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Acute poisoning with pesticides in the state of Mato Grosso do Sul, Brazil.

Exposure to pesticides has been the source of many acute and chronic health problems in the rural population, mainly in developing countries. The objective of this study was to characterize the poisonings from acute exposure to agricultural pesticides used in the state of Mato Grosso do Sul, Brazil, from 1992 to 2002, which were reported to the Integrated Center of Toxicological Vigilance of the State Health Department. A total of 1355 involuntary (accidental or occupational) and voluntary (intentional self-poisoning) cases were reported during the period of the study. The majority of the poisonings occurred with men ranging in age from 15 to 49 years of age (55.1%). One hundred seventy-six poisonings lead to death, with a case fatality rate (CFR) three times higher than the average Brazilian CFR. The pesticide poisoning rates, per 100,000 inhabitants living in rural areas, ranged from 25 to 65.7 during the period of the study. In 2000, the micro-region of Campo Grande, where the state capital is located, had the highest rate, with 100.5 exposure/100,000 inhabitants, followed by Dourados, the larger agricultural region of the state. Insecticides were involved in 75.7% of the poisoning cases, followed by herbicides, with 12.2% of the cases. The anticholinestherase insecticides methamidophos, carbofuran and monochrotophos were the primary pesticides involved in the poisonings. The insecticide dimethoate was associated with the highest CFR (30.8%). The high rates of pesticide poisoning in the rural populations of certain regions of the state of Mato Grosso do Sul indicate the need for a more detailed study concerning the risk of pesticide poisoning among these populations.

Adolescent↗

Is plasma beta-glucuronidase a novel human biomarker for monitoring anticholinesterase pesticides exposure? A Malaysian experience.

A cross-sectional study was conducted to investigate the effects of acute and chronic pesticide exposure on the plasma beta-glucuronidase enzyme activity among five patients of acute pesticide poisoning in Tengku Ampuan Rahimah Hospital, Klang, 230 farmers in the MADA area, Kedah and 49 fishermen in Setiu, Terengganu. The duration of pesticide exposure among the patients was unknown, but the plasma samples from patients were collected on day one in the hospital. The duration of pesticide exposure among the farmers was between 1 and 45 years. The beta-glucuronidase activity was compared with plasma cholinesterase activity in the same individual. The plasma cholinesterase activity was measured using Cholinesterase (PTC) Reagent set kit (Teco Diagnostics, UK) based on colorimetric method, while the plasma beta-glucuronidase activity was measured fluorometrically based on beta-glucuronidase assay. The plasma cholinesterase activity was significantly reduced (p<0.05) among the patients (1386.786+/-791.291 U/L/min) but the inhibition in plasma cholinesterase activity among the farmers (7346.5+/-1860.786 U/L/min) was not significant (p>0.05). The plasma beta-glucuronidase activity among the farmers was significantly elevated (p<0.05) (0.737+/-0.425 microM/h) but not significant among the patients (p>0.05). The plasma cholinesterase activity was positively correlated with the plasma beta-glucuronidase activity among the farmers (r=0.205, p<0.01) but not among the patients (r=0.79, p>0.05). Thus, plasma beta-glucuronidase enzyme activity can be measured as a biomarker for the chronic exposure of pesticide. However, further studies need to be performed to confirm whether plasma beta-glucuronidase can be a sensitive biomarker for anticholinesterase pesticide poisoning.

Adolescent↗

Effect of in vitro estrogenic pesticides on human oestrogen receptor alpha and beta mRNA levels.

Nine widely distributed pesticides were recently demonstrated to possess potential estrogenic properties in oestrogen receptor (ER) transactivation and/or E-screen assays. We tested the effect of these nine pesticides on the human ERalpha and ERbeta mRNA steady state levels in the mamma cancer fibroblast MCF-7BUS cells using on-line RT-PCR. Like 17beta-oestradiol (E2), fenarimol significantly decreased the ERalpha and increased the ERbeta mRNA level. Endosulfan and pirimicarb alone decreased the ERalpha mRNA level weakly. After co-exposure with E2, all the tested pesticides counteracted the E2-induced decrease of the ERalpha mRNA level, but only significantly for prochloraz, dieldrin, and tolchlofos-methyl. Alone no pesticides affected the ERbeta mRNA level significantly, but chlorpyrifos increased the mRNA level weakly. Co-exposure with E2 elicited a significant increased ERbeta mRNA level by prochloraz, fenarimol, endosulfan, dieldrin, and tolchlofos-methyl, whereas no significant effect of the carbamate pesticides on the ERbeta mRNA level was observed. This study demonstrated that organochlor and organophosphorous pesticides possess the ability to interfere with the ERalpha and ERbeta mRNA steady state levels.

