Department of Chemistry and Physics, University of Almería, Agrifood Campus of International Excellence ceiA3 (ceiA3), Carretera Sacramento s/n, La Cañada de San Urbano, 04120, Almería, Spain.
Department of Zoology, University of Córdoba, Campus of Rabanales, 14071, Córdoba, Spain.
Anal Bioanal Chem. 2022 Mar;414(7):2419-2430. doi: 10.1007/s00216-022-03882-2. Epub 2022 Feb 17.
There is an increasing concern about the use of synthetic acaricides to fight the ectoparasitic mite Varroa destructor. Natural products such as formic acid (FA) and oxalic acid (OA) have emerged as a possible alternative control strategy. However, given the difficulty of analysing these highly polar compounds and the lack of robust and reliable methods, there are very few studies of the concentration and distribution of these natural acaricides in the beehive compartments. We present a reliable and simple analytical methodology, based on sample extraction with modified quick polar pesticide (QuPPe) methods followed by ion chromatography coupled to a quadrupole Orbitrap mass analyser for the analysis of FA and OA in honeybees, honey, beeswax, and beebread. The developed methods have been used in a field study for the evaluation of the presence and distribution of FA and OA in the beehive products, as well as in adult bees and bee brood samples, before, during, and up to 3 months after the application of the treatments by the beekeeper. Beebread and honey samples presented the highest concentration levels of OA and FA, respectively, mainly due to their natural presence. As expected, the organic acids showed low persistence in wax after the treatments. The natural acaricides were found in adult and developing bees at concentration levels below the reported LD50 in all the cases; however, residue levels of OA in larvae during the treatment application were very close to the reported LD50.
人们越来越关注使用合成杀螨剂来防治外寄生螨虫瓦螨。甲酸 (FA) 和草酸 (OA) 等天然产物已成为一种可能的替代控制策略。然而，由于分析这些高度极性化合物具有难度，并且缺乏稳健可靠的方法，因此关于这些天然杀螨剂在蜂箱隔室中的浓度和分布的研究非常少。我们提出了一种可靠且简单的分析方法，该方法基于使用改良的快速极性农药 (QuPPe) 方法进行样品提取，然后用离子色谱法与四极轨道阱质谱联用仪分析蜂蜜、蜂蜡和蜂粮中的 FA 和 OA。所开发的方法已用于一项现场研究，以评估在养蜂人进行处理之前、期间和处理后 3 个月，FA 和 OA 在蜂箱产品以及成年蜜蜂和蜜蜂幼虫样本中的存在和分布。蜂粮和蜂蜜样本分别呈现出最高的 OA 和 FA 浓度水平，这主要是由于它们的天然存在。正如预期的那样，在处理后，有机酸在蜂蜡中的持久性较低。在所有情况下，天然杀螨剂在成年和发育中的蜜蜂中的浓度水平均低于报告的 LD50；然而，在处理期间幼虫中的 OA 残留水平非常接近报告的 LD50。
