氰霜唑及其代谢物4-氯-5-(4-甲苯基)-1H-咪唑-2-腈在苦瓜中的残留消解动态及膳食安全性评价

[目的]研究旨在优化苦瓜中氰霜唑(Cyazofamid)及其代谢物CCIM的QuEChERS-液相色谱-串联质谱残留分析方法;同时结合苦瓜的田间残留消解动态试验,对膳食摄入风险进行评价。[方法]苦瓜样品采用含1%乙酸的乙腈溶液提取,LC-MS/MS进行检测,通过基质匹配标准溶液外标法定量。通过在黑龙江、河北、河南、重庆、浙江和广东6地进行了100 g/L氰霜唑悬浮剂在苦瓜上残留的田间试验,研究了氰霜唑在苦瓜中的消解动态,对苦瓜中氰霜唑可能产生的膳食摄入风险安全进行评价。[结果]试验结果表明：1)氰霜唑在0.005-1.0 mg/L、CCIM在0.001-1.0 mg/L质量浓度范围内线性关系良好,相关系数均大于0.9987;在0.010、0.10、0.50 mg/kg 3个浓度下,苦瓜中氰霜唑及CCIM的回收率为80.0%～100.0%,相对标准偏差(RSD)为0.05%～12.1%。检出限(LOD)为0.364-0.654 μg/kg,方法定量限(LOQ)为添加的最低浓度0.010 mg/kg。2)田间试验结果表明：氰霜唑在苦瓜中消解符合一级反应动力学方程,半衰期为3.0～4.9 d,属易降解农药;使用100 g/L氰霜唑悬浮剂,施药剂量105-157.5 g a.i./hm2,分别施药2、3次,苦瓜中氰霜唑总的最终残留量最大值为6.54 mg/kg。3)膳食摄入风险评估结果表明：氰霜唑的风险概率为每人每日摄入总量的1.0%。[结论]在苦瓜生长期间按照推荐剂量合理使用氰霜唑对消费者的膳食健康风险极低,对消费者健康是安全的。     

1-羟基-4-(4-甲基苯基)-2-甲肟基咪唑-3-氧化物的合成工艺研究

以2,2-二氯-4'-甲基苯乙酮为原料,在六水合氯化铁促进下,与羟胺盐和乙二醛反应,得到1-羟基-4-(4-甲基苯基)-2-甲肟基咪唑-3-氧化物。研究了反应时间、物料配比、溶剂的种类和三氯化铁的用量等因素对环化反应的影响,优惠条件下的收率达到87.5%。该法原料来源广、成本低、反应条件温和、收率高,具有工业化应用前景。     

Impact of phytosanitary treatments with fungicides (cyazofamid, famoxadone, mandipropamid and valifenalate) on aroma compounds of Godello white wines

Cyazofamid, famoxadone, mandipropamid and valifenalate, four new fungicides for controlling downy mildew in vine, were applied to an experimental vineyard producing Vitis vinifera white grapes of the Godello variety. Following harvest, the grapes were subjected to single vinification runs. The odour activity values (OAVs) for the Godello white wines obtained were estimated with a view to assessing potential alterations of their aroma composition by effect of the phytosanitary treatments. Several fatty acids, their esters and acetates were formed during the winemaking process in high levels and could be expected to strongly influence the aroma of the wines by introducing floral, fruity and spicy nuances. The concentrations of six compounds (2-phenylethyl acetate, ethyl butanoate, ethyl octanoate, 4-vinylguaiacol, 3-methylbutanoic acid and methionol) were found to suffice with a view to discriminating between wines from grapes treated with fungicides under Critical Agricultural Practices (CAP) and under Good Agricultural Practices (GAP).     

Decay of fungicide residues during vinification of white grapes harvested after the application of some new active substances against downy mildew

Cyazofamid, famoxadone, mandipropamid and valifenalate are new fungicides recently proposed to control downy mildew (Plasmopara viticola) in vines. In this study, three of them were applied in an experimental vineyard producing white grapes (Vitis vinifera cv. Godello) as commercial formulations: Mildicut (2.5% cyazofamid), Equation Pro (22.5% famoxadone + 30% cymoxanil) and IR-5885 (6% valifenalate + 60% mancozeb), meanwhile mandipropamid was directly applied as an active substance. The last treatments to control this disease were made out under critical agricultural practices, without obeying the preharvest interval. Besides the above products, the control of powdery mildew (Erisiphe necator) and grey mould (Botrytis cinerea) was made by employing standard commercial formulations. Once treated white grapes were harvested, the fate of all these fungicides from vine to wine was studied. Residues of cyazofamid, famoxadone and valifenalate in grapes were higher than their EU MRL, except for mandipropamid. The white wine-making process allowed the dissipation of fungicide residues in high percentages (ca. 95%), except for valifenalate that remained in wine at 32%.