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Neutralization of 4,6-dinitro-o-cresol waste pesticide by means of detonative combustion.

Neutralization of 4,6-dinitro-o-cresol, of which the best-before date had expired and which could not be used any longer, was carried out by means of the detonative combustion method. The pesticide comprises two nitro groups and is called DNOC. Composition of the applied explosive was designed on the basis of porous ammonium nitrate as an oxidizer and the pesticide as fuel. The thermodynamic parameters of such an explosive were estimated, and then three series of experiments with detonative decomposition of the material under a shield of sand were performed: in a steel chamber, in shot-holes in soil, and in shot-holes in a quarry. The efficiency of the pesticide decomposition was examined by determination of the residual remainder of the pesticide in the environment by means of gas chromatography. It was stated that pesticide content in the analyzed samples was below the determination threshold of the applied method. Biological tests with plants were carried out as well. Suggestion was made that the energy being produced during detonative combustion can be utilized for useful work, e.g. rock mining in a quarry.

Cresols↗

Atmospheric organochlorine pesticide concentrations near the Great Lakes: temporal and spatial trends.

As a part of the Integrated Atmospheric Deposition Network, atmospheric organochlorine pesticide concentrations were measured in both the gas and particle phases at seven sites near the Great Lakes. Much higher organochlorine pesticide concentrations were found in the gas phase compared to that in the particle phase. Long-term decreasing trends were observed for most pesticides in both phases. Two different seasonal trends were observed in the particle phase: (a) in-use pesticides, such as endosulfan, showed higher concentrations in the summer, a time corresponding to their agriculture use, and (b) restricted organochlorine pesticides, such as lindane, showed higher particle-phase concentrations in the winter, presumably due to their enhanced partitioning from the gas phase to particles. Generally, Chicago had the highest concentrations of chlordanes, dieldrin, and sigmaDDT, suggesting that urban areas could be sources of these compounds to atmosphere. Point Petre had the highest concentrations of endosulfan, likely due to its agricultural application in Southern Ontario.

Air Pollutants↗

Solid phase extraction gas chromatography/electron capture detector method for the determination of organochlorine pesticides in wildlife whole blood.

A gas chromatographic method for the analysis of 10 organochlorine pesticides in 0.5 mL of whole blood is described. Sample preparation involved an ethyl ether and hexane extraction, followed by a silica solid phase extraction cleanup. The pesticides are quantified by gas chromatography/electron capture detection. Method limits of detection ranged from 1.1 to 5.2 microg/L. The mean and standard deviation for the recovery of 10 pesticides was 97.9 +/- 5.5%. Recoveries from whole blood were comparable to recoveries from plasma. This indicates that the preparation of plasma is unnecessary for the quantification of organochlorine pesticides in blood. This approach is particularly useful as a nonlethal approach for monitoring pesticide contamination in small animals for which the volume of blood is limiting.

Animals↗

Analysis of organophosphorus pesticides in honeybee by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry.

Pesticides applied in extended agricultural fields may be controlled by means of bioindicators, such as honeybees, in which are the pesticides bioaccumulate. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) experiments with positive (PI) and negative (NI) ion modes were optimized for the analysis of 22 organophosphorus pesticides in honeybee samples. The extraction required 3 g of sample, which was extracted with acetone. The extract was purified with coagulating solution and reextracted with Cl(2)CH(2). Pesticides studied could be detected by both ionization modes except for parathion, parathion-methyl, and bromophos, which did not give signals in PI mode, and triazophos, which was not detected in NI mode. Fragmentation voltage and vaporizer temperature were optimized to achieve the highest sensitivity. The spectra profile of each pesticide in PI mode showed the [M + H](+) ion as the main signal, whereas in NI mode only fragment ions were shown. The detection limit obtained in selected ion monitoring mode ranged from 1 to 15 microg kg(-1). The average recoveries from spiked honeybees at various concentration levels (0.5-5 mg kg(-1)) exceeded 65% with relative standard deviations of 4-15%. The method was applied to real samples, in which residues of coumaphos and dimethoate were detected.

Animals↗

Assessment of the stability of pesticides during cryogenic sample processing. 1. Apples.

