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Assessment of silicone as support to investigate the transformation routes of organic chemicals under environmental conditions and UV exposure. Application to selected fungicides

机译:评估有机硅作为研究环境条件和紫外线照射下有机化学物质转化途径的依据。应用于选定的杀菌剂

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The suitability of bulk silicone as support to follow the degradation of chemical compounds under environmental conditions and UV radiation is illustrated selecting three fungicides (fenhexamid, FEN; triadimenol, TRI and difenoconazole, DIF) as model compounds. These precursor species were first absorbed in silicone supports(10 mm length × 2 mm i.d. and 0.5 mm thickness) and then kept outdoors for several days (up to 2 months) or exposed to UV radiation (254 nm), from a low pressure mercury lamp, in the laboratory. Degradation of precursor fungicides and by-products formation was followed by liquid chromatography(LC) quadrupole time-of-flight (QTOF) mass spectrometry (MS), after desorption of silicone supports using 0.5 mL of acetonitrile. Half-lives (t_(1/2)) measured under UV exposure varied from 5 to 100 min. As regards environmental conditions, the most stable fungicide was DIF, degraded by just 15 % after 2 months; whereas, t_(1/2) values of 30 and 83 h were calculated for FEN during summer and autumn, respectively. Supports contained byproducts arising from precursor species through dechlorination, cleavage, hydroxylation, intra-molecular cyclation and oligomerization reactions. Most of them have been previously identified in soil surface, vegetable leaves and water after application of fungicides in agriculture fields. The low cost of silicone tubes (ca. 0.4 Euros), added to their excellent chemical stability and capability to retain precursor species and their by-products, make them ideal supports to follow the transformation routes of organic compounds under environmental and simulated conditions, even for relatively stable species with t_(1/2) in the range of weeks or months.
机译:说明了选择三种杀菌剂(苯六胺,FEN;三苯三酚,TRI和二苯并康唑,DIF)作为模型化合物时,本体有机硅作为载体在环境条件和紫外线辐射下跟随化合物降解的适用性。这些前体物质首先被有机硅载体(10毫米长×2毫米内径和0.5毫米厚)吸收,然后在室外放置几天(长达2个月)或暴露于低压汞的紫外线辐射下(254 nm)灯,在实验室里。使用0.5 mL乙腈对有机硅载体进行解吸后,通过液相色谱(LC)四极杆飞行时间(QTOF)质谱(MS)降解前体杀真菌剂和副产物。在紫外线下测量的半衰期(t_(1/2))从5到100分钟不等。就环境条件而言,最稳定的杀菌剂是DIF,在2个月后降解仅为15%。而在夏季和秋季分别计算了FEN的t_(1/2)值30和83 h。载体包含通过脱氯,裂解,羟基化,分子内环化和低聚反应从前体物种产生的副产物。在农业领域中使用杀真菌剂后,大多数已经在土壤表面,蔬菜叶和水中被鉴定出来。硅胶管的低成本(约0.4欧元),加上出色的化学稳定性和保留前驱物物种及其副产物的能力,使其成为在环境和模拟条件下遵循有机化合物转化路线的理想支撑,甚至对于相对稳定的物种,t_(1/2)在数周或数月的范围内。

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