Inhibition of herbicide photodegradation by plant products

Pesticide reactivity toward light is rarely considered at the leaf surface after crop treatment; regardless, these degradation reactions directly impact the pesticide effectiveness. The use of sunscreen adjuvants to overcome photodegradation has presented some limitations so far. Raw hydroalcoholic plant extracts have been recently proposed to be used as photoprotecting adjuvants; on a model system they significantly decreased the photodegradation of pesticide. Here it is demonstrated that their use makes possible a dose reduction. Sulcotrione, a selective herbicide for use in maize, was tested in a growth chamber equipped with simulated solar light against a typical weed in maize. Sprayed weeds were monitored by biometrical and physiological parameters. Sulcotrione minimum dose required for a good herbicidal efficacy (ED(50), corresponding to 50% of chlorophyll content decay) was estimated to be 55 g ha(-1). In the presence of grape extract added in a 3-fold excess compared to the herbicide, the ED(50) decreased to 34 g ha(-1). The use of grape extract allows extension of sulcotrione herbicidal activity and reduction of the dose by 35% in controlled conditions. This is a promising result for the effective dose field adjustment.     

Disappearance of azoxystrobin, pyrimethanil, cyprodinil, and fludioxonil on tomatoes in a greenhouse

The disappearance of azoxystrobin, pyrimethanil, cyprodinil, and fludioxonil on tomatoes in greenhouse was studied. At the preharvest interval, except for cyprodinil, the pesticide residues were below the MRL fixed in Italy. The mechanism of disappearance studied with model systems shows that the decrease in residues was due to codistillation and photodegradation in pyrimethanil, to photodegradation in fludioxonil, and to evaporation and codistillation in cyprodinil. Azoxystrobin residues were stable during all experiments.     

Simulated sunlight-induced photodegradations of triasulfuron and cinosulfuron in aqueous solutions

To elucidate the photochemical behavior of two sulfonylureas (cinosulfuron and triasulfuron) for which the chemical formulas are relatively close, their photodegradation was studied in water. All experiments were carried out under laboratory conditions using a xenon arc lamp as the source of radiation to simulate environmental conditions. Polychromatic quantum efficiencies were calculated to determine the photochemical pesticide lifetimes at pH 7, and a comparison with hydrolysis lifetimes has been performed. The results obtained showed clearly that at pH 7, photodegradation becomes a more important pathway than chemical degradation. HPLC-DAD was used to study the kinetics for both sulfonylureas and their photoproducts, whereas HPLC-MS (ESI in positive and negative modes) was used to identify photoproducts. These results suggest that the photodegradation of these two sulfonylureas proceeds via a number of reaction pathways: (1) cleavage of the sulfonylurea bridge; (2) desulfonylation, which can proceed either by a carbon-sulfur cleavage or a nitrogen-sulfur cleavage; (3) O-demethylation of methoxy moieties present on the triazine ring; and (4) O-dealkylation of benzene derivatives. In addition, it was found that the desulfonylation represented the main step and that it was wavelength dependent.     

八氯二丙醚在土壤表面的紫外光解动力学研究

以紫外灯为光源,研究了八氯二丙醚在土壤表面的光化学降解动态以及不同因子对其光解的影响。结果表明,八氯二丙醚在土壤表面的光解动态符合化学反应一级动力学方程。八氯二丙醚在不同类型土壤中的光解速率为红壤〉潮土〉水稻土,光解半衰期分别为11.44、14.00h和20.63h。八氯二丙醚在中性土壤中光解速率最快,在偏酸或偏碱性土壤中光解半衰期均明显延长。土壤含水量增加,有利于八氯二丙醚的光解,干燥土壤（含水量为2%）中八氯二丙醚的光解半衰期是潮湿土壤的1.3~2.6倍。当土壤中八氯二丙醚添加浓度为0.2~10mg·kg-1时,其光解速率与添加浓度呈负相关关系;不同添加剂量的催化剂TiO2对八氯二丙醚的光解均表现出明显的光敏化作用,光解速率常数提高1.6~2.4倍。研究结果将为明确八氯二丙醚在土壤中的环境行为及其环境安全性评价提供科学依据。     

