取代脲类除草剂光催化降解动力学比较

为研究取代脲类除草剂在TiO₂光催化降解过程中的动力学规律,以非草隆、异丙隆和利谷隆3种取代脲类除草剂为研究对象,通过Langmuir-Hinshelwood动力学模型对其TiO₂光催化降解动力学进行模拟,并系统探讨了催化剂用量、C₀(取代脲类除草剂的初始浓度)、溶液pH、温度、ROSs(活性氧物种)和电子捕获剂等的影响. 结果表明:非草隆、异丙隆和利谷隆的TiO₂光催化降解均符合假一级动力学模型,其动力学常数分别为0.082 8、0.068 7和0.095 4 min-1;取代脲类除草剂分子中的芳香环和脲桥上的取代基对降解速率常数的大小有明显的影响. ROSs试验表明,非草隆、异丙隆和利谷隆光催化降解过程中分别有91.6%、95.5%和86.8%的贡献来自·OH;而光生空穴和其他ROSs的贡献相对较小,并且电子捕获剂BrO₃-和S₂O₈2-对取代脲类除草剂的降解动力学有显著的促进作用.      

Progress in herbicide determination with the thylakoid bioassay

Chloroplast thylakoids are used as biological units to determine herbicides in different kinds of water samples as well as in aqueous extracts of compost, soil or food samples. The thylakoid bioassy shows clearly inhibition of fluorescence yield in the presence of photosystem II specific herbicides. Due to this method the ecotoxicological effect of samples with unknown pollutants can be tested fast and cost effective. It has been proven that all photosynthetic active compounds are recorded at the same time because only additive interactions occur. Therefore, the contamination level can be expressed as cumulative parameter for photosystem II active substances. Application was improved clearly by the addition of the radical scavenger sodium ascorbate to the isolation media and by a higher concentration of the measuring medium. A new data evaluation method is described yielding in a lower detection limit of 0.4 μg diuron/1. The guidelines for the quality of water for human consumption with an allowable concentration of pesticides in groups is 0,5 μg/1 [1,2] and can be controlled with the thylakoid bioassay without performing any preconcentration steps.     

HERBICIDE AND NITRATE VARIATION IN ALLUVIUM UNDERLYING A CORN FIELD AT A SITE IN IOWA COUNTY,IOWA1

ABSTRACT: A hydrologic investigation to determine vertical and seasonal variation of atrazine, alachlor, cyanazine, and nitrate at one location and to relate the variation to ground-water movement in the Iowa River alluvium was conducted in Iowa County, Iowa, from March 1986 to December 1987. Water samples were collected at discrete intervals through the alluvial sequence from the soil zone to the base of the aquifer. Alachlor, atrazine, and cyanazine were detected most frequently in the soil zone but also were present in the upper part of the alluvial aquifer. Alachlor was detected sporadically, whereas, atrazine, cyanazine, and nitrate were present throughout the year. In the alluvial aquifer, the herbicides generally were not detected during 1986 and were present in detectable concentrations for only a short period of time in the upper 1.6 meters of the aquifer during 1987. Nitrate was present throughout the alluvium and was stratified in the alluvial aquifer. The largest nitrate concentrations were detected in the middle part of the aquifer. Nitrate concentrations were variable only in the upper 2 meters of the aquifer. Vertical movement of herbicides and nitrate in the soil correlated with precipitation and degree of saturation. A clay layer retarded vertical movement of atrazine but not nitrate from the soil layer to the aquifer. Vertical movement could not account for the chemical variation in the alluvial aquifer.     

环境水体中三嗪类除草剂的SPME-GCMS联用仪测定

文章研究了固相微萃取-气相色谱/质谱联用技术测定环境水体中的11种三嗪类除草剂的方法.选择了以聚二甲基硅氧烷(PDMS)/二乙烯苯(DVB)和聚丙烯(PA)作为涂层材料的两种不同固相微萃取纤维对11种除草剂的萃取能力进行比较,PDMS/DVB萃取效果较好.为了提高萃取效果,分别从pH、解吸温度、萃取时间、盐效应等方面优...     

磺酰脲类除草剂在环境中的光降解研究——水溶液中的光解动力学

以汞灯为光源,研究了甲黄隆,苯黄隆,氯黄隆,氯嘧黄隆,苄嘧黄和胺苯黄隆６种磺酰脲类除草剂在水液中的光解动力淡。结果表明,５种磺酰的降解呈一级动力学反应;体系的ＰＨ值对降解速率影响不明显,光强的影响较明显著;Ｈ２Ｏ２丙酮和溶解有机质均可促进磺酰光解;党妥氧对该类除草剂光解的影响表现为光氧化与淬灭２种作用的竞争。     

磺酰脲类除草剂研究进展

本文较全面地概述了近几年国内外有关磺酰脲类除草剂的分析测试和降解方式等方面的研究现状,着重讨论了磺酰脲类化合物的结构活性相关和风险评价等方面的研究进展     

Effect of humic acids on photodegradation of chloroacetanilide herbicides under UV irradiation

The effects of two humic acids (HAs) of different origins on the photodegradation of the chloroacetanilide herbicides acetochlor, propisochlor and butachlor were investigated in this study. One of the tested HAs was a standard sample that was purchased from a commercial source, and the other was isolated from the black soil of Northeast China. The photolysis of all three herbicides followed pseudo-first-order kinetics under ultraviolet (UV) irradiation conditions, regardless of whether HAs were present or not. Both HAs improved the photolysis rates of acetochlor in a dose-reversed way, whereas they inhibited butachlor degradation under all experimental concentrations. The two HAs differed in their effects on propisochlor photolysis, changing from enhancement to inhibition, depending on the origin and concentration of HAs. Element and Fourier Transform Infrared spectroscopy analyses showed that the isolated HAs had more polysaccharides and less aliphatic groups than the commercial HAs, and it was indicated that some characteristic radicals (C═O, O─H and phenolic hydroxyls) in HAs were involved in the photolysis of the herbicides. Gas chromatography/mass spectrometry (GC/MS) analyses indicated that the presence of HAs had no effects on the photolysis pathway and photoproduct species of the three herbicides.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

Impact of Sublethal Doses of 2,4-D,Simulating Drift,on Tomato Yield

Abstract

Tomato is considered one of the most sensitive crops regarding 2,4-D drift. In many cases, such susceptibility has led to important restrictions in the use of 2,4-D based products. Field experiments were carried out for two consecutive years in tomato, by applying sublethal doses of 2,4-D (ranging from 0.42 to 13.44 g a.i. ha^?1) directly to plants, at different stages of growth, as a simulation of eventual drifts to the crop. The range of rates was based on the assumption of a 0.0625–2.0% drift level of a 1 L ha^?1 of the most common formulated herbicides. For this crop, the range of rates between 0.42 and 13.44 g a.i ha^?1 applied at the beginning of flowering caused a linear crop reduction. On the other hand, rates ≤13.44 g a.i. ha^?1 applied after full development of fourth truss stage or latter had no effect on crop yield or development. For tomato, tolerance to 2,4-D strongly increases with plant age.