances and pesticides.

The quantitative determination of pesticide binding to dissolved humic substances is relevant to both water treatment operation using activated carbon adsorption process and the application of transport models that predict the environmental distribution patterns of a given hydrophobic contaminant. In this study and in a first set of experiments, the extent of binding between (i) three pesticides of environmental concern, aldicarb, lindane and pentachlorophenol, and (ii) dissolved commercial humic acid and soil extracted fulvic acid, was determined using dialysis experiments and water solubility enhancement tests. In a second set of experiments, the influence of dissolved humic substances or pesticide on the retention of the other co-adsorbate onto activated carbon was investigated in binary systems. It was found that association was negligible for aldicarb and that the pesticide sorption onto activated carbon was not affected by humic acid (8.5 mg liter(-1) DOC). The association constants K for lindane and pentachlorophenol were identical in the presence of fulvic acid (logK=4.1) but lower than that observed with humic acid. In the presence of humic acid, binding affinity for pentachlorophenol (logK=4.6) was higher than the one observed for lindane (logK=4.4), despite its much higher water solubility. This observation suggests that the aromatic character of the pentachlorophenol molecule contributes to association interactions with humic acid. From co-adsorption experiments onto activated carbon it was found that fulvic acid (7.7 mg litre(-1) DOC) slightly enhances sorption kinetics of pentachlorophenol. Lindane (1 mg litre(-1)) does not affect sorption kinetics for fulvic acid but markedly enhances both the sorption kinetics and adsorptive capacity for humic acid. Activated carbon retention of dissolved humic substances or pesticide appears to be enhanced by the association potential that exists between these co-adsorbates in some binary systems.

Journal Article↗

Tobacco budworm P-glycoprotein: biochemical characterization and its involvement in pesticide resistance.

Since pesticides have been shown to interact with P-glycoprotein (P-gp), the purpose of this study was to examine the possible role of P-gp in pesticide resistance in the tobacco budworm (Heliothis virescens). Using three P-gp antibodies, P-gp expression in various resistant populations of tobacco budworms was found to be 2-6-times that of the susceptible larvae. Tobacco budworm P-gp was glycosylated and localized primarily in the cuticle and fat body with little expression in the mid gut. To determine the role of P-gp in pesticide resistance, resistant tobacco budworm larvae were treated with a P-gp inhibitor, quinidine, and challenged with various doses of thiodicarb. Inhibition of P-gp decreased the LD50 for thiodicarb by a factor of 12.5. Quinidine treatment did not result in a significant inhibition of the P-450 system nor did it alter the feeding of the larvae, suggesting the potential involvement of P-gp in pesticide resistance. An age-dependent increase in P-gp expression was detected in resistant larvae as compared to control, susceptible larvae. This correlates with the reported age-dependent increase in resistance and is further evidence supporting the role of P-gp in the development of pesticide resistance.

ATP Binding Cassette Transporter, Subfamily B, Mem↗

Rapid isolation with Sep-Pak C18 cartridges and wide-bore capillary gas chromatography of organophosphate pesticides.

A simple and rapid method for isolation of eleven organophosphate pesticides with Sep-Pak C18 cartridges from human urine and plasma, is presented. The detection of the pesticides was made by wide-bore capillary gas chromatography (GC) with flame ionization detection. The pesticide-containing samples, after mixing with water, were directly applied to the cartridges and eluted with chloroform/isopropanol (9:1). The recoveries with use of the cartridges were excellent for most pesticides. Separation of each pesticide peak from each other and from impurities on the gas chromatograms was also satisfactory with use of non-polar and slightly polar capillary columns. The isolation method with use of the cartridges, together with the wide-bore capillary GC, seems very useful in forensic and environmental chemistry and clinical toxicology.

Chromatography, Gas↗

Impacts of carbamate pesticides on olfactory neurophysiology and cholinesterase activity in coho salmon (Oncorhynchus kisutch).