An assessment of the stability of a large number (106) of pesticides and related compounds during the cryogenic sample processing of apples has been undertaken. For the first time the procedure included an assessment of the losses during the freezing of the fruits, prior to processing. The stability of each pesticide during processing was assessed by comparing the mean recovery for the laboratory-spiked samples with the mean "survival" of the pesticides in cryogenically processed samples. The results clearly demonstrate that the vast majority, 94 of 106, of pesticides were stable during cryogenic processing. Of particular importance was that losses of several pesticides [bitertanol (95%), heptenophos (50%), isofephos (40%), and tolylfluanid (48%)] reported to occur during ambient processing of apples did not occur during cryogenic processing. Losses of dichlofluanid (54%), chlozolinate (22%), and etridiazole (40%), previously reported to occur during ambient processing of apples, were reduced to barely significant levels (10, 17, and 14%, respectively) by cryogenic processing. Small apparent losses for a few of the compounds were attributable to analytical and sample handling difficulties, rather than to losses during processing, and need further investigation.

Dry Ice↗

Improved uptake models of nonionized pesticides to foliage and seed of crops.

The residual amount of nonionized pesticides incorporated to foliage and stem (foliage) and seed (fruit) of crops via root hairs from the water phase was estimated using the uptake models newly including metabolic parameters by which the amount of intact pesticide remaining in crops was considered with its proportion in a transpiration stream. A new parameter was also introduced for the seed model that accounts for the pesticide loss by adsorption to the inner surface of xylem tissue. Validation of the model was conducted using six pesticides with soybean and spinach plants. The ratio of the predicted concentration of pesticide to the measured one was 0.44-1.49 and 0.57-2.93 with foliage and seed models, respectively, showing that these improved models would be effective as a prediction tool.

Adsorption↗

Organophosphorus pesticide residues in Mexican commercial pasteurized milk.

A study was conducted to measure residues of 13 organophosphorus (OP) pesticides, widely used as dairy cattle ectoparasiticides or in crops used for animal feed, in homogenized and pasteurized Mexican milk samples. Four different milk brands with high distribution were collected biweekly during a 12 month period (n = 96) in supermarkets. OP pesticide residues were measured by gas chromatography with a flame photometric detector. Approximately 39.6% of the samples contained detectable levels of OP pesticide residues. Eight samples contained residues exceeding established maximum residue limits (MRL), and the OP pesticides present in these samples were dichlorvos (five samples), phorate, chlorpyrifos, and chlorfenvinphos (one sample, respectively). Average residues of 13 OP pesticides measured were below established MRLs ranging between 0.0051 and 0.0203 ppm.

Animals↗

Supercritical fluid extraction of pesticides from a table-ready food composite of plant origin (gazpacho).

Supercritical fluid carbon dioxide extraction (SFE) has been evaluated for the extraction of 17 organohalogen and organophosphate pesticides in gazpacho (a table-ready food composite containing crude vegetables, white bread, vegetable oil, water, and other minor components) using anhydrous magnesium sulfate as drying agent. The effects of different parameters, such as fat content in gazpacho composites, magnesium sulfate/gazpacho ratio, supercritical fluid volume, pressure, temperature, and static modifier additions, on SFE recoveries from spiked gazpacho samples have been studied. Analyses were performed by gas chromatography (GC) with flame photometric (FPD), electron capture (ECD), and mass spectrometry (MSD) detectors. In most experiments, recoveries obtained for the nonpolar organohalogen pesticides were lower than those obtained for the most polar organophosphate pesticides, but overall pesticide recoveries determined by using the optimal SFE conditions indicate that SFE could be used to determine pesticide residue levels in gazpacho.

Chromatography, Gas↗

Comparison of accelerator mass spectrometry with gas chromatography for the determination of pesticide residues in individual items in the diets of wild birds and mammals.

