Analysis of pesticides in nuts by online reversed-phase liquid chromatography-gas chromatography using the through-oven transfer adsorption/desorption interface

A new method to determine pesticide residues in nuts is presented, in which the pesticides are extracted from samples with a small amount of ethyl acetate and anhydrous sodium sulfate. No additional cleanup or concentration steps are necessary. The extract is directly injected into the high-pressure liquid chromatograph, where preseparation of the pesticide residues from other components coextracted from the nuts is carried out using methanol/water as the eluent. The selected liquid chromatography fraction containing the pesticides is automatically transferred to the gas chromatograph using the through-oven transfer adsorption/desorption interface. The calculated limits of detection for each pesticide varied from 0.1 to 61.3 microg/kg. The repeatabilities of the analysis and the overall procedure (extraction and analysis) were satisfactory. No variations in the retention time were observed. The method was applied to the analysis of pistachio nut, peanut, walnut, hazelnut, and sunflower seed.     

化学农药施用技术与粮食安全

化学农药在保证粮食供应方面发挥了重要作用,这是粮食安全的传统意义。但是农药大量投入导致农产品中农药残留超标,影响了粮食安全的另一个方面。化学农药对农产品的负面影响与农药的施用方法有密切的关系。发达国家在改善环境质量、提高农产品品质的同时,建立了完善的农药使用和管理法规,并通过农药施用技术改造,大大提高了农药的利用率,从而基本解决了农药环境污染和农产品农药残留超标的问题。我国在农药施用过程中,由于长期忽视施用质量的提高,加之缺乏相应的管理措施,农药对病虫草害的防治效果一直是以农药的大量投入来保证的,对农产品质量造成了很大的影响。要解决农药的使用问题,首先须通过行政管理和立法限制单位土地面积上农药的施用量,其次建立农户农药购买登记制度,保证农户实际所用农药不会超过允许使用量,最后加强农药施用者的培训,培训合格后发给操作证,持证施用农药。确保这3个环节的落实,可激发农户农药施用技术的改进,使有限投入的农药发挥最大的效用,减少农药用量,缓解农药与环境及农产品质量之间的矛盾     

Dynamics of pesticides in potato crops

This study investigated the behavior of pesticides commonly used on potato in a part of northwestern Spain with a large area devoted to this crop. Experimental potato plots were treated with commercial formulations of two insecticides, a nematicide, a herbicide, and a combination of two fungicides, and the concentrations of the active ingredients were monitored throughout the growing season in the 0-1 and 1-15 cm soil layers, in water dripping off the potato plants, and in the potatoes themselves. The technique used for pesticide determination was gas chromatography with mass selective detection. For potato analyses, pesticide extraction was optimized. The only pesticide ever detected in potato tubers was metalaxyl, the concentration of which never exceeded half the maximum residual limit even when it was applied several times more often than is officially recommended for potato crops. Metalaxyl was also the only pesticide detected in wash-off, apparently due to its being more soluble in water than the other pesticides applied to the growing plants. A mathematical model of pesticide transport in soil was fitted to the experimental data using the program HYDRUS-1D.     

Emission of Pesticides into the Air

During and after the application of a pesticide in agriculture, a substantial fraction of the dosage may enter the atmosphere and be transported over varying distances downwind of the target. The rate and extent of the emission during application, predominantly as spray particle drift, depends primarily on the application method (equipment and technique), the formulation and environmental conditions, whereas the emission after application depends primarily on the properties of the pesticide, soils, crops and environmental conditions. The fraction of the dosage that misses the target area may be high in some cases and more experimental data on this loss term are needed for various application types and weather conditions. Such data are necessary to test spray drift models, and for further model development and verification as well. Following application, the emission of soil fumigants and soil incorporated pesticides into the air can be measured and computed with reasonable accuracy, but further model development is needed to improve the reliability of the model predictions. For soil surface applied pesticides reliable measurement methods are available, but there is not yet a reliable model. Further model development is required which must be verified by field experiments. Few data are available on pesticide volatilization from plants and more field experiments are also needed to study the fate processes on the plants. Once this information is available, a model needs to be developed to predict the volatilization of pesticides from plants, which, again, should be verified with field measurements. For regional emission estimates, a link between data on the temporal and spatial pesticide use and a geographical information system for crops and soils with their characteristics is needed.

