The stability and degradation of a new biological pesticide,pyoluteorin

BACKGROUND: Pyoluteorin (Plt) is a polyketide metabolite produced by fluorescent Pseudomonas. It controls a wide range of pests, including bacteria, epiphytes and weeds. It could become widely used as a new biological pesticide. However, ignorance of the stability of Plt is an obstacle to its use. This work studied the stability of Plt and its degradation under different conditions, including temperature, pH and UV–visible light irradiation. RESULTS: Degradation of Plt followed first‐order reaction kinetics. The degradation rate increased with increased temperature. The derived activation energy was 11.06 J mol^?1 K^?1. Plt was relatively stable in neutral solutions, in contrast to acid and alkaline solutions. Visible irradiation had no obvious effect on Plt stability, while UV irradiation greatly decreased its half‐life to 3–4 days, in contrast to its half‐life of 25 days in the dark. CONCLUSION: Plt is relatively stable in pure water solutions and at room temperature, with a half‐life of more than 20 days. However, UV irradiation and acidic or alkaline solutions will enhance its degradation, reducing its half‐life by a factor of 0.1–0.3. Before Plt is widely used as a pesticide, it might be necessary to modify the structure of Plt to make it more stable. Copyright © 2009 Society of Chemical Industry     

Considering degradation kinetics of pesticides in plant uptake models: proof of concept for potato

BACKGROUND

Degradation kinetics of pesticides in plants are crucial for modeling mechanism-based pesticide residual concentrations. However, due to complex open-field conditions that involve multiple pesticide plant uptake and elimination processes, it is difficult to directly measure degradation kinetics of pesticides in plants. To address this limitation, we proposed a modeling approach for estimating degradation rate constants of pesticides in plants, using potato as a model crop. An operational tool was developed to backward-estimate degradation rate constants, and three pesticides were selected to perform example simulations.

RESULTS

The simulation results of thiamethoxam indicated that the growth dynamics of the potato had a significant impact on the degradation kinetic estimates when the pesticide was applied during the early growth stage, as the size of the potato determined the uptake and elimination kinetics via diffusion. Using mepiquat, we demonstrated that geographical variations in weather conditions and soil properties led to significant differences in the dissipation kinetics in both potato plants and soil, which propagated the variability of the degradation rate constant. Simulation results of chlorpyrifos differed between two reported field studies, which is due to the effect of the vertical distribution of the residue concentration in the soil, which is not considered in the majority of recent studies.

CONCLUSIONS

Our proposed approach is adaptable to plant growth dynamics, preharvest intervals, and multiple pesticide application events. In future research, it is expected that the proposed method will enable region-specific inputs to improve the estimation of the degradation kinetics of pesticides in plants. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

腈菌唑在番茄果实中的立体选择性降解

为明确田间条件下手性杀菌剂腈菌唑对映体在番茄果实中的降解规律,采用Lux Cellulose-1手性色谱柱及超高效液相色谱-串联三重四极杆质谱 (UPLC-MS/MS) 分析方法,研究了腈菌唑对映体的分离及其在番茄果实中的选择性降解。样品经乙腈提取,采用QuEChERS 方法净化。分析方法验证结果表明:在0.000 5~0.05 mg/L线性范围内,腈菌唑对映体的峰面积与其浓度间呈良好的线性关系,R2均大于0.99;在0.005、0.05和0.25 mg/kg 3个添加水平下,腈菌唑对映体在番茄中的平均回收率在92%~96%之间,相对标准偏差 (RSD) 在1.0%~3.0%之间。降解试验结果显示:腈菌唑对映体在番茄果实中的降解规律符合一级反应动力学方程,其降解半衰期在2.77~4.08 d之间;腈菌唑对映体在番茄果实中的降解具有明显选择性,随时间延长,其对映体分数 (F_E) 值由最初的0.47下降为0.24,其中S-(+)-腈菌唑优先降解,从而导致R-(–)-腈菌唑的相对富集。本研究从对映体的角度评价了腈菌唑在番茄中的降解,可为手性农药对映体的环境行为研究提供基础数据。     

