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[National surveillance system for acute poisoning caused by pesticides].

In the present paper is presented the surveillance system for pesticide-related illnesses proposed by the Istituto Superiore di Sanità, in collaboration with the Ministry of Health. Through the collaboration of local or regional poison control centres and local health departments with public hospitals and emergency departments, cases of acute pesticide-related illnesses among persons seeking health care will be registered according to standard procedures. Data collected locally will be transmitted to the Istituto Superiore di Sanità for registration and evaluation of the association between symptoms and type of exposure and for severity of illnesses related to pesticide exposure. These data will be analysed at regular intervals in order to estimate the magnitude of the problem of acute pesticide-related illnesses in Italy and to identify priority areas for implementing public health prevention and intervention programs.

Acute Disease↗

Micronuclei frequency in lymphocytes of individuals occupationally exposed to pesticides.

Pesticides have been widely used in developing countries over the years. A large amount of these remains in the environment and organisms. Pesticide pollution is detrimental to human health. The effects can be seen on a short or a long-term basis and the symptoms can vary from headache to cancer. Only a minority of studies focuses on their genotoxic effect. This study assesses the genotoxic effect of the pesticides used at banana-packaging plants with binucleate micronuclei assay using cultured lymphocytes. The studied population included 32 exposed and 37 unexposed women from Costa Rica. There is no significant difference between the two groups. However, women who worked at the packaging plant and had stillbirths or spontaneous abortions were 1.45 times more (alpha = 0.06) likely to have an increased micronuclei frequency than their coworkers who lacked those disorders; this may indicate genetic susceptibility. In vitro pesticides studies and susceptibility biomarkers are needed to identify subgroups with higher risks.

Adolescent↗

[Study on the analytical method for organochlorine pesticide residue using gas chromatography-mass spectrometry].

A gas chromatographic-electron ionization--mass spectrometric method (GC-EIMS) was developed for determining organochlorine pesticide residues. Ten organochlorine pesticides including alpha, beta, gamma and delta isomers of hexachlorocyclohexane(HCH), pp'-DDE, pp'-DDT,op'-DDT,pp'-DDT,pentachloronitrobenzene (Quintozene, PCNB) and hexachlorobenzene(HCB) were determined respectively. Targeted pesticide analyses were separated on DB-5 capillary column. The optimum chromatographic conditions and MS parameter were determined. In test condition, each constituent in the standard mixture was separated efficiently. The retention time of each compound and its characteristic ion were determined in fullscan mode from 50 to 450 amu. The values of their mass spectrum on the total ion current(TIC) with fullscan mode agree with those of NIST and pesticide libraries. The characteristic ions were selected to quantify at m/z 181 for the isomers of HCH, m/z 284 for HCB, m/z 295 for PCNB, m/z 246 for pp'-DDE, m/z 235 for pp'-DDD, op'-DDT and pp'-DDT. The accuracy and reliability were proved respectively by linear test, precise test and recovery test. The linear ranges of PCNB and pp'-DDT are 0.0025-0.50 microgram/ml. The ranges of the isomers of HCH, pp'-DDE, pp'-DDD and op'-DDT are 0.0020-0.40 microgram/ml. The limits of detection are 0.0025 ng for PCNB and pp'-DDE, but 0.0020 ng for the isomers of HCH, HCB, pp'-DDE, pp'-DDD and op'-DDT.

Gas Chromatography-Mass Spectrometry↗

Runoff characteristics of pesticides from paddy fields and reduction of risk to the aquatic environment.

Simultaneous rice-transplanting and subsequent application of pesticides to the paddy fields in the catchment of a rural river on weekends from late May to mid June caused high concentrations and high loadings of pesticides in the river. Imperfections in irrigation water management and the overflow discharge from paddy fields during heavy storm events increased the risk of drinking water contamination and threatened the aquatic ecosystems. Several pesticides were detected at nearly ten ppb in the biofilms on the river bed. In order to reduce the risks due to runoff pesticides, it is necessary to improve the management of irrigation and to strengthen the biodegradation capacity of biofilms on the river bed by maintaining a long retention time in drainage channels.

Biodegradation, Environmental↗

Pesticide residues in agricultural products monitored in Hyogo Prefecture, Japan, FYs 1995-1999.