     

Lysimeter experiment to investigate the potential influence of diffusion-limited sorption on pesticide availability for leaching

Pesticide leaching from soil has been shown to decrease with increasing time from application to irrigation. It is hypothesized that the availability of compounds for leaching decreases due to diffusion and sorption inside soil aggregates. Previous work showed that pesticide sorption inside soil aggregates increases significantly during the first days after application. The study presented here tested if diffusion into aggregates could explain the leaching of four aged pesticides from manually irrigated soil cores. Azoxystrobin, chlorotoluron, cyanazine, and bentazone were applied to 30 undisturbed cores (25 cm long, 23.7 cm diameter) from a clay loam soil. The soil cores were irrigated 1, 3, 7, 14, and 28 days after application. Leachate was collected and analyzed. The amount of pesticide found in leachate decreased rapidly with time from application. Pesticide losses in leachate declined 2.5-27 times faster than total residues in soil. The decline was 4-5 times faster for the more strongly sorbed pesticides (azoxystrobin, chlorotoluron, and cyanazine) than for bentazone. In previous work, we derived a model to describe sorption and diffusion of the pesticides in small aggregates from the same soil. The diffusion model was used here to describe sorption inside the large aggregates in the soil cores and extended to describe pesticide leaching by interaggregate flow. The model showed a significant decline in leaching with time from application, which supports the theory that diffusion-limited sorption in aggregates influences the availability for pesticide leaching, although it does not exclude alternative explanations for this decline. The model well described the decline in leaching for three out of four pesticides. The interaggregate transport model could, however, not account for the amount of preferential flow in the cores and underestimated the leaching of bentazone.     

Signaling by glutamate dehydrogenase in response to pesticide treatment and nitrogen fertilization of peanut (Arachis hypogaea L.).

The responses of glutamate dehydrogenase (GDH) to NH(4)(+) and herbicides offer a new approach for probing the effects of NH(4)(+)-pesticide interactions at the whole-plant level. Although pesticides and fertilizers have greatly enhanced food production, their combined biochemical effects are not known in detail. Peanut plants were treated with different rates of Basagran (3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide), Bravo 720 (tetrachloroiso-phthalonitrile), and Sevin XLR Plus (1-naphthyl N-methylcarbamate), with and without 25 mM NH(4)Cl fertilization. Isoelectric focusing, followed by native 7.5% polyacrylamide gel electrophoresis (PAGE) fractionated the peanut seed GDH fully to its isoenzyme population patterns. The pesticide treatments induced positive skewing of the GDH isoenzymes, but NH(4)Cl-pesticide cotreatments induced a negatively skewed distribution. Basagran, Sevin, and Bravo increased the amination activities of GDH from 30.0 +/- 2.8 units in the control assay to 479.0 +/- 20.7, 63.0 +/- 5.8, and 35.2 +/- 2.2 units, respectively, therefore indicating a direct GDH-pesticide interaction. Neither the NH(4)(+) nor the pesticides increased the peanut seed protein yields above the threshold of 3.8 +/- 0.7 g per pot. But in the GDH combination of the signals from a pesticide and NH(4)(+), at least 70% of the pesticide signal was overridden by NH(4)(+) with concomitant increases in peanut seed protein yields to 7.0 +/- 1.8 g per pot. Basagran, Sevin, and Bravo possess different pesticidal properties, but their effects on GDH activity were related in the decreasing order of their nucleophilicity, viz. Basagran > Sevin > Bravo.     

Wet deposition of current use pesticides at a rural location on the Delmarva Peninsula: impact of rainfall patterns and agricultural activity

Event-based precipitation samples were collected during the main agricultural season (April-September) over 4 years (2000-2003) at one site in the Choptank River Watershed on the Delmarva Peninsula. The samples were analyzed for 19 agricultural pesticides to determine the contribution of wet deposition as a source of these compounds to the Chesapeake Bay and the factors affecting the temporal trends in deposition. Chlorothalonil was detected most frequently (92% samples) followed by metolachlor (66%) and endosulfans (49%). Although chlorothalonil is the single biggest contributor to pesticide flux (33-46%), pesticide wet deposition is dominated by herbicides (46-61%), with the greatest fluxes occurring during the time of herbicide application on corn and soybeans. The analysis suggests that the extent of wet deposition of herbicides depends on the timing of precipitation relative to herbicide application. The insecticide and fungicide flux was greater in years with above-average rainfall (2001 and 2003), suggesting that for these pesticides deposition flux is dependent on the total amount of rainfall in the agricultural season. The data indicate that the use of chlorpyrifos, an organophosphate insecticide which is on the Toxics of Concern list for the Bay, is on the increase. Total pesticide flux ranged from 90 microg/m2 (2001) to 180 microg/m2 (2000). Wet deposition can account for up to 10-20% of the annual loadings of pesticides to the Bay.     