Methods to refine the assessment of exposure of wild birds and mammals to pesticides required measurement of pesticide residues in very small samples of their diets. Sample sizes were in the 1-100 mg range, and the target residue for measurement was 0.01 mg/kg. Gas chromatography-mass spectrometry (GC-MS) with large volume injection was compared with the use of an accelerator mass spectrometer (AMS) to measure residues of pesticide labeled at near-background levels with carbon-14. The GC-MS method was able to detect residues down to 0.1 ng per item of diet, and the AMS detected the radiolabel down to 1 mBq (0.06 disintegration per minute, 1 ng of pesticide at the specific activity used) per sample. The target residue level was achieved by the GC-MS method for samples down to 10 mg. The GC method appeared to be best suited to monitoring residues in field studies, and the AMS shows great potential for use in laboratory experiments concerning pesticide degradation.

Animals↗

Levels of organochlorine pesticides in soils and rye plant tissues in a field study.

The organochlorine pesticides are lipophilic and persistent and tend to accumulate in soils and growing plants. The contamination of growing plants occurs by adhesion of volatile substances from the air to the plant surface and by the migration of contaminants through xylem in inner ascendant transport. Persistent organochlorine pesticides (HCB, alpha,gamma-HCH, pp'DDE, op'DDT, pp'DDT) levels were determined in soils and rye plants. The aims of the study were the monitoring of organochlorine pesticide concentrations and the comparison of these levels among soil, rye straw, and rye grains. Fifty soil samples and 50 rye plant (50 straw and 50 grains) samples were taken. The GLC-ECD chromatographic results indicated the following contamination levels distributed among soil, straw, and grains: HCB (0.7-1.2-0.7 microg.kg(-1)), alpha-HCH (0.6-3.4-1.2 microg.kg(-1)), gamma-HCH (1.8-27.3-4.4 microg.kg(-1)), Sigma-HCH (2.5-30.7-5.6 microg.kg(-1)), pp'DDE (1.0-7.8-5.5 microg.kg(-1)), op'DDT (16.1-20.4-17.0 microg.kg(-1)), pp'DDT (38.0-41.7-49.6 microg.kg(-1)), and Sigma-DDT (54.2-63.2-72.1 microg.kg(-1)). The study verified the presence of organochlorine pesticides in the Mexican agricultural environment and their migration from soil to the growing rye plants. However, DDT has been banned since 1999 for sanitary reasons, and Lindane is applied only in some cases as a seed dresser. The determined organochlorine pesticide levels in rye plants are low, at residual levels that are below Codex Alimentarius Commission maximum residue limits.

DDT↗

Use of stable tracer studies to evaluate pesticide photolysis at elevated temperatures.

New methods were developed to determine photolysis rates of medium-weight pesticides in the gas phase using elevated air temperatures and solid-phase microextraction (SPME). A 57-L glass chamber was constructed that utilized collimated xenon arc irradiation that could heat chamber air to increase the amount of pesticide in the gas phase. Gas-phase photolysis rates were determined at various air temperatures by comparing the rate of loss of each of the tested pesticides to a photochemically stable tracer, hexachlorobenzene. Interval sampling of gas-phase constituents was performed using SPME immediately followed by GC-ECD or GC-MSD analysis. The two pesticides under examination were the dinitroaniline herbicide trifluralin and the organophosphorus insecticide chlorpyrifos. The gas-phase photolysis for trifluralin was found to be rapid with half-lives of 22-24 min corrected for sunlight. These results were comparable to photochemical lifetime estimates from other investigators under sunlight conditions. Elevating temperatures from 60 to 80 degrees C did not affect photolysis rates, and these rates could be extrapolated to environmental temperatures. From 60 to 80 degrees C, gas-phase chlorpyrifos photolysis lifetimes were observed to range from 1.4 to 2.2 h corrected for sunlight and will thus be important together with hydroxyl radical reactions for removing this substance from the atmosphere. At these elevated temperatures, pesticides and tracer compounds were found to be substantially in the gas phase, and possible effects on reaction rates from wall interactions were minimized.

Chromatography, Gas↗

Pesticides and cancer.