Many freshwater aquatic environments in the Pacific Northwest of North America contain neurotoxic pesticides, an issue of concern given the use of many of these habitats by Pacific salmon (Oncorhynchus sp.). Pesticides such as carbamates are known to affect fundamental physiological systems (such as the enzyme acetylcholinesterase (AChE)), and have been shown to affect salmonid olfactory-mediated behaviors. A neurophysiological measure of olfactory function, the electro-olfactogram (EOG), was used in this study to examine the impacts of acute localized exposure to three carbamates (the insecticide carbofuran, the antisapstain IPBC, and the fungicide mancozeb) on olfactory function in the coho salmon (Oncorhynchus kisutch). We also examine the potential for these pesticides to alter AChE levels in the primary olfactory system and brain with brief exposures (30 min to only the olfactory rosette (OR)). In results, we find that the EOG in coho salmon is highly sensitive to brief localized exposures of two of these three carbamate pesticides. The effective nominal concentration required to cause a 50% reduction in EOG amplitude (EC50) for carbofuran was 10.4 microg/l and for IPBC was 1.28 microg/l. For mancozeb, the EC50 was higher at 2.05 mg/l. All three carbamates also affected AChE activity levels in the OR and brain (BR): carbofuran exposure at 200 microg/l significantly inhibited AChE activity in the OR, and both IPBC and mancozeb significantly increased AChE activity in BR at multiple concentrations with acute localized exposure. These carbamate effects highlight the sensitivity of salmon olfactory neurophysiology to pesticides acting not only potentially via AChE-inhibition, but also by other currently unknown modes of action.

Analysis of Variance↗

A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils.

Batch adsorption and desorption experiments were performed using thirteen agricultural soil samples and five pesticides. Experimental data indicated a gradient in pesticide adsorption on soil: trifluralin >> 2,4-D > isoproturon> atrazine >> bentazone. Atrazine, isoproturon and trifluralin adsorption were correlated to soil organic matter content (r2 = 0.7, 0.82, 0.79 respectively). Conversely, bentazone adsorption was governed by soil pH (r2 = 0.68) while insignificant effect has been shown in the case of 2,4-D. Multiple linear regressions were used to combine relationships between the various soil parameters and the Freundlich adsorption coefficient (K(f)) of each pesticide. Then desorption was assessed since it may reflect some of the interactions involved between the pesticides and the soil components. Adsorbed molecules were released into aqueous solution in the following order: bentazone >> atrazine> isoproturon> 2,4-D >> trifluralin. The occurrence of hysteresis did not allow an accurate interpretation of the pesticide desorption data because of the possible interplay of several processes.

2,4-Dichlorophenoxyacetic Acid↗

Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China.

Tonghui River, a typical river in Beijing, People's Republic of China, was studied for its water and sediment quality, by determining the levels of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs) and 18 organochlorine pesticides in water and sediment samples. Total PAHs, PCBs and organochlorine pesticides concentrations in water varied from 192.5 to 2651 ng/l, 31.58-344.9 ng/l and 134.9-3788 ng/l, respectively. The total PAHs, PCBs and organochlorine pesticides concentrations in surficial sediments were 127-928 ng/g, 0.78-8.47 ng/g and 1.79-13.98 ng/g dry weight, respectively. The results showed that the concentration of these selected organic pollutants in sediment was higher than those in surface water. It may be due to the fact that organic hydrophobic pollutants tend to stay in the sediments. The PAHs were dominated by 2-, 3-ring components in water samples and by 3- and 4-ring compounds in sediment. For organochlorines, alpha-HCH, delta-HCH, Heptachlor, Endosulfan II, DDT are the major organochlorine pesticides in water while Heptachlor, Dieldrin and DDE composed of 95% of total organochlorine pesticides in sediment. For HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH), the predominance of alpha-HCH of total HCHs were clearly observed in water and sediment. PCB18, PCB31 and PCB52 were predominant in water, on average these compounds collectively accounted for 67% of total PCBs. But in sediment, the predominant compounds were PCB28, PCB31 and PCB153, which accounted for 71% of total PCBs in sediment. The levels of micro pollutants in our study areas were compared with other studies.

China↗

The in vitro effects of some pesticides on carbonic anhydrase activity of Oncorhynchus mykiss and Cyprinus carpio carpio fish.