Cell Line, Tumor↗

A study on pesticide runoff from paddy fields to a river in rural region--2: development and application of a mathematical model.

A mathematical model was developed to predict the runoff of pesticides from paddy fields to a river in a rural region. The model comprises three submodels: (1) submodel for river flow, (2) submodel for pesticide behavior in paddy fields, (3) submodel for pesticide behavior in a river. The tank model was applied to predict the river flow and the paddy water. In order to reproduce the actual behavior of pesticides in paddy fields, the kinetics of the transport and reaction mechanisms of pesticides applied to paddy fields were considered in the model. The model was applied to the Kozakura River Basin where the detailed field survey was conducted. The model reflected well the runoff characteristics of pesticides obtained from the detailed field survey.

Agriculture↗

Organophosphate pesticide exposure in a group of Washington State orchard applicators.

As part of a study to investigate the potential for organophosphates to cause chronic neurologic sequelae, we assessed the pesticide exposure experience of a group of Washington State apple orchard applicators. Seasonal monitoring of cholinesterase activity for 48 regular organophosphate applicators and a control group of 40 slaughterhouse workers was performed. A subset of the pesticide applicators participated in an in-depth exposure assessment. This involved observation of spraying activities during 1 spray day, as well as cholinesterase monitoring and dermal exposure assessment using a fluorescent tracer in the pesticide formulation. Comparison of seasonal red blood cell cholinesterase change in pesticide workers according to exposure level, characterized by frequency of pesticide spraying and protective equipment use, showed lower cholinesterase levels among higher exposed groups compared to lesser exposed groups. In-depth exposure assessment revealed exposure primarily on the head and hand regions. Subclinical changes (less than 15% inhibition) in red cell cholinesterase correlated well with dermal exposure calculations. This study suggests that cholinesterase monitoring may be a useful biological marker for even subclinical organophosphate pesticide effects.

Agricultural Workers' Diseases↗

Application of liquid chromatography with mass spectrometry combined with photodiode array detection and tandem mass spectrometry for monitoring pesticides in surface waters.

Liquid chromatography with photodiode array detection (LC-DAD) and liquid chromatography with mass spectrometry (LC-MS) are two techniques that have been widely used in monitoring pesticides and their degradation products in the environment. However, the application of liquid chromatography with tandem mass spectrometry (LC-MS-MS) for such purposes, once considered too costly, is now gaining considerable ground. In this study, we compare these methods for the multi-residue analysis of pesticides in surface waters collected from the central and southeastern regions of France, and from the St. Lawrence River in Canada. Forty-eight pesticides belonging to eight different classes (triazine, amide, phenylurea, triazole, triazinone, benzimidazole, morpholine, phenoxyalkanoic), along with some of their degradation products, were monitored on a regular basis in the surface waters. For LC-MS, we used the electrospray ionization (ESI) interface in the negative ionization mode on acidic pesticides (phenoxyalkanoic, sulfonylurea), and the atmospheric pressure chemical ionization (APCI) interface in the positive ionization mode on the remaining chemicals. Different extraction techniques were employed, including liquid-liquid extraction with dichloromethane, and solid-phase extraction using C18-bonded silica and graphitized carbon black cartridges. Eleven of the target chemicals (desethylatrazine, desisopropylatrazine, atrazine, simazine, terbuthylazine, metolachlor, carbendazime, bentazone, penconazole, diuron and isoproturon) were detected by LC-MS at concentrations ranging from 20 to 900 ng/l in the surface waters from France, and six pesticides (atrazine, desethylatrazine, desisopropylatrazine, cyanazine, simazine and metolachlor) were detected by LC-MS and LC-MS-MS at concentrations ranging from 3 to 52 ng/l in the samples drawn from the St. Lawrence River. There was good correlation between the LC-DAD and LC-MS techniques for 60 samples. The slope of the curves expressing the relationship between the results obtained with LC-DAD versus those obtained by LC-MS was near 1, with a correlation coefficient (r) of over 0.93. The identification potential of the LC-MS technique, however, was greater than that of the LC-DAD; its mass spectra, mainly reflecting the pseudomolecular ion resulting from a protonation or a deprotonation of the molecule, was rich in information. The LC-MS-MS technique with ion trap detectors, tested against the LC-MS on 10 surface water samples, gave results that correlated well with the LC-MS results, albeit generating mass spectra that yielded far more information about the structure of unknown substances. The sensitivity of the LC-MS-MS was equivalent to the selected ion monitoring (SIM) acquisition mode in LC-MS. The detection limits of the target pesticides ranged from 20 to 100 ng/l for the LC-MS technique (under full scan acquisition), and from 2 to 6 ng/l for LC-MS-MS. These limits were improved by a factor of almost 10 by increasing the sample volume to 10 l.