Epidemiologic evidence on the relationship between chemical pesticides and cancer is reviewed. In animal studies, many pesticides are carcinogenic, (e.g., organochlorines, creosote, and sulfallate) while others (notably, the organochlorines DDT, chlordane, and lindane) are tumor promoters. Some contaminants in commercial pesticide formulations also may pose a carcinogenic risk. In humans, arsenic compounds and insecticides used occupationally have been classified as carcinogens by the International Agency for Research on Cancer. Human data, however, are limited by the small number of studies that evaluate individual pesticides. Epidemiologic studies, although sometimes contradictory, have linked phenoxy acid herbicides or contaminants in them with soft tissue sarcoma (STS) and malignant lymphoma; organochlorine insecticides are linked with STS, non-Hodgkin's lymphoma (NHL), leukemia, and, less consistently, with cancers of the lung and breast; organophosphorous compounds are linked with NHL and leukemia; and triazine herbicides with ovarian cancer. Few, if any, of these associations can be considered established and causal. Hence, further epidemiologic studies are needed with detailed exposure assessment for individual pesticides, taking into consideration work practices, use of protective equipment, and other measures to reduce risk.

Animals↗

Dermal exposure to pesticides in greenhouses workers: discrimination and selection of variables for the design of monitoring programs.

Dermal exposure to pesticides is one of the main sanitary problems which greenhouses workers face. With the dual aims of establishing both the body part that receives the greatest exposure and the variable that has greatest influence on this exposure level, 22 pesticide application trials were performed. Trials were carried out in different greenhouse vegetable crops, using different pesticides and different spray diameters from the spray gun. In order to determine dermal exposure, the whole body method was used. Pieces of the applicator suit were subject to an extraction procedure and their pesticide content determined using GC-NPD analysis. Multivariate analysis were applied to the data obtained. Principal component analysis showed that all trials produced a high exposure level on lower left leg and lower right leg. Cluster analysis distinguished between three sample groups. The most and the least affected parts were clearly distinguished. Discriminant analysis indicated that the thin drop size of the spray gun is responsible for both the differences between groups and the minimum or maximum exposure level measured on the applicator suit. Therefore, selecting the variables, lower legs and thin drop size, is considered fundamental in designing programs for monitoring pesticide exposure.

Administration, Cutaneous↗

Childhood cancer and paternal employment in agriculture: the role of pesticides.

Previous studies have suggested that the offspring of men potentially exposed to pesticides at work may be at increased risk of kidney cancer (Wilms' tumour), brain tumours, Ewing's bone sarcoma and acute leukaemia. This paper examines the association between potential occupational exposure of fathers to pesticides and offspring's death from cancer in a large national database. Records for 167703 childhood deaths occurring during 1959-63, 1970-78 and 1979-90 in England and Wales have been analysed. Among the offspring of men with potential occupational exposure to pesticides there were 5270 deaths, of which 449 were due to cancer. Associations were assessed using proportional mortality ratios (PMRs), with adjustment for age, year of death and paternal social class. Of the childhood cancers previously linked with potential paternal occupational exposure to pesticides, the only statistically significant excess was for kidney cancer (PMR=1.59, 95% CI=1.18-2.15, based on 42 deaths). Although these results offer some support for the suggestion that paternal occupational exposure to pesticides may be related to the subsequent development of kidney cancer in offspring, other explanations cannot be excluded. In the light of the findings presented here and elsewhere, further, more detailed, research into the nature of this relationship is warranted.

Adolescent↗

Design strategy for assessing multi-pathway exposure for children: the Minnesota Children's Pesticide Exposure Study (MNCPES).

Although children are exposed to a variety of environmental hazards, including pesticides, there is a scarcity of information available to estimate exposures realistically. This article reports on one of the first attempts to measure multi-pathway pesticide exposures in a population-based sample of urban and non-urban children. A design strategy was developed to assess multi-pathway pesticide exposures in children using personal exposure measurements in combination with complimentary measurements of biological markers of exposure, concentrations in relevant environmental media, and time spent in important microenvironments and participating in exposure-related activities. Sample collection and analysis emphasized measurement of three insecticides (i.e., chlorpyrifos, diazinon, and malathion) and one herbicide (i.e., atrazine). These compounds were selected because of their frequent use, presence in multiple environmental media, expected population exposures, and related hazard/toxicity. The study was conducted during the summer of 1997 in Minnesota and involved a stratified sample of households with children ages 3-12 years. Participants resided in either (a) the cities of Minneapolis and St. Paul (urban households), or (b) Rice and Goodhue Counties just south of the metropolitan area (non-urban households). Results from a residential inventory documenting storage and use of products containing the target pesticides were used to preferentially select households where children were likely to have higher exposures. The study successfully obtained pesticide exposure data for 102 children, including measurements of personal exposures (air, hand rinse, duplicate diet), environmental concentrations (residential indoor/outdoor air, drinking water, residential surfaces, soil), activity patterns (obtained by questionnaire, diary, videotaping), and internal dose (metabolites in urine).