微生物降解二苯醚类除草剂的研究进展

本文概述了降解二苯醚类除草剂的微生物种类、降解机理及影响微生物降解二苯醚类除草剂的因素,指出利用微生物修复土壤中二苯醚类除草剂残留是一个有效的手段; 同时指出二苯醚类除草剂微生物降解过程中起关键作用的酶及基因有待于进一步研究。     

Fenton试剂降解除草剂溴嘧草醚的反应动力学研究

探讨了Fenton试剂对超高效除草剂溴嘧草醚(ZJ0777)的降解反应。考察了溴嘧草醚、过氧化氢、硫酸亚铁的初始浓度和反应温度等因素对溴嘧草醚降解反应的影响,建立了Fenton试剂降解溴嘧草醚的动力学方程。结果表明:在溴嘧草醚初始浓度分别为0.12和0.24 mmol/L时,达到其降解率90%以上所需的时间分别为32和48 h,而在溴嘧草醚为0.48 mmol/L时,反应84 h只有87%的溴嘧草醚降解;过氧化氢初始浓度在150~300 mmol/L范围内,浓度增加有利于降解反应进行;溴嘧草醚降解反应随亚铁离子浓度的增加而加快(5~20 mmol/L),但过高的亚铁离子浓度对降解反应无效。温度在25~45℃范围内,反应的表观活化能Ea为75.34 kJ/mol。溴嘧草醚的氧化降解符合假一级反应动力学模型。     

Oxidative degradation of chlortoluron,propiconazole, and metalaxyl in suspension cultures of various crop plants

The metabolism of chlortoluron, (N′-(3-chloro-4-methylphenyl)-N,N-dimethylurea), propiconazole (1-[2-(2′,4′-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole), and metalaxyl (dl-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl) alanine methyl ester) was investigated in suspension cultures of crop species for which differences in metabolism had been demonstrated at the intact plant level. Uptake and metabolism of chlortoluron by cultures of Italian rye-grass (Lolium multiflorum) was slow, the metabolites detected (42% of applied radioactivity after 13 days) being products of ring methyl oxidation and N-monodealkylation reactions. In sharp contrast, metabolism in a cotton (Gossypium hirsutum) suspension culture was extremely fast (72% after 4 hr) and was attributed to extensive N-didealkylation in addition to rapid ring methyl oxidation. This rate of metabolism also implied a very rapid uptake of chlortoluron by the cotton culture. ¹⁴C-labelled propiconazole became rapidly associated with cells of wheat (Triticum aestivum) and rice (Oryza sativa) following treatment of suspension cultures. Uptake was initially more rapid in the rice culture (36% of applied radioactivity after 8 h compared to 19% for wheat) which, together with a slower rate of metabolism, resulted in more unchanged propiconazole being associated with rice cells. On a parts-per-million basis these results indicated an apparent 10-fold accumulation of propiconazole in rice cells compared to 5-fold in the wheat culture. Propiconazole metabolite patterns were similar in cultures of both species and indicated side-chain hydroxylation as the principal pathway. Uptake of metalaxyl was slow in suspension cultures of both lettuce and potato (≅ 20% after 17 days). Subsequent metabolism was also slow but appeared to be limited by the poor rate of uptake. Both cultures were found to be similarly versatile with respect to metabolic attack on metalaxyl, which included ring methyl hydroxylation, aryl hydroxylation, ester cleavage, ether cleavage (O-dealkylation), and N-dealkylation (side-chain cleavage), the hydroxylation reactions being quatitatively the more important. The results for all three pesticides are compared to those obtained previously from studies with intact plants of the same species.     