Systemic carbonic anhydrase (CA) inhibitors are among the most powerful agents to lower intraocular pressure. Unfortunately, their use is frequently accompanied by undesired side effects. Some are due to the relatively large amounts of drug that have to be systematically administered to inhibit the CA in the ciliary processes. The aim of the present work was to study in vitro effects of some pesticides on CA enzyme obtained from blood of fish, which play a key role in salt- and osmoregulation and acid-base balance in the fish, Oncorhynchus mykiss and Cyprinus carpio carpio living in freshwaters, and compared with CA inhibitors. CA activities were significantly inhibited by pesticides and inhibitors. I(50) values of O. mykiss CA enzyme inhibited by lambda-cyhalothrin, deltametrin, diozinon, dorzolamide and brinzolamide were 6.05 x 10(-4), 1.48 x 10(-5), 6.84 x 10(-3), 3.82 x 10(-5) and 1.80 x 10(-6) mol/l, and that for C. c. carpio 6.86 x 10(-4), 4.70 x 10(-4), 3.92 x 10(-3), 8.34 x 10(-6) and 1.42 x 10(-6) mol/l, respectively. The pesticides used in this study inhibited the CA activity from different fish species to various degrees. It was found that the most effective inhibitor of CA enzyme within pesticides used was detrametrin. These findings observed in vitro could be useful in the understanding of the toxic effects that pesticides elicit on aquatic organisms in vivo.

Animals↗

Effect of organochlorine pesticides on human androgen receptor activation in vitro.

Many persistent organochlorine pesticides (OCs) have been implicated in adverse effects, that is, reproductive and developmental effects, in man and in wildlife alike. It has been hypothesized that these so-called xeno-hormones could be responsible for the increased incidence in various male sexual differentiation disorders such as hypospadias, cryptorchidism, low sperm counts and quality. In this report, OCs, called endocrine disrupters, were tested for their interaction with the androgen receptor. The stable prostatic cell line PALM, which contains a human androgen receptor (hAR) expression vector and the reporter MMTV-luciferase, was used to characterize the response of hAR to OC and was compared with synthetic androgen compound R1881. We found that all the OC pesticides tested were able to shift the agonist [(3)H]-R1881 from its binding site to the AR in competitive binding assays. In addition, these compounds antagonize-in a dose-dependent manner-the AR-mediated transcription by synthetic AR ligand R1881. None of the pesticides reacted as agonists. These results demonstrate that OC endocrine activities in vivo probably result from direct and specific binding to the AR ligand-binding domain. Although the antagonistic potential of OC pesticides is lower than that of hydroxyflutamide, they are capable of disrupting the male hormone signaling pathway. Because these chemicals are extremely persistent and tend to bioaccumulate, these results support the hypothesis that the recent increase in the incidence of male sexual disorders could be due to long exposure to ubiquitous OC pesticides found in the environment.

Androgen Antagonists↗

Pyrethroid pesticide-induced alterations in dopamine transporter function.

Parkinson's disease (PD) is a progressive neurodegenerative disease affecting the nigrostriatal dopaminergic pathway. Several epidemiological studies have demonstrated an association between pesticide exposure and the incidence of PD. Studies from our laboratory and others have demonstrated that certain pesticides increase levels of the dopamine transporter (DAT), an integral component of dopaminergic neurotransmission and a gateway for dopaminergic neurotoxins. Here, we report that repeated exposure (3 injections over 2 weeks) of mice to two commonly used pyrethroid pesticides, deltamethrin (3 mg/kg) and permethrin (0.8 mg/kg), increases DAT-mediated dopamine uptake by 31 and 28%, respectively. Using cells stably expressing DAT, we determined that exposure (10 min) to deltamethrin and permethrin (1 nM-100 microM) had no effect on DAT-mediated dopamine uptake. Extending exposures to both pesticides for 30 min (10 microM) or 24 h (1, 5, and 10 microM) resulted in significant decrease in dopamine uptake. This reduction was not the result of competitive inhibition, loss of DAT protein, or cytotoxicity. However, there was an increase in DNA fragmentation, an index of apoptosis, in cells exhibiting reduced uptake at 30 min and 24 h. These data suggest that up-regulation of DAT by in vivo pyrethroid exposure is an indirect effect and that longer-term exposure of cells results in apoptosis. Since DAT can greatly affect the vulnerability of dopamine neurons to neurotoxicants, up-regulation of DAT by deltamethrin and permethrin may increase the susceptibility of dopamine neurons to toxic insult, which may provide insight into the association between pesticide exposure and PD.