Chromatography, Liquid↗

Solid-phase microextraction for organochlorine pesticide residues analysis in Chinese herbal formulations.

Solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used to determine pesticide residues in Chinese herbal formulations. Fibers coated with a 100-microm film thickness of poly(dimethylsiloxane) was used to extract 19 organochlorine pesticides (OCPs). The pesticides in the study consisted of alpha-, beta-, gamma-and delta-hexachlorocyclohexane, p,p'-DDD, p,p'-DDE, p,p'-DDT, o,p'-DDT, aldrin, dieldrin, endrin, endrin aldehyde, endrin ketone, endosulfan (I, II and sulfate), heptachlor, heptachlor epoxide, and methoxychlor. The optimal experimental procedures for the adsorption and desorption of pesticides were evaluated. The linearity was obtained with a precision below 11% RSD for the studied pesticides expect endosulfan sulfate (21%) in a wide range from 1 to 200 ng/g. Detection limits were reached at below ng/g levels. Heptachlor epoxide was determined at a calculated limit of 0.03 ng/g. Comparison between SPME and Soxhlet extraction showed that SPME has a less than one order detection limit for residue pesticide determination. The proposed method was tested by analyzing herbal formulations from a local market for OCP multiresidues. Some residues studied were detected in the analyzed samples. The results demonstrate the suitability of the SPME-GC-MS approach for the analysis of multi-residue OCPs in Chinese herbal formulations.

Drugs, Chinese Herbal↗

CAPA--Computer Aided Pesticide Analysis. Computer program for the automated evaluation of chromatographic data for residue analysis of foods.

Pesticide residue analysis in food by means of gas chromatography with columns of different polarity and several selective detectors provides the analyst with a great number of chromatographic data. The introduction of personal computer based chromatographic data systems into research laboratories increased the efficiency of information management and organization; user designed software packages now have direct access to the stored data. The computer program CAPA (Computer Aided Pesticide Analysis) was developed for the interpretation and evaluation of chromatographic results. The program is written in TURBO PASCAL 3.0 and consists of several subprograms. In the main database all pesticides are filed in a multidimensional structure. The various subprograms have access to this catalog of retention and response data. Using the subprogram INTERPRET, which is the core of CAPA, the analyst is provided with all information necessary to interpret a gas chromatogram: identification of calibrated pesticides and estimation of their concentration. Automated screening analyses can be evaluated with the subprogram AUTOINTERPRET, an automated of INTERPRET that uses all relevant information stored in the data base. A report is produced containing the pesticides found in the sample and proposals how to confirm them best with the equipment and methods available. Finally the analyst has to make the decision about the probable presence and quantity of the indicated pesticides and to project the next confirmatory step by using INTERPRET.

Autoanalysis↗

Multiresidue method for determination of 90 pesticides in fresh fruits and vegetables using solid-phase extraction and gas chromatography-mass spectrometry.