用P20型植保无人机减量施药防治稻纵卷叶螟

为探讨植保无人机（UAV）减量施药对水稻病虫害的防治效果,该研究采用P20型植保无人机进行水稻田间施药作业。分别在水稻分蘖末期、孕穗期开展了两种施药液量（15、22.5 L/hm2）的水稻冠层雾滴沉积试验,以及两种施药液量下480、540、600 mL/hm2 3种农药剂量（阿维·氯苯酰推荐剂量的80%、90%、100%）的防治稻纵卷叶螟减量施药田间药效试验,并与背负式电动喷雾器（Knapsack Electric Sprayer,KES）人工施药的常规防治方法进行施药效果对比。雾滴沉积试验结果表明,水稻冠层上部的雾滴分布均匀性优于水稻冠层下部;施药液量15、22.5 L/hm2的冠层上部雾滴沉积有显著差异,且施药液量22.5 L/hm2的冠层上部雾滴沉积显著优于施药液量15 L/hm2。药效试验结果表明,农药剂量越大稻纵卷叶螟防治效果越好,采用农药剂量100%的植保无人机施药防治效果最好,并优于KES人工施药;施药液量15、22.5 L/hm2的稻纵卷叶螟防治效果有显著差异,且施药液量22.5 L/hm2较15 L/hm2的防治效果更好;处理T2（施药液量15 L/hm2、农药剂量90%）、处理T4（施药液量22.5 L/hm2、农药剂量80%）与KES人工施药的防治效果没有显著差异。采用植保无人机施药防治稻纵卷叶螟,施药液量22.5 L/hm2可以获得更好的雾滴沉积和稻纵卷叶螟防治效果;施药液量22.5 L/hm2时,减少20%的农药剂量也能保证稻纵卷叶螟防治效果。该结果对水稻田间植保无人机减量施药具有实践指导意义。     

动力学因素和药箱充满程度对喷雾机液力搅拌器搅拌效果的影响

农药的喷施质量在农业生产中极为重要,评价农药喷施质量的重要指标是农药有效物质在喷施靶标上的均匀沉积分布,其前提条件是农药有效物质与载体从喷洒部件喷出前就要搅拌均匀。针对邯农－６５０型大田喷杆式喷雾机的药箱,对影响搅拌效果的动力学因素及药箱充满程度进行了研究。结果表明,当其他参数确定后,加大搅拌压强或流量,搅拌效果都明显改善,但加大流量比加大压强的效果要好;药箱中药液装得越满,越易搅拌均匀,充满程度越小,越不易搅拌均匀。     

戊唑醇在土壤中的光降解行为动力学研究

以高压汞灯为光源, 研究了戊唑醇在土壤中的光化学降解行为及各种因素对光降解的影响.结果表明, 戊唑醇在高压汞灯下的光降解符合化学反应一级动力学方程.戊唑醇在不同类型土壤中的光解速度为砂姜黑土>河潮土>红壤>棕壤>紫泥土, 这与土壤有机质和黏粒含量有关;随土壤含水量增加, 戊唑醇的光解速率加快, 主要是因为水分增加了农药分子在土壤中的移动性;中性环境较酸或碱性环境更有利于戊唑醇的光解;当土壤中戊唑醇的浓度为20～100 mg·kg-1时, 其光解速率与浓度呈负相关关系;表面活性剂十二烷基苯磺酸钠和十六烷基三甲基溴化铵对戊唑醇的降解均具有光猝灭作用;不同添加剂量的尿素对戊唑醇的光解几乎均表现出光猝灭作用, 氯化钾则表现为敏化作用.高压汞灯下, 戊唑醇在土壤中降解半衰期为10～22 min.     

New insights into the photoreactivity of the organophosphorus pesticide fenthion: a sigma aryl cation as a key intermediate in the photodecomposition

The primary photodegradation processes of fenthion (FN), one of the most photosensitive pesticides used in agriculture, have been investigated by combining laser flash photolysis and steady-state measurements. The triplet state of FN is produced quite efficiently (Phi(isc) approximately 0.3). However, this excited state does not seem to trigger the primary photodecomposition pathways of the pesticide. It is demonstrated that FN undergoes photoheterolysis via the excited singlet state and gives the corresponding singlet "sigma aryl cation". Chemical evidence for the generation of this transient species is given by trapping with typical "sigma nucleophiles" such as chloride and methanol. This photodegradation mechanism is, in part, quite different with respect to what is known to date and may account for the formation of the O,O-dimethyl S-[3-methyl-4-(methylthio)phenyl] phosphorothioate discovered as a novel photodegradation product of FN.     

Residues and half-life times of pyrethrins on peaches after field treatments

The behavior of pyrethrins and piperonyl butoxide (PB) on peaches has been studied after field treatment. Three experiments were carried out at 1, 5, and 10x the concentration recommended by the manufacturer. In all experiments, the initial deposition was below the maximum residue level (MRL), and the half-life time calculated in the 10x experiment for total pyrethrins within 2.3 days was in agreement with the preharvest interval (PHI) recommended. In a model system, the photodegradation rates of the pyrethrins in three commercial products were compared with pyrethrum pale (PP), with and without the presence of peach waxes. The pyrethrins in formulations containing PB showed higher half-life times but were not influenced by the presence of waxes, whereas in the case of PP that does not contain any PB, photodegradation was significantly affected by the presence of waxes.     