Animals↗

Removal of organophosphate pesticides from wastewater by supercritical carbon dioxide extraction.

Organophosphate pesticides including fenitrothion chlorpyrifos, diazinon, methamidophos, edifenphos, mevinphos, fenthion, and acephate present in agro-wastewater can be effectively removed by supercritical carbon dioxide (SC-CO2) extraction. Near quantitative removal of the pesticides from the aqueous solution can be achieved by SC-CO2 at 90 degrees C and 325 atm for 20 min of static extraction followed by 40 min of dynamic extraction. The extracted pesticides were collected in a small amount of Fenton's solution. The pesticides in Fenton's solution were degraded completely within an hour after the collection. A combination of SC-CO2 extraction and subsequent degradation by Fenton's reagent may provide an alternative water purification strategy for treating organophosphate pesticides in agro-wastewater.

Agriculture↗

Effects of tetradifon on Daphnia magna during chronic exposure and alterations in the toxicity to generations pre-exposed to the pesticide.

Daphnia magna was exposed to some nominal sublethal tetradifon concentrations (0.10, 0.18, 0.22 and 0.44 mg/l) during 21 days. Chronic toxicity tests were carried out using neonates of F(1) first brood (F(1)-1st) and F(1) third brood (F(1)-3rd) offspring generations from parentals (F(0)) pre-exposed to the pesticide. The effect of tetradifon on survival, reproduction and growth was monitored for the selected daphnid generations. The parameters used to evaluate pesticide effect on reproduction were: mean total young per female, mean brood size, time to first reproduction, mean number broods per female and intrinsic rate of natural increase (r). Survival and growth (body length) were also determined after 21 days of exposure to the pesticide. Reproduction was significantly reduced when tetradifon concentration increased in the medium. This effect was higher in F(1)-1st and F(1)-3rd offsprings compared to the parental generation (F(0)) daphnids. The intrinsic rate of natural increase (r) decreased with increasing concentrations of tetradifon especially in those animals from F(1)-3rd. However, the growth of the exposed organisms decreased in the same order of magnitud in all the generations tested. Survival was not affected after exposure to the selected tetradifon concentrations. The maximum acceptable toxicant concentration (MATC) was calculated for F(0), F(1)-1st and F(1)-3rd generations exposed to the pesticide using as parameter of evaluation the intrinsic rate of natural increase (r). The interpolation of these results gave MATC values of 0.13 mg/l pesticide for F(0) and F(1). The EC50 values have been derived for some selected parameters on D. magna exposed to tetradifon. EC50 values decreased in F(1)-1st and F(1)-3rd generations compared to the parental generation F(0), these results mean that less amount of toxicant would be necessary to reduce the selected parameters to 50% in the first and third broods of D. magna. Expanding the reproduction tests to several broods of a parental generation revealed important information on chronic toxicity that could be used in the protection of aquatic environment.

Journal Article↗

Organochlorine pesticide residues in catfish, Tachysurus thalassinus (Ruppell, 1835), from the South Patches of the Bay of Bengal.

Organochlorine pesticides (p,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, lindane, and heptachlor) were measured in muscle tissue of catfish (Tachysurus thalassinus) during the dry and wet season. Catfish were collected from the South Patches of the Bay of Bengal during October-December 1997 and May-July 1998. Tissue residues were analyzed by using gas-chromatography (GC) in electron capture detector (ECD) mode and were verified by thin layer chromatography (TLC). The pesticide residues levels were found in order of sigma DDT > Heptachlor > Lindane > Aldrin. Higher levels of pesticide residues were found in all samples during dry season, as compared with the wet season, primarily due to elevated lipid content in fishes. A positive correlation and linear relationship was observed between the pesticide residues (sigmaDDT and sigmaOCs) and lipid content of fishes. However, the concentrations of pesticide residues in the muscle were found to be lower than the FAO/WHO [(1993) Food standards programme. Codex Alimentarius Commission. vol. 9 (4) pp. 149-158] recommended permissible limit for human consumption.

Animals↗