Stereoselective degradation of ethofumesate in turfgrass and soil

The stereoselective degradation of ethofumesate in turfgrasses and several agricultural soils was investigated to provide details of the fate of this chiral herbicide. Racemic ethofumesate was either foliar applied to two species of turfgrass or fortified into four types of agricultural soils. (+)- and (−)-Enantiomers were extracted and analyzed by a validated chiral HPLC method which involved extraction of samples with organic solvent followed by separation on cellulose-Tris-(3,5-dimethylphenylcarbamate)-based chiral column and quantification by UV absorbance at 230 nm. Mean recoveries of each enantiomer fortified at 0.5, 5, and 10 μg g⁻¹ ranged from 82.3 ± 5.84 to 92.5 ± 2.87% in turfgrasses and from 86.0 ± 5.09 to 98.1 ± 2.51% in soil. As a measure of this composition, the enantiomeric ratio (ER) was used, defined as the concentration ratio of (+)/(−)-enantiomer. Similarly, preferential degradation of the (−)-enantiomer was observed in both grass species with the largest ER of about 3 and in one of the test soil with ER = 1.65, resulting in residues enriched with (+)-enantiomer. This stereoselective degradation in this soil led to significant difference on half-lives between the two enantiomers. No stereoselective degradation was observed in other soils.     

烟嘧磺隆的微生物降解研究进展

烟嘧磺隆属磺酰脲类除草剂,因其对玉米安全,对一年生和多年生禾本科杂草及部分阔叶杂草、莎草科杂草高效而在玉米田广泛应用,但其在土壤中的残留则易对后茬敏感作物产生药害。微生物对烟嘧磺隆的降解有望成为修复污染土壤的有效措施。文章从烟嘧磺隆的使用及危害,可降解烟嘧磺隆的微生物种类及降解特性、降解途径、降解酶及其编码基因等方面进行了综述。目前有关烟嘧磺隆微生物降解的研究多集中于其降解菌的筛选、降解特性及降解途径等方面,对于其微生物降解过程中起关键作用的酶和基因方面的研究仍较少,因此未来的研究趋势将主要体现在降解复合菌系的培养、降解微生物的环境生态学、降解基因以及降解酶制剂等方面。     

微生物降解三唑类杀菌剂研究进展

三唑类杀菌剂因具有高效、低毒的特性已在中国得到广泛使用,但同时也因其残留期较长、易污染土壤而备受关注。微生物降解被认为是修复被污染土壤的有效措施。文章从降解三唑类杀菌剂的微生物种类、降解机理及影响微生物降解的因素等方面进行了综述,同时指出,目前有关微生物降解三唑类杀菌剂的研究多数仅限于降解菌的筛选及影响降解的因素分析等方面,对于三唑类杀菌剂的微生物代谢途径、降解过程中起关键作用的酶和基因,以及对手性三唑类杀菌剂的对映体选择性降解机制等机理方面的研究仍较少,相关研究有待进一步加强。     

Factors controlling degradation of pesticides in soil

Rates of pesticide degradation in soil exhibit a high degree of variability, the sources of which are usually unclear. Combining data from incubations performed using a range of soil properties and environmental conditions has resulted in greater understanding of factors controlling such degradation. The herbicides clomazone, flumetsulam, atrazine, and cloransulam-methyl, as well as the former insecticide naphthalene offer examples of degradation kinetics controlled by coupling competing processes which may in turn be regulated separately by environmental conditions and soil properties. The processes of degradation and volatilization appear to compete for clomazone in solution; sorbed clomazone is degraded only after the solution phase is depleted. Similarly, volatilization of naphthalene is enhanced when degradation has been inhibited by high nutrient levels. Degradation of the herbicide flumetsulam has been shown to be regulated by sorption, even though the compound has a relatively low affinity for the soil. The fate pathway for cloransulam-methyl shifts from mineralization to formation of metabolities, bound residues and physically occluded material as temperature increases. Atrazine degradation in soil may be controlled in part by the presence of inorganic nitrogen, as the herbicide appears to be used as a nitrogen source by micro-organisms. New insight gained from measurement of multiple fate processes is demonstrated by these examples.     