During a 5-year monitoring survey (April 1995-March 2000) of pesticide residues in agricultural products, 765 samples (478 domestic; 287 imported) collected in Hyogo Prefecture, Japan, were analyzed. The number of pesticides tested increased from 107 in fiscal year (FY) 1995 to 204 in FY 1999. The purpose of the study was to promote consumer safety by excluding the food illegally containing pesticide residues from markets. Overall, 51 % of domestic and 32% of imported samples contained no detectable residues. Multiple residues were detected in 152 (32%) of domestic and 146 (51%) of imported samples. The limit of quantitation was set at 0.01 microg/g and the limit of detection was 0.001 microg/g. Most of the residues were present at low concentrations; 70% of detections in domestic samples were <0.05 microg/g, and 97% were <0.5 microg/g. Although 86% of antifungal agent residues in imported citrus fruits were > or = 0.1 microg/g, 59% of the other residues in imported samples were <0.05 microg/g, and 96% were <0.5 microg/g. Violations of maximum residue limits (MRL) were observed in 3 samples: diazinon in chrysanthemums, dieldrin in cucumbers, and bitertanol in bananas. Of the detectable residues above 0.01 microg/g, 55% in domestic and 38% in imported samples were <10% of the MRL. Of all the samples, 2.4% contained more than 5 different pesticides; tomatoes, strawberries, apples, and citrus fruits tended to have more multiple residues.

Food Analysis↗

Validation of a method for the determination of multiclass pesticide residues in fruit juices by liquid chromatography/tandem mass spectrometry after extraction by matrix solid-phase dispersion.

A multiresidue method was developed and validated for the determination of pesticide residues (omethoate, dimethoate, carbendazim, propoxur, thiabendazole, carbaryl, pirimicarb, azinphos-methyl, methidathion, and iprodione) in fruit juices. The samples were extracted by matrix solid-phase dispersion with diatomaceous earth and analyzed by liquid chromatography/tandem mass spectrometry. The method detection limits were <0.2 ppb for all pesticides; the relative standard deviations for analyses of samples fortified over the range of 2-50 ng/g were <9%, and the recoveries for each pesticide were all between 77 and 102%. The proposed method was used to analyze 21 commercial fruit juices; pesticide residues were found in 71% of the samples.

Beverages↗

Analysis of various Iowa waters for selected pesticides: atrazine, DDE, and dieldrin-1974.

Atrazine, DDE, and dieldrin were extracted and concentrated from various surface, subsurface, and finished waters using the macroreticular resin method. Organic components in the concentrates from these waters were separated by gas chromatography; the amounts of the three pesticides in the waters ranged from 0.5 to 42,000 parts per trillion by weight. Every major watershed in the State of Iowa revealed some degree of pesticide contamination and seasonal variations were consistent with agricultural runoff models. Atrazine concentrations were highest of the three pesticides, a symptom of its widespread use in the corn belt. DDE also appeared in substantial quantities, providing further evidence of the persistence of DDT and its metabolites. Water from several shallow wells and finished water from many water treatment plants were also contaminated. Current treatment processes do not effectively remove these pesticides.

Atrazine↗

Determination of pesticide residues in nonfatty foods by supercritical fluid extraction and gas chromatography/mass spectrometry: collaborative study.