An evaluation of methods for measurement of pesticides in sorption experiments

Abstract

The concentration of four pesticides (2,4‐D, atrazine, phorate, and terbufos) in soil solution during sorption experiments was measured using UV spectrophotometry, Gas Liquid Chromatography (GLC), High Performance Liquid Chromatography (HPLC), and radiotracer technique. The presence of water soluble organic matter in soil solution interfered with the measurement of pesticide using the UV spectrophotometry. The use of GLC, HPLC, and radiotracer technique involving ¹⁴C gave a good estimate of the concentration of pesticide in soil solution. The pesticide remaining in soil can be quantitatively analyzed by extracting with a scintillation solution containing an organic solvent such as toluene or dioxane. Among the various centrifuge tubes glass tubes with Teflon caps sorbed negligible amount of pesticides and these tubes can be used for the sorption measurements.     

Sorption and aging of corn and soybean pesticides in tropical soils of Brazil

The efficacy and fate of pesticides in soil strongly depend on sorption reversibility that is known to decrease with increasing contact time (aging). We elucidated the aging dynamics of eight different pesticides in two contrasting agricultural soils of tropical Brazil (Ustox and Psamments), using batch equilibrium experiments and sequential extractions of field samples. Adsorption was best described by Langmuir isotherms for the entire and by Freundlich equations for the lower concentration range. In field samples, water extractable pesticide fractions mostly dissipated at least twice as fast as did the solvent extractable fractions. Hence, in comparison to 0 days K(OC) values, measured field K(OC) values were higher by a factor of 2.6-38 for the clayey Ustox and 2.1-72 for the sandy Psamments toward the end of the experimental period at 80 days after application. The extent of such aging basically increased with increasing polarity of the pesticide. An absolute enrichment of polar pesticides within the final exhaustive acetone--ethyl acetate--water extracts was observed during the experimental period, so that we may deduce that pesticides had redistributed into stronger sorption sites. The time course of the K(OC) development was well-described using a semiempirical equation, which had been employed for temperate soils before.     

Comparative study of methods for the extraction of eleven organophosphorus pesticide residues in rice.

Several extraction methods are compared for the simultaneous analysis of organophosphorus pesticides in unpolished rice. Four stationary phases were used for the subsequent gas-liquid chromatographic (GLC) determination of the selected pesticides. Using 3 different GLC columns, 11 pesticides were completely separated and identified. The efficiency of the cleanup and the sensitivity of the analytical method were evaluated by using powdered unpolished rice samples fortified with the pesticides and also wheat and dried bean samples. Average recoveries ranged from 74.7% for disulfoton to 97.4% for malathion in unpolished rice and from 68.1% for disulfoton to 108.3% for malathion in other crops. The method described is applicable to the analysis of selected organophosphorus pesticide residues in unpolished rice, wheat, buckwheat, and dried beans.     

Determination of organochlorine and organophosphorus pesticide residues in eggs using a solid phase extraction cleanup

A multiresidue solid phase extraction (SPE) method for the isolation and subsequent gas chromatographic determination of nonpolar organochlorine and polar organophosphorus pesticide residues in eggs is described. The method uses an acetonitrile extraction followed by an SPE cleanup using graphitized carbon black and aminopropyl SPE columns. Organophosphorus pesticides are determined by gas chromatography with flame photometric detection. After further cleanup of the extract using Florisil SPE columns, organochlorine pesticides are determined by gas chromatography with electron capture detection. Studies were performed using eggs containing both fortified and incurred pesticide residues. The average recoveries were 86-108% for 8 fortified organochlorine pesticide residues and 61-149% for 28 fortified organophosphorus pesticide residues.     