北方五省(区)马铃薯晚疫病菌对甲霜灵和精甲霜灵的敏感性检测

为了明确我国不同地区马铃薯晚疫病菌对甲霜灵和精甲霜灵的抗性状况,2007-2009年从河北、黑龙江、吉林、辽宁和内蒙古马铃薯主产区采集马铃薯晚疫病菌,采用菌丝生长速率法和叶盘漂浮法测定其对甲霜灵的敏感性,采用叶盘漂浮法测定其对精甲霜灵的敏感性.结果表明:以菌丝生长速率法检测的380株晚疫病菌中和以叶盘漂浮法检测的222株晚疫病菌中对甲霜灵的抗性菌株分别占80％和73.5％;菌丝生长速率法检测结果显示,河北省对甲霜灵的抗性菌株所占频率从2007年的100％降为2008年的66.4％,2009年又回升至74.2％,而吉林和黑龙江两省对甲霜灵的抗性菌株分布频率呈上升趋势.叶盘漂浮法检测的95个菌株中对精甲霜灵的抗性菌株占54.5％,其中河北省40个菌株对精甲霜灵的中间型菌株占优势(62.5％),抗性菌株仅占34.9％,而其他4省55个菌株对精甲霜灵的抗性菌株占优势(69.1％).受检测的北方五省(区)马铃薯晚疫病菌群体中对甲霜灵和精甲霜灵的抗性菌株已占优势,马铃薯晚疫病菌已普遍对甲霜灵及精甲霜灵产生抗性.在对甲霜灵和精甲霜灵普遍产生抗性的地区,应优先选用与甲霜灵、精甲霜灵作用机理不同的药剂防治马铃薯晚疫病.     

甲草胺在水稻上的残留及消解动态

采用气相色谱电子捕获检测(GC-ECD)建立了水稻中除草剂甲草胺的残留分析方法。样品经乙酸乙酯提取,乙二氨基-N-丙基硅烷(PSA)和石墨化炭黑(GCB)净化后采用GC-ECD检测。结果表明:在0.01~1mg/L范围内甲草胺浓度与响应值线性关系良好,相关系数(r)为0.998 8。当甲草胺在水稻植株、稻壳、糙米、田水和土壤中的添加水平为0.01~0.5mg/kg时,平均回收率为79.5%~113.6%,相对标准偏差(RSD)为2.5%~12.7%。甲草胺的最低检出浓度为0.01mg/kg。采用该方法对甲草胺在田间水稻中的消解动态和最终残留进行了测定。甲草胺在稻田植株和田水样品中的消解均符合一级动力学方程。半衰期分别为11.17~26.65d和1.56~1.78d,属于易降解农药。     

溴虫腈在不同溶剂中的光化学降解

研究了高压汞灯光源下溴虫腈在不同溶剂中的光化学降解特性及其影响因素。在室内模拟条件下,初始质量浓度为2 mg/L的溴虫腈在纯水中的光解半衰期为25.86 min,在1~10 mg/L范围内,其光解速率随初始浓度的增大而降低;溴虫腈在pH值为5、7和9的缓冲溶液中的光解半衰期分别为42.52、24.49和32.39 min,即其在中性条件下光解最快;不同形态含氮离子(NO2-、NO3-、NH4+)对溴虫腈的光解均表现为抑制作用,且在离子质量浓度＜20 mg/L时,NO3-、NO2-的抑制作用较强,≥20 mg/L时则NH4+的抑制作用较强;溴虫腈在不同有机溶剂中的光解速率从大到小依次为:正己烷>甲醇>乙酸乙酯>丙酮,其光解速率与有机溶剂的极性大小无关。研究结果可为溴虫腈的环境风险评价提供参考。     

咪唑啉酮类除草剂的应用及降解

咪唑啉酮类除草剂虽具有高效广谱的特点,但有较长的残留活性,长期使用会造成作物药害,并且会制约正常的作物轮作。因此,如何解决其残留问题已成为目前的重要课题。本文介绍了咪唑啉酮类除草剂的种类和特性,阐述了此类除草剂在杂草体内的作用方式、代谢机制、应用情况及其在土壤中的降解途径,并对该类除草剂的应用与降解研究进行了展望。     

Disposition kinetics of cypermethrin and fenvalerate in black bengal lactating goats

Disposition kinetics of cypermethrin and fenvalerate were investigated in lactating black Bengal goats following single dose intravenous administration at 57 and 45 mg kg^?1 respectively. The maximum and minimum blood concentrations of cypermethrin were 18.49 (±3.17) and 0.06 (±0.002) μg ml^?1, while the corresponding values for fenvalerate were 14.58 (±2.37) and 0.04 (±0.005) μg ml^?1 respectively. Both cypermethrin and fenvalerate remained present in blood for 36 h. The mean t1/2β) and Vd_area values were 5.56 (±0.28) h and 10.38 (±2.20) litre kg^?1 for cypermethrin and 5.66 (±0.35) h and 11.31 (±2.20) litre kg^?1 respectively for fenvalerate. Both cypermethrin and fenvalerate persisted in goat milk for 36 h. The t1/2β) and AUC values of fenvalerate were 7.37 (±1.84) h and 122.38 (±11.65) μg h ml^?1 whilst the corresponding values for cypermethrin were 6.66 (±1.54) h and 99.48 (±7.81) μg h ml^?1 in milk respectively.     

