摘要
水稻是世界上历史悠久、食用人口众多的农作物之一。以稻米、高粱、小麦等谷物为原料酿造而成的白酒、米酒,是中国的传统产品。水稻及其他谷物种植和储存中不可避免要使用农药,酒类饮品中的农药残留风险是重要的科学问题。本研究建立了稻米和白酒(蒸馏酒)、米酒中的7种农药多残留的检测方法；考察了基质效应、稳定性；并对发酵及烹饪过程中农药的迁移规律及去除情况等进行研究,为制定相关的政策或风险评估及风险管理提供科学依据与参考。
对氰氟草酯、唑草酮、双草醚、2甲4氯钠四种除草剂在水稻、土壤和田水中的残留分析及消解动态进行了研究,并对氰氟草酯的活性代谢物进行了考察。建立了氰氟草酯、唑草酮、双草醚、2甲4氯钠在水稻植株、糙米、稻壳、土壤和田水中的残留分析方法。氰氟草酯、唑草酮、双草醚、2甲4氯钠的田间残留试验在北京、湖南、江苏三地进行,于水稻分蘖末期施约,按照推荐剂量高值和1.5倍推荐剂量高值各施药1次。根据最终残留试验结果,高、低剂量施药1次,水稻收获期的水稻植株、土壤、糙米和稻壳样品中氰氟草酯、唑草酮、双草醚、2甲4氯钠的最终残留量均低于本方法的检出限和国际上现有的MRLs。考虑到残留试验结果中几种除草剂残留量均低于本方法的检出限和国际上现有的MRLs,本论文选取的研究白酒发酵酿造过程迁移规律的农药多为熏蒸剂、杀虫剂及杀菌剂。
对固相萃取法(SPE)和QuEChERS法两种前处理方法进行了考察,对目标农药在稻米、白酒和米酒中的回收率为60-120%之间,在0.05-2mg/L范围内线性关系良好,相关系数大于0.99。相比而言,QuEChERS法更加快速简便、节约成本,该方法的添加回收率在67-113.5%之间,方法检出限LOD在3-20μg/L之间,定量限LOQ在10-50μg/I之间。QuEChERS法回收到的7种农药为甲基嘧啶磷、乙草胺、毒死蜱、丁草胺、戊唑醇、高效氯氰菊酯、嘧菌酯。
在此基础上,考察了气相色谱质谱联用检测稻米、白酒和米酒中的甲基嘧啶磷等7种农药的基质效应。研究结果表明,在白酒和米酒基质中,基质减弱效应多于基质增强效应.甲基嘧啶磷、毒死蜱、高效氯氰菊酯在白酒和米酒中的基质减弱效应最为明显。在稻米基质中,大多数农药显示出基质增强效应；乙草胺、丁草胺、高效氯氟氰菊酯的基质增强效应最为明显。浓度越小,基质效应相对越明显。对7种农药在不同基质提取液中不同储存条件下的稳定性进行了考察。结果表明,溶剂挥发效应与分解或降解效应同时存在,储存时间越长,溶剂挥发效应越占优势；较短冷藏储存期(20天)内,农药的含量变化受温度的影响基本可以忽略。
论文研究了甲基嘧啶磷等7种农药在稻米浸泡、淘洗、蒸煮过程中的降解情况。结果发现,浸泡、淘洗过程对水溶性大的农药去除率较高。对于实验农药,2次淘洗和浸泡后淘洗的效果相差不大,均比只淘洗一次的样本中农药去除率高。蒸煮过程对添加样本中的农药去除率最高,为67.4%至95.7%。并进而研究了甲基嘧啶磷等7种农药在白酒酿造过程中的降解情况。生料酿酒过程中,发酵4天后白酒中农药检出浓度均在1mg/L以下,其中乙草胺、丁草胺、戊唑醇的检出浓度较大。甲基嘧啶磷在发酵第12天时已检测不到,是消解最快的农药。蒸馏过程使7种农药均呈现浓度下降的情况。其中沸点较低的乙草胺、丁草胺、戊唑醇三种农药的损失率较小。而在熟料酿造过程中,由于原料经过蒸煮步骤,熟料酿酒过程第4天检测到的农药浓度明显减小。乙草胺、甲基嘧啶磷、丁草胺在发酵第7天已检测不到。发酵7-12天时,各农药在发酵液中的浓度均呈减小趋势。蒸馏步骤后,馏出液中仅毒死蜱与嘧菌酯能检测到微量浓度。
本论文研究了甲基嘧啶磷等7种农药在米酒酿造过程中的降解情况。米酒酿造的过程中农药消解程度较大。丁草胺在发酵的第3天已检测不到,戊唑醇、乙草胺在发酵的第7天检测不到。发酵过程中,多数农药在发酵液中的浓度均呈递减趋势。发酵结束时,甲基嘧啶磷、毒死蜱、高效氯氰菊酯与嘧菌酯有微量残留。煮沸后的酒液中未检测到农药残留。
本论文研究了甲基嘧啶磷等7种农药在大米淘洗、蒸煮过程中的降解情况及在白酒、米酒发酵过程中残留浓度的变化。论文的研究结果对我国今后开展稻谷酿酒过程风险评估、制定白酒、米酒中农药残留相关限量及法律法规有一定的参考价值。
Rice is the most common food all over the world. White spirit and rice wine are both popular traditional drink in China, produced by rice, sorghum or wheat. Pesticides used on rice plant induce inevitable safety problems in wine-making industry. Risk of pesticide residues is an important scientific problem. This study established a multi-residue detection method for the commonly used pesticides in rice, white spirit and rice wine using gas chromatography with mass spectrometry detector, evaluated matrix effects and the stability of selected pesticides in different matrix extracts, and studied on the degradation of pesticides in cooking and fermentation process of rice.
