农药的科学使用问题与农药应用工艺学

农药应用工艺学是研究提高农药利用率和施药效率,减轻或消除农药对环境的污染和对人、畜及有益生物危害风险的一门综合性学科。近20年来,中国在农药的吸收传导、控制释放、剂型研发、省力化施药、雾滴运动、高效装备及智能精准施药等方面取得了长足的进步：建立了药剂吸收量与种子包衣剂量之间的关系模型;阐明了农药控制释放的动力学规律,揭示了缓释农药提高作物安全性的生物学机制;研发了超低容量制剂、烟雾剂、粉尘剂、展膜油剂、缓释颗粒剂等省力化农药剂型和与之匹配的省力化施药技术;探明了农药雾滴在作物冠层的沉积流失规律,建立了农药利用率模型;建立了农药施用定量分析计算理论,提出了农药雾滴“杀伤半径”概念,推动了农药低容量喷雾技术发展;建立了植保无人飞机低容量喷雾技术体系,开启了人工智能 (AI) 施药技术的研究和应用,初步建立人工智能精准喷雾技术。中国农药应用已逐步实现从简单、粗放向科学、安全、智能精准的转变,为农药减施增效提供理论依据和技术支撑。     

Movement of pesticides to surface waters from a heavy clay soil

A field experiment at Cockle Park, Northumberland on a clay loam soil (Dunkeswick series) cropped with winter wheat investigated the effects of drainage and season of application on pesticide movement. Isoproturon, mecoprop, fonofos and trifluralin were applied in two consecutive seasons at normal agricultural rates to three hydrologically isolated plots each of 0.25 ha. Two of the plots were mole-drained and the third was an undrained control. Surfacelayer flow and drainflow from each plot were monitored at 10-min intervals. Samples of flow were analysed for pesticides to evaluate transport of applied chemicals from the site. Despite widely differing properties (K_oc 20–8000 ml g^?1, t_1/2 10–60 days), all four pesticides were found in surface-layer flow and mole drainflow from the site. Maximum concentrations of pesticides in flow ranged from 0.1 to 121 μg litre^?1 (aqueous phase) and < 0.2 to 48 μg litre^?1 (particulate phase). Over two contrasting seasons, total losses of pesticides in flow followed total amounts of flow and were approximately four and five times larger, respectively, in 1990/91 than in 1989/90. The maximum loss occurred from the undrained plot and was 2.8 g isoproturon (0.45% of that applied). Total losses of autumn-applied pesticides from an undrained plot were up to four times greater than losses from a mole-drained plot. Mole drainage decreased movement of pesticides from this slowly permeable soil by reducing the amount of surfacelayer flow. Maximum concentrations of mecoprop and isoproturon in drainflow were 10–20 times larger following spring application than after application in autumn. Bypass flow down soil cracks was an important process by which pesticide was lost from the site, with transport to the drainage system via mole channels (55 cm depth) after less than 0.5 and 6.7 mm net drainage in the two winters.     

Photocatalytic degradation of pesticides and bio-molecules in water

Two approaches are suggested for the acceleration of the photocatalytic oxidation of organic contaminants of water: acceleration by oxidants and photo-enhancement by dyes. These processes were examined with several substances: two widely applied herbicides, bromacil (a uracil) and metribuzin (a triazine), and three proteins, studied as models of biocontaminated waters. The effects of oxygen and hydrogen peroxide indicated two different reaction patterns of photo-oxidation of the herbicides. With metribuzin, oxygen had a pronounced effect on the rate of photo-oxidation, while the influence of hydrogen peroxide was quite moderate; with bromacil, oxygen had a limited effect on the rate of photo-oxidation, which however was considerably enhanced by hydrogen peroxide. Acceleration of the photo-catalytic oxidation of colourless refractory contaminants by photo-excited dye was observed. Both UV and visible light were required for the enhanced decomposition. The mechanism of the reaction seems to involve a combination of oxidation by hydroxyl radicals, via the hole-electron semiconductor route, with subsequent oxidation of photo-intermediates by singlet oxygen formed by dye sensitization. The TiO2-photocatalyzed oxidation of proteins (albumin, ovalbumin and gamma-globulin) showed the susceptibility of proteins to photocleavage and of the amino acids to photocatalytic degradation. Tyrosine was the most sensitive, while the degradation of the aliphatic amino acids Gly and Asp was slow.     

