Doulia Danae S, Anagnos Efstathios K, Liapis Konstantinos S, Klimentzos Demetrios A
a Laboratory of Organic Chemical Technology, School of Chemical Engineering, National Technical University of Athens , Athens , Greece.
b Pesticide Residue Laboratory, Benaki Phytopathological Institute , Athens , Greece.
J Environ Sci Health B. 2018 Aug 3;53(8):534-545. doi: 10.1080/03601234.2018.1462937. Epub 2018 Apr 30.
The aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol-water partition coefficient (log K) 2.7-6.3 and water solubility 0.0002-142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log K, water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.
本研究的目的是确定七种澄清剂去除红葡萄酒中农药的潜力。葡萄酒中农药的存在对酿酒师来说是个大问题，因此，澄清去除农药的结果对于决定合适的吸附剂非常有用。鉴于使用的农药数量众多且种类繁多，高效吸附剂的选择可以基于将红葡萄酒中农药去除与农药性质相关的数据。所以，本实验工作专注于收集关于使用大量农药和澄清剂通过澄清去除农药的结果。研究了一种希腊红葡萄酒，该葡萄酒添加了23种或9种农药的单一溶液及混合物。使用的七种澄清剂在两种浓度下进行测试，分别是活性炭、膨润土、聚乙烯聚吡咯烷酮（PVPP）、明胶、蛋清、鱼胶和酪蛋白。选择的农药具有广泛的性质（辛醇 - 水分配系数（log K）为2.7 - 6.3，水溶性为0.0002 - 142），属于11个化学组。采用固相萃取（SPE），随后用带电子捕获检测器（ECD）的气相色谱（GC）分析澄清强化葡萄酒中的农药残留。研究了澄清剂的有效性与农药化学结构和性质（log K、水溶性）之间的相关性。通过指数计算混合物中农药之间产生的拮抗和/或协同效应。将红葡萄酒的农药去除效果结果与在相同实验条件下白葡萄酒的结果进行比较并讨论。吸附剂有效性降低的顺序（23种农药混合物）为：活性炭40% > 明胶23% > 蛋清21% > PVPP 18% > 酪蛋白12% > 膨润土7%。鱼胶在最高允许浓度下显示出12%的去除率。在9种农药混合物的情况下，有效性相当高，但与23种农药混合物相比顺序保持不变。从其单一溶液中去除每种农药通常是最高的（特别是对于疏水性农药）。有机农药分子疏水性增加和亲水性降低会增加其在澄清剂上的吸附。