A multiresidue method for analysis of 90 pesticides with different physico-chemical properties in fruits and vegetables was developed. The method involves a rapid and small-scale extraction procedure with acetone using vortex mixing. Solid-phase extraction (SPE) on a highly cross-linked polystyrene divinylbenzene column (LiChrolut EN) was used for clean-up and pre-concentration of the pesticides from the water-diluted acetone extracts. For most fruit and vegetable samples this partial clean-up was sufficient, but some of them with more co-extracting substances need further clean-up (cereals, spinach, carrots, etc.). Diethylaminopropyl (DEA) modified silica was used for efficient removal of interferences caused by various organic acids, sugars, etc. The pesticide residues were determined by gas chromatography with a mass selective detector (GC-MS). The majority of pesticide recoveries for various fruits and vegetables were >80% in the concentration range from 0.01 to 0.50 mg/kg, except for the most polar pesticides (methamidophos, acephate, omethoate) which cannot be determined by this method. The limit of quantitation for most of the pesticides was 0.01 mg/kg with majority of relative standard deviations (R.S.D.s) below 10%.

Calibration↗

Electrophysiological responses of three chemosensory systems in the carp to pesticides.

Responses of three chemical senses, olfaction, taste, and pit organ sense, to three pesticides were studied electrophysiologically in carp, Cyprinus carpio. Only olfaction was responsive to the three pesticides at behavioral avoidance levels, which were determined in a previous study. The olfactory thresholds for benthiocarb, isoprothiolane, and fenitrothion were 1.7 x 10(-1) micrograms/l (4 log units lower concentration than 48-h LC50), 6.7 x 10(-3) micrograms/l (6 log units lower than 48-h LC50), and 4.9 x 10(2) micrograms/l (1 log unit lower than 48-h LC50), respectively. There were two distinctive features in the olfactory response to pesticides. One is that these pesticides barely indicated the concentration dependency that is usually recognized in the olfactory response to a typical stimulant such as L-alanine or NaCl. Another is that these pesticides indicated a power spectrum with an overall increase in frequency ranges of less than 10.0 Hz, unlike L-alanine or NaCl, which show a marked peak ranging from 8.0 to 12.0 Hz. These findings suggest that there is a specific mechanism in the chemoreception for these pesticides.

Animals↗

Combined toxicity effects of MTBE and pesticides measured with Vibrio fischeri and Daphnia magna bioassays.

Methyl-tert-butyl ether (MTBE), a fuel oxygenate that is added to gasoline, commonly contaminates aquatic systems, many of which are already contaminated with pesticides. The toxic effects (EC(50) value) of several pure pesticides (Diuron, Linuron, Dichlofluanid, Sea nine, Irgarol and tributyltin (TBT)) were measured and compared with the EC(50) value of the pesticide mixed with MTBE, using the Vibrio fischeri and Daphnia magna acute toxicity assays. The interaction between chemicals was evaluated in terms of the effects of mixing on the EC(50) value (i.e. the concentration (mg/L) of a compound or mixture that is required to produce a 50% change in a toxic response parameter) and the time required to generate the toxic response. Presence of MTBE enhanced the EC(50) value of several pesticides (Diuron, Dichlofluanid, TBT and Linuron) and/or the toxic response manifested more rapidly than with pure pesticides. Toxicity enhancements were quite substantial in many cases. For example, the presence of MTBE increased the toxicity of Diuron by more than 50% when tested with the V. fischeri assay (5, 15 and 30 min exposure). Also, the toxic response manifested itself within 5 min whereas without the MTBE the same response arose in 30 min. Presence of MTBE increased the toxicity of Dichlofluanid by 30% when measured with the D. magna assay. Toxicities of only two pesticides (Sea nine and Irgarol) were not raised by the presence of MTBE.

Animals↗

Comparison of different sampling techniques for the evaluation of pesticide spray drift in apple orchards.

An analytical method using gas chromatography-mass spectrometry has been developed for the evaluation of different sampling techniques to characterise spray drift in a commercial apple orchard. Eleven pesticides were studied (fungicides, insecticides and herbicides). A collection of airborne spray-drift pesticides released from a low-profile air-blast orchard sprayer was investigated using six types of samplers: (1) a Perkin-Elmer low volume automatic air sampler using with glass tube packed with Supelpak-2; (2) a high volume air sampler: (3, 4) an impinger containing cyclohexane that could be preceded by a glass fibre filter; and (5, 6) glass cartridges packed with Supelpak-2 that could be preceded by a glass fibre filter. Retention efficiencies of the different sampling techniques are compared, and physical forms of the retained pesticides are discussed. These techniques have allowed us to evaluate pesticide spray-drift in the orchard. Results have shown that the molecules' properties (k(H) and vapour pressure) and weather conditions (temperature and relative humidity) strongly influence pesticide gas and particles distribution. However, in the studied orchard, it is difficult to differentiate pesticide spray-drift and post-application transfers since treatment duration was > 2 days.