A collaborative study was conducted to determine multiple pesticide residues in apple, green bean, and carrot by using supercritical fluid extraction (SFE) and gas chromatography/mass spectrometry (GC/MS). Seventeen laboratories from 7 countries participated in the final study, and a variety of different instruments was used by collaborators. The procedure simply entails 3 steps: (1) mix 1.1 g drying agent (Hydromatrix) per 1 g frozen precomminuted sample, and load 4-5.5 g of this mixture into a 7-10 mL extraction vessel; (2) perform SFE for 20-30 min with a 1-2 mL/min flow rate of carbon dioxide at 0.85 g/mL density (320 atm, 60 degrees C); and (3) inject the extract, which was collected on a solid-phase or in a liquid trap, into the gas chromatograph/mass spectrometer, using either an ion-trap instrument in full-scan mode or a quadrupole-type instrument in selected-ion monitoring mode. The ability of GC/MS to simultaneously quantitate and confirm the identity of the semivolatile analytes at trace concentrations is a strong feature of the approach. The selectivity of SFE and GC/MS avoids the need for post-extraction cleanup steps, and the conversion of the CO2 solvent to a gas after SFE eliminates the solvent evaporation step common in traditional methods. The approach has several advantages, but its main drawback is the lower recoveries for the most polar analytes, such as methamidophos and acephate, and the most nonpolar analytes, such as pyrethroids. Recoveries for most pesticides are >75%, and recoveries of nonpolar analytes are still >50%. The (within-laboratory) repeatability relative standard deviation (RSDr) values of the recoveries are generally <15%. More specifically, the average results from the 9-14 laboratories in the final analysis of 6 blind duplicates at 3 concentrations for each pesticide are as follows: carbofuran in apple (75-500 ng/g), 89% recovery, 7% RSDr, 9% reproducibility relative standard deviation (RSDR); diazinon in apple (60-400 ng/g), 83% recovery, 13% RSDr, 17% RSDR; vinclozolin in apple (6-400 ng/g), 97% recovery, 13% RSDr, 18% RSDR; chlorpyrifos in apple (50-300 ng/g), 105% recovery, 11% RSDr, 13% RSDR; endosulfan sulfate in apple (150-1000 ng/g), 95% recovery, 15% RSDr, 17% RSDR; trifluralin in green bean (30-200 ng/g), 58% recovery, 11% RSDr, 27% RSDR; dacthal in green bean (60-400 ng/g), 88% recovery, 11% RSDr, 17% RSDR; quintozene in green bean (60-400 ng/g), 79% recovery, 13% RSDr, 18% RSDR; chlorpyrifos in green bean (50-300 ng/g), 84% recovery, 11% RSDr, 17% RSDR; p,p'-DDE in green bean (45-300 ng/g), 64% recovery, 14% RSDr, 27% RSDR; atrazine in carrot (75-500 ng/g), 90% recovery, 11% RSDr, 15% RSDR; metalaxyl in carrot (75-500 ng/g), 89% recovery, 8% RSDr, 12% RSDR; parathion-methyl in carrot (75-500 ng/g), 84% recovery, 14% RSDr, 15% RSDR; chlorpyrifos in carrot (50-300 ng/g), 77% recovery, 13% RSDr, 19% RSDR; and bifenthrin in carrot (90-600 ng/g), 63% recovery, 12% RSDr, and 25% RSDR. All analytes except for the nonpolar compounds trifluralin, p,p'-DDE, and bifenthrin gave average Horwitz ratios of <1.0 when AOAC criteria were used. These 3 analytes had high RSDr values but lower RSDR values, which indicated that certain SFE instruments gave consistently lower recoveries for nonpolar compounds. The collaborative study results demonstrate that the method meets the purpose of many monitoring programs for pesticide residue analysis, and the Study Director recommends that it be adopted Official First Action.

Food Analysis↗

Perpest model, a case-based reasoning approach to predict ecological risks of pesticides.

The PERPEST model is a model that predicts the ecological risks of pesticides in freshwater ecosystems. This model simultaneously predicts the effects of a particular concentration of a pesticide on various (community) endpoints. In contrast to most effect models, PERPEST is based on empirical data extracted from the literature. This model is based on case-based reasoning, a technique that solves new problems (e.g., what is the effect of pesticide A?) by using past experience (e.g., published microcosm experiments). The database containing the past experience has been constructed by performing a review of freshwater model ecosystem studies. This review assessed the effects on various endpoints (e.g., community metabolism, phytoplankton, and macroinvertebrates) and classified them according to their magnitude and duration. The PERPEST model searches for analogous situations in the database, based on relevant (toxicity) characteristics of the compound. This allows the model to predict effects of pesticides for which no effects on a semifield scale have been published. The PERPEST model results in a prediction showing the probability of classes of effects (no, slight, or clear effects, plus an optional indication of recovery) on the various grouped endpoints. This paper discusses the scientific background of the model as well as its strengths, limitations, and possible applications.

Atrazine↗

Pesticide residues in human food and wildlife in The Netherlands.

Several monitoring programmes for pesticide residues in food are currently operative in the Netherlands, some of which are related to EU directives. These programmes cover a range of products. This paper reviews the 1997 and 1998 data for fruit and vegetables, meat, milk, livestock and fish, as well as presenting data on pesticide residues in wildlife. The aim of the paper is to provide an overview of what is known about pesticide residues in the Netherlands, including indications of the origins of the compounds found. A total of 281 different compounds were monitored on fruit and vegetables. Of these compounds, 45% were actually found on products and 28% exceeded the standard. Expressed as percentages of the number of measurements, the data show that 0.3% of the measurements detected a compound, and standards were exceeded in 0.02% of the measurements. Some of the cases in which standards were exceeded concerned the use of compounds in minor crops, for which their use is not permitted. Other cases involved excessive dosages or application within the safety interval before harvest. In meat, milk and livestock, 10 persistent organochlorine compounds were measured. Most of these compounds, with the exception of lindane, are no longer in use, but are still being found as residues. The concentrations found were very low and have not exceeded standards for human consumption since 1993. No assessment was made, however, of products currently in use. Organochlorine compounds have also frequently been found in fish (eel), in higher concentrations than in meat, but in nearly all cases in quantities below the standards for human consumption. Ecological standards for accumulation in the food chain were exceeded on a larger scale and indications of exposure effects on piscivorous birds (cormorants) were found. No data on pesticide residues in wildlife are known for terrestrial organisms.