Residue analysis and dynamics studies of cyhalofop-Butyl, carfentrazone-ethyl, bispyribac-sodium and MCPA-Na in Rice, Soil and Paddy Water were performed. The active metabolite of cyhalofop-Butyl was studied as well. Residue analysis methods of cyhalofop-Butyl, carfentrazone-ethyl, bispyribac-sodium and MCPA-Na in rice plant, brown rice, rice hull, soil and paddy water were established. The field trials were carried out in Beijing, Hunan and Jiangsu. The pesticides were applicated at the end of tillering period of rice plant. According to the results of terminal residue trials, the terminal residues of cyhalofop-Butyl, carfentrazone-ethyl, bispyribac-sodium and MCPA-Na in rice plants, soil, brown rice, rice hulls were lower than the detection limits and the existing MRLs at the harvest time. In consideration of these results, the pesticides in the work were mostly chosen from insecticide, fungicide and fumigant.
This study investigated two pre-treatment methods, solid-phase extraction (SPE) and QuEChERS. The recoveries for both methods of the pesticides in rice, white spirit and rice wine are60-120%, and good linearities between0.05mg/L and2mg/L are shown, with the correlation coefficients greater than99%. The QuEChERS method is easier and cheaper, compared with the solid-phase extraction method. So we choose the QuEChERS method. The recoveries of the method are between67-113.5%, with the limit of detection of3-20μg/L and the limit of quantification of10-50μg/L. Pirimiphos-methyl, acetochlor, chlorpyrifos, butachlor, tebuconazole, cypermethrin and azoxystrobin were the seven pesticides recycled by the QuEChERS method.
Baesd on this method, the work studied on matrix effects of7pesticides including pirimiphos-methyl in rice, white spirit and rice wine using gas chromatography mass spectrometry detection. The results showed that the7pesticides had matrix enhancement effect in rice matrix, especially acetochlor, butachlor and beta-cypermethrin. The7pesticides had matrix-weakening effect in white spirit and rice wine matrix, especially pirimiphos-methyl, chlorpyrifos and beta-cypermethrin. The lower the concentration is, the more obvious the matrix effect is. We used corresponding matrix standard solutions to reduce the matrix effects. The stability of7pesticides in different matrix extracts under different storage conditions was evaluated. It was found that the stability of pesticides in solution is related with the pesticides'physicochemical property. The unstable pesticides should be analyzed as soon as possible. The stability of solutions is relevant with both the solvent evaporation and the decomposition of compounds.
The study investigated the degradation of7pesticides including pirimiphos-methyl in the steeping, washing and steaming process of rice. According to the results, the steeping and washing process showed higher removal rate for the water-soluble pesticides. The removal rates of double washing process and steeping-washing process were in similar level, which showed advantage over washing process. The steaming process showed the highest removal rate as67.4%-95.7%. Then the degradation of7pesticides in the white spirit fermentation process was studied. The fermentation process included raw material fermentation and ripe material fermentation. In the raw material fermentation process, the results showed that the7pesticides were all below1mg/L on the5mg/kg addition level to rice four days after fermentation. The detective concentration decreased with time. The fermentation is in a strong period after3days. The pesticides concentration all decreased after distillation. In the ripe material fermentation process, the pesticides concentrations were obviously less than in the raw material fermentation process at the forth day of fermentation. Acetochlor, butachlor and pirimiphos-methyl could not be detected after seven days.The pesticide concentration decreased with time. Only trace chlorpyrifos and azoxystrobin could be detected after distillation.
The degradation of7pesticides in the rice wine fermentation process were studied. Butachlor could not be detected after three days. Tebuconazole and acetochlor could not be detected after seven days. The pesticides concentration all decreased with time. Only trace chlorpyrifos, beta-cypermethrin, pirimiphos-methyl and azoxystrobin could be detected after fermentation. There were no pesticide residues in rice wine after boiled.
This work studied on the degradation of7pesticides in the white spirit and rice wine fermentation process. The study applies important scientific basis for the establishment of China's pesticide residues in wine-related laws and regulations in the future.
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