Agriculture↗

Effect of soil composition and dissolved organic matter on pesticide sorption.

The effect of the solid and dissolved organic matter fractions, mineral composition and ionic strength of the soil solution on the sorption behaviour of pesticides were studied. A number of soils, chosen so as to have different clay mineral and organic carbon content, were used to study the sorption of the pesticides atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), 2,4-D ((2,4-dichlorophenoxy)acetic acid), isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) and paraquat (1,1'-dimethyl-4,4'-bipyridinium) in the presence of low and high levels of dissolved organic carbon and different background electrolytes. The sorption behaviour of atrazine, isoproturon and paraquat was dominated by the solid state soil components and the presence of dissolved organic matter had little effect. The sorption of 2,4-D was slightly affected by the soluble organic matter in the soil. However, this effect may be due to competition for adsorption sites between the pesticide and the soluble organic matter rather than due to a positive interaction between the pesticide and the soluble fraction of soil organic matter. It is concluded that the major factor governing the sorption of these pesticides is the solid state organic fraction with the clay mineral content also making a significant contribution. The dissolved organic carbon fraction of the total organic carbon in the soil and the ionic strength of the soil solution appear to have little or no effect on the sorption/transport characteristics of these pesticides over the range of concentrations studied.

Adsorption↗

Sources of uncertainty in pesticide fate modelling.

There is worldwide interest in the application of probabilistic approaches to pesticide fate models to account for uncertainty in exposure assessments. The first steps in conducting a probabilistic analysis of any system are: (i) to identify where the uncertainties come from; and (ii) to pinpoint those uncertainties that are likely to affect most of the predictions made. This article aims at addressing those two points within the context of exposure assessment for pesticides through a review of the different sources of uncertainty in pesticide fate modelling. The extensive listing of sources of uncertainty clearly demonstrates that pesticide fate modelling is laced with uncertainty. More importantly, the review suggests that the probabilistic approaches, which are typically being deployed to account for uncertainty in the pesticide fate modelling, such as Monte Carlo modelling, ignore a number of key sources of uncertainty, which are likely to have a significant effect on the prediction of environmental concentrations for pesticides (e.g. model error, modeller subjectivity). Future research should concentrate on quantifying the impact these uncertainties have on exposure assessments and on developing procedures that enable their integration within probabilistic assessments.

Animals↗

Evaluation of the genotoxicity potential (by Mutatox test) of ten pesticides found as water pollutants in Cyprus.

Ten pesticides: aldicarb, aldicard sulfone, aldicarb oxide, carbofuran, propoxur, methomyl, diuron, linuron, alachlor and parathion-methyl, found as water pollutants in Cyprus, were evaluated for their genotoxicity potential with the Mutatox test, both directly and after exogenous activation with S9 hepatic enzymes. A dark variant (M 169) of the Photobacterium phosphoreum was used as the test organism. Trials were undertaken in triplicate using ground-water spiked with pesticides solutions at testing concentration theoretically corresponding to acute effects of 0.004%, up to a maximum of 2%. All tested pesticides were found to be 'suspect genotoxic' directly and after S-9 activation, except for Alachlor which after S-9 activation was found to be 'genotoxic' at 30 micrograms/l. Among the ten pesticides Linuron was found to be 'suspect genotoxic' after S-9 activation at the lowest concentration, i.e. 2 micrograms/l. Genotoxicity after activation with S-9 was demonstrated at a concentration 1-3 orders of magnitude lower than the respective concentration for direct genotoxic effects. Moreover, genotoxicity after S-9 was developed at levels where the acute toxic effects (Microtox) were 'non measurable' to 'negligible'. The investigation of possible genotoxic effects provides essential information on the impacts of pesticides on the Ecosystem and can contribute to the selection of pesticides with the least possible effects.