Chemical control of late blight epidemics incited by metalaxyl-resistantPhytophthora infestans in potato crops in Israel

Four field trials were conducted to evaluate the efficacy of various fungicide formulations in controlling late blight in potato crops artificially inoculated with A₂ metalaxyl-resistant isolates ofPhytophthora infestans. Two trials (Winter 1986, Spring 1987) were performed at the research farm of Bar-IIan University (central coastal plain) and two trials (Winter 1987, Spring 1988) at the Besor Experiment Farm (western Negev), with seven formulations tested in each trial. At Bar-IIan, Mancur (mancozeb + cymoxanil, 4:1) applied once a week was most effective in controlling the blight. Sandocur-M and Pulsan (mancozeb + oxadixyl + cymoxanil, 7:1:2 and 7:1:0.4, respectively) applied at biweekly intervals were the second best, while SAN 518F (mancozeb + oxadixyl, 7:1) and Ridomil-MZ (mancozeb + metalaxyl, 7.5:1) applied at biweekly intervals, and mancozeb or cymoxanil applied once a week, were the least effective. At the Besor farm Ridomil-MZ at biweekly intervals was the least effective, but the efficacy of the other formulations varied between the two trials. Mancur, Sandocur-M, Previcur-N and mancozeb were highly effective in Winter 1987 but less so in Spring 1988. In the latter season Mancur, Sandocur-M and Previcur-N were significantly more effective than mancozeb or Ridomil-MZ. The correlation coefficient between yield and final disease level was -0.5322.     

泾河下游可降解污染物的自净特征

泾河近30年来污染日趋严重。通过分析泾河下游枯水期可降解污染物的自净特征,建立了河流点源排污和侧向污染物均匀补排条件下的水质衰减模型,并提供了一种简便的求自净特征参数的方法。     

Translocation and degradation of pyrazosulfuron-ethyl in rice soil

BACKGROUND: Pyrazosulfuron‐ethyl {ethyl 5‐[(4,6‐dimethoxypyrimidin‐2‐ylcarbamoyl)‐sulfamoyl]‐1‐methylpyrazole‐4‐carboxylate} is a new rice herbicide belonging to the sulfonylurea group. This study reports the translocation of ¹⁴C‐pyrazosulfuron‐ethyl to rice plants and its degradation in rice‐planted and unplanted soil. RESULTS: Pyrazosulfuron‐ethyl did not show any appreciable translocation to rice shoots, as ¹⁴C‐activity translocated to the aerial portion never exceeded 1% of the initially applied ¹⁴C‐activity over a 25 day period. Results suggested that the dissipation of pyrazosulfuron‐ethyl from soils followed first‐order kinetics with a half‐life of 5.5 and 6.9 days in rice‐planted and unplanted soils respectively. HPLC analysis of the organic extract of soil samples showed the formation of three metabolites, namely ethyl 5‐(aminosulfonyl)‐1‐methyl‐1‐H‐pyrazole‐4‐carboxylate, 5‐[({[(4,6‐dimethoxy‐2 pyrimidinyl)‐amino]‐carbonyl} amino)‐sulfonyl]‐1‐methyl‐1H‐pyrazole‐4‐carboxylic acid and 2‐amino‐4,6‐dimethoxy pyrimidine, in both rice‐planted and unplanted soils. CONCLUSION: The study indicates that pyrazosulfuron‐ethyl was a short‐lived compound in the soil and was degraded relatively faster in rice‐planted soil than in unplanted soil. The herbicide did not show any appreciable translocation to rice plants. Copyright © 2011 Society of Chemical Industry