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.     

表层土壤中菲的紫外光降解研究

多环芳烃化合物（PAHs）由于致癌、致畸和致突变而受到广泛关注。本实验以多环芳烃菲（Phe）为目标污染物,研究了温度、腐植酸和紫外辐射强度对Phe光降解的影响并对不同因素对降解动力学的影响作了研究。结果表明,Phe的降解在20 ℃到30 ℃范围内,随着温度的升高,光降解率增加;腐植酸在Phe污染土壤的光降解中起敏化作用,可显著促进光解,腐植酸浓度为5 mg·kg^-1足以达到敏化的效果;Phe光降解速率常数随辐射强度的降低而降低,呈正相关,光解的半衰期随着辐射强度的降低而增加,呈负相关。     

Effect of the epicuticular waxes of fruits and vegetables on the photodegradation of rotenone

The effect of epicuticular waxes extracted from fruits (apple, nectarine, pear, and plum) and vegetables (tomato and eggplant) on the photodegradation of rotenone was studied. The waxes affected the decay rate and the degradation pathway of this botanical insecticide. Tomato, nectarine, and plum waxes decreased the photodegradation rate compared to controls, whereas apple and pear waxes increased it. Rotenone irradiated under sunlight without waxes gave seven photoproducts; in contrast, in the presence of waxes it changed its behavior, leading to different pathways according to the wax employed. The main photoproduct formed was 12abeta-rotenolone.     

无人植保机施药雾滴空间质量平衡测试方法

为了研究精准作业参数(速度、高度)下的无人植保机施药雾滴空间分布和下旋气流场特性,该文提出了一种无人机施药雾滴空间质量平衡测试试验方法,并且使用该方法对3种无人机进行了田间实际试验研究,结果表明:该方法可以有效获得准确飞行速度和高度下无人机施药雾滴空间分布情况和下旋气流场分布情况,在平均风速1.7 m/s、平均气温31.5℃、平均相对湿度34.1%的条件下,飞行高度2.5 m、速度5.0 m/s时,3WQF80-10型无人机喷雾作业雾滴在上风向部、顶部、下风向部和底部的平均分布比例为4.4%,2.3%,50.4%和43.7%;CG-Q60S型无人机雾滴在4个方向上平均分布比例为2.5%,1.5%,43.2%和52.8%;LXD8-3WD10型无人机雾滴在4个方向上平均分布比例为1.9%,2.0%,21.9%和74.7%。雾滴空间质量平衡分布规律符合下旋气流场分布规律,无人机下旋气流风场的测量是分析雾滴在空间不同部位分布的重要手段。研究结果可为低空低量无人植保机施药技术研究和建立无人植保机低空低量施药田间雾滴沉积与飘失测试标准提供参考。     

Rotenone residues on olives and in olive oil

The disappearance of rotenone on olives under field conditions was studied. The field data showed that rotenone residues on olives decreased with a half-life (t(1/2)) of 4.0 days. After pre-harvest time (10 days) the residues were higher than the maximum residue level fixed in Italy (0.04 mg/kg). Experiments with model systems showed that the mechanism of disappearance of rotenone is not related to evaporation, thermodegradation, or co-distillation, but only to photodegradation. When the olives were processed for oil, the residues in the oil were higher than the residues on the olives by a factor of 2.4-4.8.     

阿维菌素3种剂型的光解研究

以太阳光为光源,利用玻片药膜法和高效液相色谱法研究浓度、水质硬度、pH和共存离子等因子对阿维菌素乳油、水乳剂和微乳剂3种液体剂型光解的影响。结果表明：3种阿维菌素液体剂型光解率随光照时间延长而逐渐增大。在试验初始浓度范围内,3种阿维菌素制剂光解均符合一级动力学方程,且与药液浓度呈负相关。在不同浓度、pH、共存离子条件下,阿维菌素的光解速率均表现为乳油〉水乳剂〉微乳剂,pH对单一剂型光解有较大影响,而共存离子对其影响作用较小。在不同浓度硬水条件下则表现为随水质硬度增加,微乳剂半衰期减少,水乳剂和乳油略微增大,在蒸馏水下的半衰期为微乳剂〉水乳剂〉乳油,而在684mg·L-1硬水时半衰期为水乳剂〉微乳剂≈乳油。相比于乳油,微乳剂和水乳剂光解速率较慢,可以有效延长阿维菌素持效期,进一步提高阿维菌素在田间的应用效果。     