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.     

提高防治棉花害虫效果的施药新技术方案

针对棉花不同生育期和害虫的发生及危害特点，提出了棉花全程动态施药的策略和技术方案，从而提高了农药的有效利用率和防治效果。经由手动喷雾器和机动喷雾机为核心组成的两套技术方案实验测定，表明其在防治棉花害虫，特别是防治棉铃虫方面，有较好的效果。     

Subcritical water extraction to evaluate desorption behavior of organic pesticides in soil

We evaluated the feasibility of extracting organic pesticides in soil using a hot-water percolation apparatus at 105 degrees C and 120 kPa pressure. Efficiency of the method was assessed by extracting six selected pesticides (acetochlor, atrazine, diazinon, carbendazim, imidacloprid, and isoproturon) from previously equilibrated soil at 13.6-65.8 mg/kg concentration range. Studies were performed on brown forest soil with clay alluviation (Luvisol). The method developed was compared to the traditional batch equilibrium method in terms of desorbed amount of pesticides from soil and extraction time. Pesticides in the liquid phase from the batch sorption experiment and in the effluent from the hot-water percolation were quantified by high-performance liquid chromatography with UV detection. The results of the percolation experiment are in close correlation with those of the conventional soil testing method. Desorbed quantities by hot-water percolation were 85% acetochlor, 62% atrazine, 65% carbendazim, 44% diazinon, 95% imidacloprid, and 84% isoproturon, whereas using batch equilibrium method 101, 66, 64, 37, 81, and 90% were desorbed, expressed as the percentage of the adsorbed amount of pesticide on soil following equilibration. The average time for hot-water extraction was 3.45 min, in contrast to the 16 h time consumption of the traditional batch method. The effect of temperature on stability of selected compounds was also evaluated using pesticide-spiked sand without soil. Recoveries of analytes ranged between 84.6 and 91.1% with reproducibility of 7.9-10.2%, except for diazinon, for which recovery was 59.4% with 14.4% relative standard deviation since decomposition occurred at elevated temperature. The percolation process has been described by a first-order kinetic equation. The parameters calculated from the equation provide an opportunity to estimate the amount of compound available for desorption, the rate of desorption processes in the studied soil-pesticide-water system, and modeling the leaching process to obtain additional information on the environmental behavior of the examined pesticide.     

Effect of cellulose and glucose on the proliferation of PCP (pentachlorophenol)-degrading microorganisms in soil suspension

The pesticide pentachlorophenol (PCP) of which application to rice fields was prohibited in Japan after the 1970s is still used as a fungicide for upland crops or timber. In many cases the pesticide dropped into soil is microbially degraded, and microbial degradation of PCP in soil was studied by many authors (Watanabe and Hayashi 1972; Kuwatsuka and Igarashi 1975; Watanabe 1977). The PCP-degrading microorganisms so far isolated are common ones which are not nutritionally fastidious (Watanabe 1973; Suzuki 1983a, b). It is, therefore, plausible that PCP-degradability of the microorganisms is influenced by the presence of some nutrients because, in general, the microorganisms may preferentially use nutrients to pesticides which are biostatic or biocidal to the microorganisms.     

Reduction of pesticide residues on produce by rinsing

In 1997 this laboratory initiated a research program with the objective of examining the effect that rinsing of produce with tap water would have on pesticide residues. Samples were obtained from local markets and/or grown at our experimental farm. Because approximately 35% of produce from retail sources contains pesticide residues, growing and treating produce at an experimental farm had the advantage that all such samples contain pesticide residues. Pesticides were applied under normal field conditions to a variety of food crops and the vegetation was allowed to undergo natural weathering prior to harvest. The resulting samples contained field-incurred or "field-fortified" residues. This experimental design was employed to mimic as closely as possible real world samples. Crops were treated, harvested, and divided into equal subsamples. One subsample was processed unwashed, whereas the other was rinsed under tap water. The extraction and analysis method used was a multi-residue method developed in our laboratory. Twelve pesticides were included in this study: the fungicides captan, chlorothalonil, iprodione, and vinclozolin; and the insecticides endosulfan, permethrin, methoxychlor, malathion, diazinon, chlorpyrifos, bifenthrin, and DDE (a soil metabolite of DDT). Statistical analysis of the data using the Wilcoxon signed-rank test showed that rinsing removed residues for nine of the twelve pesticides studied. Residues of vinclozolin, bifenthrin, and chlorpyrifos were not reduced. The rinsability of a pesticide is not correlated with its water solubility.     

