García-Reyes Juan F, Gilbert-López Bienvenida, Molina-Díaz Antonio, Fernández-Alba Amadeo R
Analytical Chemistry Research Group, Department of Physical and Analytical Chemistry, University of Jaén, 23071 Jaén, Spain.
Anal Chem. 2008 Dec 1;80(23):8966-74. doi: 10.1021/ac8012708.
Here we report the first worldwide reconnaissance study of the presence and occurrence of pesticides in fruit-based soft drinks. While there are strict regulations and exhaustive controls for pesticides in fruits, vegetables, and drinking water, scarce attention has been paid to highly consumed derivate products, which may contain these commodities as ingredients. In the case of the fruit-based soft drinks industry, there are no clear regulations, relating to pesticides, which address them, even when there is significant consumption in vulnerable groups such as children. In this work, we have developed a screening method to search automatically for up to 100 pesticides in fruit-based soft drinks extracts based on the application of liquid chromatography-electrospray time-of-flight mass spectrometry (LC-TOF MS). The sample extracts injected were obtained by a preliminary sample treatment step based on solid-phase extraction using hydrophilic-lipophilic balanced polymer-based reverse phase cartridges and methanol as eluting solvent. Subsequent identification, confirmation, and quantitation were carried out by LC-TOF MS analysis: the confirmation of the target species was based on retention time matching and accurate mass measurements of protonated molecules ([M + H]+) and fragment ions (obtaining accuracy errors typically lower than 2 ppm). With the proposed method, we measured over 100 fruit-based soft drink samples, purchased from 15 different countries from companies with brands distributed worldwide and found relatively large concentration levels of pesticides in most of the samples analyzed. The concentration levels detected were of the micrograms per liter level, low when considering the European maximum residue levels (MRLs) set for fruits but very high (i.e., 300 times) when considering the MRLs for drinking or bottled water. The detected pesticides (carbendazim, thiabendazole, imazalil and its main degradate, prochloraz and its main degradate, malathion, and iprodione) are mainly those applied to crops in the final stages of production (postharvest treatment), some of them contain chlorine atoms in their structures. Therefore, steps should be taken with the aim of removing any traces of pesticides in these products, in order to avoid this source of pesticide exposure on the consumer, particularly on vulnerable groups with higher exposure, such as children.
在此，我们报告了第一项关于水果基软饮料中农药存在情况的全球普查研究。虽然对水果、蔬菜和饮用水中的农药有严格规定和详尽管控，但对于大量消费的衍生产品却很少关注，而这些产品可能含有这些农产品作为原料。就水果基软饮料行业而言，即使在儿童等弱势群体大量消费的情况下，也没有关于农药的明确规定来对其进行规范。在这项工作中，我们开发了一种筛查方法，基于液相色谱 - 电喷雾飞行时间质谱（LC - TOF MS）的应用，自动在水果基软饮料提取物中搜索多达100种农药。注入的样品提取物是通过基于使用亲水亲脂平衡聚合物基反相柱和甲醇作为洗脱溶剂的固相萃取的初步样品处理步骤获得的。随后通过LC - TOF MS分析进行鉴定、确认和定量：目标物种的确认基于保留时间匹配以及质子化分子（[M + H]+）和碎片离子的精确质量测量（获得的精度误差通常低于2 ppm）。使用所提出的方法，我们测量了从15个不同国家购买的、来自全球销售品牌公司的100多个水果基软饮料样品，发现大多数分析样品中的农药浓度水平相对较高。检测到的浓度水平为每升微克级，相对于为水果设定的欧洲最大残留限量（MRLs）较低，但相对于饮用水或瓶装水的MRLs则非常高（即高出300倍）。检测到的农药（多菌灵、噻菌灵、抑霉唑及其主要降解产物、咪鲜胺及其主要降解产物、马拉硫磷和异菌脲）主要是在生产最后阶段施用于作物的那些（采后处理），其中一些在其结构中含有氯原子。因此，应采取措施以去除这些产品中的任何农药痕迹，以避免消费者接触这种农药来源，特别是对于接触风险较高的弱势群体，如儿童。