Pesticide Leaching from Agricultural Fields with Ridges and Furrows

In the evaluation of the risk of pesticide leaching to groundwater, the soil surface is usually assumed to be level, although important crops like potato are grown on ridges. A fraction of the water from rainfall and sprinkler irrigation may flow along the soil surface from the ridges to the furrows, thus bringing about an extra load of water and pesticide on the furrow soil. A survey of the literature reveals that surface-runoff from ridges to furrows is a well-known phenomenon but that hardly any data are available on the quantities of water and pesticide involved. On the basis of a field experiment with additional sprinkler irrigation, computer simulations were carried out with the Pesticide Emission Assessment at Regional and Local scales model for separate ridge and furrow systems in a humic sandy potato field. Breakthrough curves of bromide ion (as a tracer for water flow) and carbofuran (as example pesticide) were calculated for 1-m depth in the field. Bromide ion leached comparatively fast from the furrow system, while leaching from the ridge system was slower showing a maximum concentration of about half of that for the furrow system. Carbofuran breakthrough from the furrow system began about a month after application and increased steadily to substantial concentrations. Because the transport time of carbofuran in the ridge soil was much longer, no breakthrough occurred in the growing season. The maximum concentration of carbofuran leaching from the ridge-furrow field was computed to be a factor of six times as high as that computed for the corresponding level field. The study shows that the risk of leaching of pesticides via the furrow soil can be substantially higher than that via the corresponding level field soil.     

农药残留的表面增强拉曼光谱快速检测技术研究现状与展望

果蔬农药残留危害人类健康,施药后,农药分布于其表皮和内部组织,果蔬表面农药绝对残留量低、不均匀,直接光谱检测表征难,而表面增强拉曼散射(surface-enhanced Raman scattering,SERS)技术具有分子级检测精度,可以有效扩增信号,在实现微量物质检测方面优势明显。为此,论文综述了国内外表面增强拉曼散射技术的研究现状,特别是详细介绍了通过设计合理的表面增强拉曼基底结构,实现农药残留信号增强的主要技术手段和表面增强拉曼光谱信号分析方法。在此基础上,指出农药残留的表面增强拉曼检测技术研究中的前沿热点问题,探讨并展望了表面增强拉曼技术在农药残留快速检测方面的发展趋势。基于表面增强拉曼的农药高灵敏度、快速检测表征技术,将在农药违禁使用和农药残留超标监管中有广阔应用前景。     

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.     

Factors Affecting the Fate of Ciprofloxacin in Aquatic Field Systems

Ciprofloxacin (cipro) is a broad-spectrum antibiotic used in human and veterinary medicine that is readily transported into the environment via domestic wastewaters and through direct runoff. Although factors governing cipro fate are becoming understood, an integrated evaluation of disappearance mechanisms in aquatic systems has not been performed. Here we examined cipro disappearance rate in surface waters using both laboratory and field systems under different light, and dissolved (DOC) and particulate organic carbon (POC) conditions to determine when photodegradation versus adsorption dominates cipro fate. Initial laboratory experiments showed that cipro rapidly photodegraded (t _1/2 ～ 1.5 h) with numerous photodegradation products being noted when POC levels were low. However, even moderate water column POC levels resulted in reduced photodegradation (no breakdown products detected) and soluble cipro disappearance rates were accelerated. ¹⁴C-ciprofloxacin studies confirmed significant adsorption onto aquatic POC (K _OC values of 13,900 to 20,500 L/kg at neutral pH). In contrast, a follow-up mesocosm-scale field study using low POC water showed that photodegradation could also dominate cipro fate. In conclusion, both adsorption and photodegradation strongly influence cipro fate in aquatic systems, although the dominant mechanism appears to depend upon the ambient POC level.     

Metolachlor photodegradation study in aqueous media under natural and simulated solar irradiation

To elucidate the photochemical behavior of pesticide metolachlor, degradation was carried out in aqueous media of different compositions such as sea, river, lake, and distilled water under natural and simulated solar irradiation. In addition, the effect of important constituents of natural water such as dissolved organic matter (DOM, isolated from Pamvotis Lake) and nitrate ions was also examined. It was found that photodegradation proceeds via a pseudo-first-order reaction in all cases. The presence of DOM inhibits the photolysis reaction with half-lives ranging from 87 to 693 h whereas the degradation rate was accelerated up to 11 times in the presence of NO(3)(-). In addition, the toxicity of the degradation products formed (generally through hydroxylation, dealkylation, and cyclization reactions) was also performed using the marine luminescent bacterium Vibrio fisheri. Our results indicated a toxicity increase of the irradiated solution showing that photoproducts of higher acute toxic effects were formed.