水稻螟虫化学防治药剂的筛选及抗性水平的测定

根据5年的多点对比试验,从几十个农药品种(配方)的防治效果、对天敌的杀伤力及螟虫抗药性情况等综合考查分析,获得防治二化螟的优先药剂及配方:即每667m2用5%氟虫腈SC(锐劲特)30ml、50%敌.氟腈SC(灵蛙)100ml、27%辛.唑磷EC(螟盖)75ml及5%氟虫腈SC20ml与8%高渗三唑磷ME(庄螟)100～120ml或18%杀虫双AS250～300ml、30%乙酰甲胺磷EC100 ml、90%敌百虫SP100g、8000IU/lμ苏云金杆菌WP50g的桶混配方。防治三化螟以667m2用5%氟虫腈SC40ml或20%阿维.唑磷EC50ml效果较好。     

Evaluation of the membrane approach to solid-phase extractions of pesticide residues in drinking water

The purpose of this work was to compare the method and analytical results obtained by liquid/liquid extraction with those of solid-phase extraction, in particular with the use of an Empore disc, in the investigation of pesticide residues in drinking water.     

Factors influencing entry of pesticides into soil water

Leaching of pesticides and hence the risk of contamination of ground-water depends on the physicochemical properties of the pesticide, the properties of the soil and the weather. Lipophilicity is the most important physicochemical property influencing the movement of un-ionised pesticides through soil. Water solubility is usually only an important factor in leaching for a few moderately polar solids with high melting points. Organic matter content is the most important property of the soil for un-ionised pesticides whilst the mobility of weak acids depends on soil pH. Permanent anions and weak acids can be very weakly adsorbed and hence might easily reach groundwater. Applications in autumn are more likely to reach groundwater than those in spring because soil temperatures are low and rainfall exceeds evaporation in winter, enabling mobile pesticides to penetrate to subsoils where degradation rates can be very slow. Concentrations of pesticide in water entering subsoils cannot be reliably simulated to an accuracy of better than an order of magnitude because the complex patterns of water flow and the slow diffusion processes of the pesticide are insufficiently understood. The consequences of applying a mobile pesticide to soil where drainage is impeded or where the water table is near the surface need to be anticipated before it is registered for treatment of the soil.     

Experimental design and response surface analysis of pesticide trials

The search for combinations of pesticides or herbicides which have a synergistic effect is an important area of study and one which presents challenges for the statistician as well as for the experimenter. The aim is to find and to describe the interaction between a number of quantitative factors, and having done so to determine a combination which is economically optimal for a given level of control. The present paper discusses the role of a family of response functions called Inverse Polynomials to describe such phenomena. Examples are given of such functions and it is shown how it is possible to fit these functions to data and to plot the results on a routine basis. The importance of the experimental design for the estimation of such nonlinear regression models is investigated, and examples are given of experimental designs which are ‘optimal’ with respect to particular aims of the experimenter.     

中药材上农药应用现状及其炮制加工过程对农药残留的影响

中医药是我国独特的医药资源,中药材作为中医药的重要组成部分,其质量安全广受关注.在中药材病虫草害防治过程中,由于农药不规范使用导致的农药残留问题直接影响着中药材产品质量安全甚至出口贸易.本文对我国中药材上农药登记情况及残留限量(maximum residue limit,MRL)标准进行了概述,并重点归纳了炮制加工过程...     

Solid-phase extraction of pesticides from surface water using discs,bulk sorbents and supercritical fluid extraction (SFE)

Extraction of pesticides from river water samples using the classical liquid-liquid extraction (LLE) approach is a labour-intensive procedure that requires relatively large volumes of solvent. With the solid-phase extraction (SPE) technique using membranes, the volumes of solvent are reduced. However, it is necessary to pre-filter and often also to acidify the river water to pH < 2 to prevent plugging of the capillary pores. This low pH may decompose some pesticides and therefore a fast and inexpensive technique with bulk sorbent and without prefiltration and acidification was developed. To reduce the solvent volumes further, extractions of discs and bulk sorbent were performed with supercritical fluids (SF). Seven pesticides with different polarities were studied. Mean recoveries from the bulk sorbent and the discs were of the same order (61%). However, recoveries from the latter improved to 82% with SFE of the discs, providing results comparable to LLE (94%) recovery.     