Determinants of high pesticide exposure events in the agricultural health cohort study from enrollment (1993-1997) through phase II (1999-2003)

We conducted an analysis of the determinants of high pesticide exposure events (HPEEs), which are defined as self-reported incidents of high exposure to pesticides, fertilizers, or other chemicals in the Agricultural Health Study, a cohort of private applicators and their spouses residing in North Carolina or Iowa, and commercial applicators residing in Iowa. We examined the risk of HPEEs occurring between enrollment (phase 1: 1993-1997) and follow-up (phase II: 1999-2003) among participants who completed the phase II questionnaire (n=43,149) by calculating hazard rate ratios and 95% confidence intervals using Cox proportional-hazard regression. During the followup period, 1,582 HPEEs were reported (3.8%). HPEE risk was significantly higher among Iowa residents, younger participants, those with a hearing deficit, a risk-taking personality, and an HPEE prior to enrollment. Among private applicators (n=30,102), larger farm size, higher frequency and duration of pesticide use, spraying pesticides with open cab windows, using a tractor cab without a charcoal filter, repairing spray equipment, wearing work clothing more than two days without changing, not removing work boots before entering the home, and storing pesticides in the home were associated with significantly higher HPEE risk. Among commercial applicators (n=2326), higher frequency of pesticide use was associated with a significantly higher HPEE risk. Among spouses (n=10,721), higher frequency of pesticide use, using an application vehicle with a cab, and storing pesticides in the home were associated with a significantly higher HPEE risk. Our findings indicate that HPEEs were associated with several modifiable pesticide handling procedures that can be targeted in safety training and education.     

Organochlorine pesticide residues in leek (Allium porrum) crops grown on untreated soils from an agricultural environment

Leek (Allium porrum) plants from organic farming were harvested at 15, 59, and 210 days after seed germination. Organochlorine pesticide (OCP) levels were quantified by GC-ECD in vegetative tissues (roots and aerial), bulk soil and rhizosphere. Leek plant bioaccumulate OCPs efficiently in their aerial and root tissues and alter the concentration of the soil where they are grown. OCPs distribution pattern of bulk soil was endosulfans > DDTs > dieldrin, while it was endosulfans > HCHs > DDTs in leek tissues. There were statistically significant declines in DDTs, chlordane, dieldrin, and heptachlor in the rhizosphere, indicating that recalcitrant residues of OCPs may be removed from contaminated soil using leek crops under normal growing conditions. The DDE/DDT and alpha-/gamma-HCH ratios of < 1 would indicate recent inputs of DDT and lindane in the environment. The occurrence of OCPs in this farm could be the result of atmospheric deposition and/or surface runoff of these pesticides.     

Characterization of nicosulfuron availability in aged soils

Sorption-desorption interactions of pesticides with soil determine their availability for transport, plant uptake, and microbial degradation. These interactions are affected by the physical-chemical properties of the pesticide and soil, and for some pesticides, their residence time in the soil. This research evaluated changes in sorption/availability of nicosulfuron (2-[[[[(4,6-dimethoxy-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamide) herbicide with aging in different soils, using a radiolabeled ((14)C) tracer. Aging significantly increased sorption. For instance, after the 41-day incubation, calculated K d,app increased by a factor of 2 to 3 in Mollisols from the Midwestern United States and by a factor of 5 to 9 in Oxisols from Brazil and Hawaii, as compared to freshly treated soils. In view of this outcome, potential transport of nicosulfuron would be overpredicted if freshly treated soil K d values were used to predict transport. The fact that the nicosulfuron solution concentration decreased faster than the soil concentration with time suggested that the increase in sorption was because the rate of degradation in solution and on labile sites was faster than the rate of desorption of the neutral species from the soil particles. It may have also been due to nicosulfuron anion diffusion to less accessible sites with time, leaving the more strongly bound neutral molecules for the sorption characterization. Regardless of the mechanism, these results are further evidence that increases in sorption during pesticide aging should be taken into account during the characterization of the sorption process for mathematical models of pesticide degradation and transport.