Animals↗

Effect of dithiocarbamate pesticide zineb and its commercial formulation, azzurro. IV. DNA damage and repair kinetics assessed by single cell gel electrophoresis (SCGE) assay on Chinese hamster ovary (CHO) cells.

Single cell gel electrophoresis (SCGE) was used to analyse dithiocarbamate zineb- and the zineb-containing technical formulation azzurro-induced DNA damage and repair in CHO cells. Cells were treated with zineb (50.0 microg/ml) or azzurro (100.0 microg/ml) for 80min, washed and reincubated in pesticide-free medium for 0-12h until SCGE. Viability of treated cells (0 h) did not differ from control remaining unchanged up to 6h of incubation. After 12h, viability decreased up to 70 and 54% in zineb- and azzurro-treated cultures, respectively. SCGE revealed at 0 h the absence of undamaged cells and an increase of slightly damaged and damaged cells in zineb-treated cultures or by an increase in damaged cells in azzurro-treated cultures. For both chemicals, a time-dependent repair of pesticide-induced DNA damage within a 0-12h post-treatment incubation period was observed. Overall, damaged cells decreased as a function of the repair time for both pesticides while the slightly damaged cells decreased as a function of the repair time of zineb-induced DNA damage. Concomitantly, a time-dependent increase of undamaged cells was observed within the 0.5-12h repair time for both pesticides. At 12h after treatment, no differences in the frequencies of undamaged, slightly damaged and damaged cells were found between both zineb- or azzurro-treated cultures and control values as well as between zineb- and azzurro-treated cells. Immediately after exposure, nuclear DNA from zineb and azzurro-treated cells were larger and wider than nuclear DNA from untreated cells. When damaged cells were allowed to repair, a time-dependent decrease of the amount of free DNA migrating fragments was observed committed only to damaged cells but not in slightly or undamaged cells. On the other hand, no time-dependent alteration on nuclear DNA width within the 0-12h repair period was observed.

Animals↗

[Determination of organochlorine pesticide multi-residues in Astragalus membranaceus (Fisch.) Bge. var. mongholicus (Bge.) Hsiao, Panax notoginseng (Burk.) F. H. Chen and P. quin quefolium L].

OBJECTIVE: To determine 15 organochlorine pesticide residues in Astragalus membranaceus, Panax notoginseng and P. quinquefolium. METHODS: The 15 organochlorine pesticides were extracted from samples with mixed solvents by ultrasonication, cleaned up by a column packed with Florisil, and then separated by capillary gas chromatography with electron capture detector(CGC-ECD). The capillary column was DB-5(15 m x 0.32 mm x 0.25 microns); injector temperature 240 degrees C; detector temperature 320 degrees C; the column temperature program initial 100 degrees C (hold 0.5 min), rate of 20 degrees C min-1 to 210 degrees C (hold 0.5 min), rate of 8 degrees C min-1 to 240 degrees C (hold 10 min). The column head-pressure was 58.84 kPa. The injection was splitless and the injection volume was 1 microliter. RESULT AND CONCLUSION: The average recoveries and RSD are in the range of 78.30%-130.1% and 0.75%-31.9% at two spiked mixed organochlorine pesticide levels, respectively. All the samples have organochlorine pesticide residues.

Astragalus propinquus↗

[Effect of organophosphorus pesticide toxicity on soil animal].

The test of organophosphorus pesticide on toxicity of soil animal showed that soil animal is sensitive to organophophorus toxicity, the species and quantities of soil animal treated by four kinds of pesticide are decreased. The species of soil animals was decreased with decreasing common population and rare population, while the amount change of soil animal was associated with the amount change of dominant populations of Acarina and Collembola. Toxicology and toxicity experiment showed that the pesticide has a deadly effect to earthworm, and its toxicity constrained the respiration intensity of big soil animals obviously, which weakened with the increasing pesticide concentration and prolonging poisoning time.

Animals↗

Effects of agricultural pesticides on the immune system of Rana pipiens and on its resistance to parasitic infection.