Uptake of pesticides from water and soil by earthworms

The uptake of pesticides by earthworms from aqueous solutions was examined and shown to be a reversible physical process. Measurements of distributions of pesticides between aqueous solutions and worm solids showed that adsorption coefficients were related to octanol-water distribution coefficients, as are soil-water distributions. From these relationships it was calculated that concentration factors of stable chemicals in earthworms from soil should be similar, except for polar substances which penetrate poorly, and be determined mainly by the soil organic matter content. Examination of uptake from soils indicated that the calculated concentration factors are unlikely to be achieved because of slow diffusion of chemicals in soils and because of metabolism in the soil or the worm.     

Modelling pesticide run-off to surface waters. Part I: Model theory and development

A conceptual model is presented to estimate the concentrations of pesticides appearing in surface waters following their application as part of agricultural production. The model has been formulated particularly to deal with soils that are prone to bypass flow and require artificial sub-surface drainage. Pesticide concentrations and loads can be calculated at field drainage outlets or for whole headwater catchments. The data required to run the model are generally readily available from published sources (within the UK) and these data have been detailed. The assumptions made in the model are stated and the limitations with respect to the general applicability of the model are discussed. © 1998 Society of Chemical Industry     

Separation of pesticides,related compounds,polychlorobiphenyls and other pollutants into four groups by silica-gel microcolumn chromatography (application to surface water analysis)

Multi-residue analyses of pesticides and related compounds generally require clean-up procedures for the elimination of interfering substances. An analytical procedure for use in the recovery and determination of pesticides and other pollutants in water samples is described, in which the purification of the extracts is improved by the separation of pesticides into four groups. The separation of pesticides by silica-gel microcolumn chromatography is explained in detail.     

两种双发光镧系金属有机框架材料联用检测水中农药残留

传统单发射响应发光传感器因发射光波长单一易受环境因素干扰而灵敏度低,以及双/多元镧系共掺杂发光传感器由于体系内镧系元素之间的能量转移效率易受温度等因素影响而使得检测灵敏度与选择性低,本文提出联用两种双发光镧系金属有机框架材料(lanthanide metal-organic frameworks,Ln-MOFs)实现水...     

气相色谱-质谱法测定水-沉积物系统中39种农药残留

建立了气相色谱-质谱(GC-MS)同时测定水体和沉积物中39种农药残留的检测方法。水体样品由乙酸乙酯萃取,无水硫酸钠干燥;沉积物样品经乙腈超声提取,采用N-丙基乙二胺(PSA)和石墨化碳黑(GCB)净化,选择离子监测模式(SIM)进行检测,外标法定量。结果表明：39种农药在10～1 000μg/L范围内线性关系良好,决定系数(R2)均大于0.995 0。空白水样在0.25、0.5、5.0μg/L 3个添加水平下的平均回收率在72%～111%之间,相对标准偏差(RSD,n=5)在1.1%～10%之间,检出限(LOD)为0.02～0.06μg/L,定量限(LOQ)为0.04～0.18μg/L;空白沉积物在5.0、20.0、100.0μg/kg 3个添加水平下的回收率在65%～119%之间,RSD (n=5)在2.1%～12%之间,LOD为0.7～1.5μg/kg,LOQ为2.1～4.3μg/kg。该方法灵敏、准确,结果可靠,可满足水体和沉积物中39种目标农药的残留分析要求。     

Extended summary SCI pesticides group/BCPC international symposium comparing glasshouse and field pesticide performance. Comparing glasshouse and field performance of pesticides: An appraisal

The following is an extended summary based on a concluding paper presented at the above symposium, which was organised by G. Hewitt, D. Tyson, L. C. Copping, B. T. Grayson and J. C. Caseley on behalf of the British Crop Protection Council and the SCI Pesticides Group, and held at the University of Kent, Canterbury, on 12–14 April 1994. The summary is entirely the responsibility of the author, and does not necessarily reflect the views of the Editorial Board of Pesticide Science.