Animals↗

Parkinson's disease, pesticides, and glutathione transferase polymorphisms.

BACKGROUND: Parkinson's disease is thought to be secondary to the presence of neurotoxins, and pesticides have been implicated as possible causative agents. Glutathione transferases (GST) metabolise xenobiotics, including pesticides. Therefore, we investigated the role of GST polymorphisms in the pathogenesis of idiopathic Parkinson's disease. METHODS: We genotyped by PCR polymorphisms in four GST classes (GSTM1, GSTT1, GSTP1, and GSTZ1) in 95 Parkinson's disease patients and 95 controls. We asked all patients for information about pesticide exposure. FINDINGS: The distribution of the GSTP1 genotypes differed significantly between patients and controls who had been exposed to pesticides (controls vs patients: AA 14 [54%] of 26 vs seven [18%] of 39; AB 11 [42%] of 26 vs 22 [56%] of 39; BB 1 [4%] of 26 vs six [15%] of 39; AC 0 vs four [10%] of 39, p=0.009). No association was found with any of the other GST polymorphisms. Pesticide exposure and a positive family history were risk factors for Parkinson's disease. INTERPRETATION: GSTP1-1, which is expressed in the blood-brain barrier, may influence response to neurotoxins and explain the susceptibility of some people to the parkinsonism-inducing effects of pesticides.

Aged↗

[Validation of a questionnaire for retrospectively measuring occupational pesticide exposure].

OBJECTIVE: The aim of this study is to validate a questionnaire intended to assess retrospective occupational exposure to pesticides in a case control study of workers exposed to pesticides and congenital malformations. METHODS: Occupational data were gathered through personal interviews to 56 agricultural workers and this information was compared to: 1) personal interviews with the workers' foremen, 2) direct observation of working places and 3) another questionnaire self-administered previously by the workers as a part of the "Training Program for Pesticide Applicators". RESULTS: Accuracy and reliability indices are high for variables such as the crops where the interviewees have been working, the time period of the treatments with pesticides and the use of personal protection during treatments (sensitivity ranges between 0.81 and 1 and Kappa index ranges between 0.65 and 0.80). However, for variables such as the duration of the treatments and the pesticides used, sensitivity values range between 0.32 and 0.50. CONCLUSIONS: The results suggest that the questionnaire is a valid tool for measuring some items but in order to improve the quality of the exposure assessment the questionnaire was modified, including a question about size of treated areas (as a proxy variable for duration of treatments) and prompt lists were developed to make easier recall by the workers of specific pesticides used in treatments.

Abnormalities, Drug-Induced↗

Persistent chlorinated pesticides and polychlorinated biphenyls in selected fish species from Lake Tanganyika, Burundi, Africa.

Concentrations of selected organochlorine pesticides and PCBs in seven fish species (cichlids) from the north end of the Lake Tanganyika, Burundi, Africa were determined. Results were compared to previous work on the Lake Tanganyika and other water bodies and to the European Community maximum residue levels (MRLs) in edible fat. The analytical method included a hot Soxhlet extraction with a mixture of acetone: hexane (1:3, v/v), gravimetrically lipid determination, and a single step clean-up. For PCBs and stable pesticides, the clean-up was done on activated silica gel impregnated with concentrated sulfuric acid, while for non acid-stable pesticides superposed layers of alumina, silica and florisil impregnated with 15% methanolic solution of KOH were successively used. Recoveries of organochlorine pesticides from certified reference material (CRM 430) were ranging from 86% for p,p'-DDT to 107% for endrin, while recoveries from blank fat spiked fortified at three different levels were between 65% for alachlor at the lowest fortification level and 107% for mirex at the highest fortification level. The limits of detection for each analyte were ranging from 0.1 ng/g to 0.5 ng/g fat. All chlorinated pesticides were found in the analyzed species but at low concentrations. Boulengerochromis microlepis contained the highest concentrations of HCHs (288.2 +/- 15.5 ng/g fat) and DDTs (909.1 +/- 42.5 ng/g fat), while the highest PCB levels (166.7 +/- 37.4 ng/g fat for the sum of 12 congeners) were found in Oreochromis niloticus. However, there is no evidence that Lake Tanganyika is more contaminated with pesticides than other African water bodies.

Animals↗