In the past 30 years, many amphibian species have suffered population declines throughout the world. Mass mortality have been frequently reported, and in several instances, infectious diseases appear to be the cause of death. The role that contaminants could play in these die-offs through immunotoxic effects has been poorly investigated. In this study, juvenile leopard frogs (Rana pipiens) were exposed for 21 d to a mixture of six pesticides (atrazine, metribuzin, aldicarb, endosulfane, lindane, and dieldrin) and subsequently challenged with a parasitic nematode, Rhabdias ranae. Exposure to the mixture at environmentally realistic concentrations significantly reduced lymphocyte proliferation. Three weeks after the end of the exposure, lymphocyte proliferation had recovered and was stimulated in frogs challenged with parasites with the exception of those previously exposed to the highest concentration. No pesticide effects on phagocytosis and splenocyte numbers were detectable at the end of the exposure period, but these two parameters were diminished 21 d after the infection challenge in frogs previously exposed to the highest levels of pesticides. In these animals, the prevalence of lung infection by R. ranae also tended to be higher. These results suggest that agricultural pesticides can alter the immune response of frogs and affect their ability to deal with parasitic infection.

Agriculture↗

[Pesticide soil pollution on the territory of the Russian Federation as a potential hazard for public health].

Pesticides belong to persistent pollutants and pose a potential danger to people's health. The conditions of storing and utilizing the wastes do not meet, in many cases, the sanitary-and-hygienic requirements. The control over residual pesticides in foodstuffs and in the environment is indicative, in an number of cases, of that they exceed the admissible content values. The methodical basis does not ensure, to the full extent, a quantitative analysis of pesticides. An evaluation of risk within the system of social-and-hygienic monitoring must comprise a potential danger of pesticides.

Environmental Pollution↗

Determination of seventeen polar/thermolabile pesticides in apples and apricots by liquid chromatography/mass spectrometry.

A simple liquid chromatography/mass spectrometry (LC/MS) approach for the determination of widely used representatives of polar/thermolabile pesticides in fruits was developed and validated. The group of pesticides comprised benzimidazoles and azoles (carbendazim, thiabendazole, imazalil, propiconazole, prochloraz, epoxiconazole, flusilazole, tebuconazole, bitertanol); N-methylcarbamates (carbaryl, carbofuran, methiocarb); and phenylureas and benzoylphenylureas (linuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron). Matrixes (apple, apricot) were extracted with acetonitrile and crude extracts were cleaned up by solid-phase extraction (SPE) using either mixed cation exchange or hydrophilic lipophilic balance cartridges. LC separation of pesticides was performed on a reversed-phase column, Discovery C18. Electrospray ionization and ion trap MS/MS detection were applied. For most pesticides, overall recoveries ranged from 75 to 122%, and repeatability (as relative standard deviation) from 5 repetitive determinations of recovery ranged from 3 to 21%. Carbofuran was the only compound for which recovery was not satisfactory due to its loss in the SPE cleanup step. Limits of detection were 0.1-3 microg/kg for benzimidazole and azole fungicides and carbamate insecticides. For urea insecticides, detection limits were slightly higher (3-10 microg/kg).

Calibration↗

[Occupational hygiene during pesticide use].

The study covered assortment and amount of pesticides varying in purpose and chemical class and applied in Saratov region in 2002 vs in 1980s and 1990s. Findings are changed assortment, occurrence of new generation pesticides, significantly lower pesticide load, and seed mordants predominant over other pesticide groups. These findings necessitate special attention to occupational hygiene for health preservation among rural agricultural workers.

Agricultural Workers' Diseases↗

DRIPS--a decision support system estimating the quantity of diffuse pesticide pollution in German river basins.

The GIS based decision support system DRIPS--Drainage Spraydrift and Runoff Input of Pesticides in Surface Waters--has been developed to estimate the predicted environmental concentration (PECsw) of pesticides in surface waters resulting from diffuse sources. PECsw can be calculated on a catchment scale by quantifying the expected mean daily inputs of pesticides via surface runoff, tile drainage and spraydrift for various types of river basins characterized by their daily discharges. DRIPS is fitted with a Graphical User Interface (GUI) to provide easy access to the model algorithms. Model parameters like dose rate, DT50, Koc and date of pesticides application, etc. can be modified by the user in order to generate customized scenarios predicting PECsw for a choice of field crops, orchards and vineyards. Results are available as grid cell maps for the territory of Germany with high temporal and spatial resolution featuring distinct PECsw values for approximately 400 catchments.

Algorithms↗

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