Biomarkers↗

Collecting urine samples from young children using cotton gauze for pesticide studies.

To estimate pesticide exposure, urine samples are often needed to analyze pesticide metabolites. However, this is difficult for children wearing diapers because simple and feasible techniques suitable for field collection are not available. The objectives of this study were to test the validity of using cotton gauze pad as a medium for collecting urine samples from young children and to examine the stability of the recoveries for creatinine and pesticide metabolites over 24 h. Urine spiked with a pesticide and four metabolites, 2,4-dichlorophenoxyacetic acid (which is mainly eliminated from urine unchanged), 3-phenoxybenzoic acid (metabolite for synthetic pyrethroids), atrazine mercapturate (metabolite for atrazine), malathion dicarboxylic acid (metabolite for malathion), and 2-isopropyl-4-methyl-6-hydroxypyrimidine (metabolite for diazinon) was added to the gauze pads and kept in jars at 37 degrees C in a water bath. Urine was expressed from the gauze pads immediately and after 1, 2, 4, 8, and 24 h, then analyzed. The recoveries, calculated as the percentage of concentration in expressed urine divided by that of the control urine sample, were within a range of 70-130%. The metabolite and creatinine concentrations did not change with time in either expressed urine samples or controls. The results suggest that cotton gauze pad is a promising candidate for collecting urine samples from young children wearing diapers for studies in which these five urinary pesticide metabolites are to be analyzed.

Child↗

Can synthetic pesticides be replaced with biologically-based alternatives?--an industry perspective.

Agricultural chemical companies have invested in the discovery and development of biological pesticides to complement synthetic pesticides for the control of insects, diseases, and weeds on agronomic and horticultural crops. For plant disease control, companies envisage biological fungicides entering markets where they have the best chance of performing and which are most receptive to using biological control methods. Fewer regulatory requirements can mean faster registration for a biological than a synthetic pesticide. However, industry's requirements for competitive performance, effective formulations, and economic production can mean significant investments in time and money for a biological pesticide, although total investment may be less than for a synthetic pesticide. One biocontrol project in which industry has invested is baculoviruses for insect control. Insect baculoviruses, genetically modified to kill insects faster than wild-type viruses, are attractive biocontrol agents because their selectivity to insect pests and safety to beneficial insects and mammals enable them to compete with synthetic insecticides. Industry is looking for similar biocontrol opportunities in disease control. Biocontrol agents for seedling disease, root rot, and postharvest disease control have been registered by the EPA and are trying to compete with synthetic fungicides for market share. To date, effective biocontrol agents have not been identified for the control of serious foliar diseases, such as grape downy mildew, potato late blight, wheat powdery mildew, and apple scab. Farmers must rely on synthetic fungicides and agronomic methods to control these diseases for the foreseeable future.

Animals↗

Determination of organophosphorus pesticides in foods using an accelerated solvent extraction system.

Residual organophosphorus pesticides in foods were determined by accelerated solvent extraction (ASE), gel permeation chromatography and GC-FPD. Pesticides were extracted at 100 degrees C under 1500 psi pressure in less than 20 min. Wet samples were extracted after mixing with Extrelut drying agent. Four foods were spiked with 19 pesticides at 0.1 ppm or less. The average recoveries of these pesticides were 80-90% and the precision was < 10%. Both methamidophos and acephate gave 37-50% recoveries and 6-40% precision. These results suggested that ASE can be used to extract residues of organophosphorus pesticides in foods.

Food Analysis↗