Multidimensional capillary liquid chromatography-tandem mass spectrometry for the determination of multiclass pesticides in ``sugarcane spirits{''} (cachacas)

Cachaca or ``sugarcane spirit{''} is a Brazilian beverage considered the third most consumed beverage worldwide. Sugarcane, its raw material, is one of the main crops developed in the country, placing Brazil as the largest producer of this commodity on a global scale. Considering the growth in sugarcane production, many farmers use pesticides in their crops. However, excess pesticides can be accumulated in products derived from sugarcane, creating an environmental and public health concern. In this context, the development of analytical methods capable of identifying residues of pesticides in cachacas and other sugarcane-derived products is essential to ensure the beverage's quality. This work presents a method to quantify multiclass pesticides in Brazilian sugarcane spirits (cachacas) through an automated multidimensional system. The first dimension consists of an extraction column packed with a graphene-silica phase, followed by a capillary liquid chromatography-tandem mass spectrometry system as the second dimension. The method was optimized by an experimental design, in which the influence of three variables was evaluated on the extraction process: percentage of acetonitrile, loading flow, and loading time. Afterward, twenty-two cachacas were analyzed to ascertain the applicability of the proposed method. The analyses reported five samples containing clomazone (a type of herbicide widely used in sugarcane production). The method showed good linearity under optimized conditions, with correlation coefficients greater than 0.981, and limits of detection and quantification of 5 mu g L(-1)and 10 mu g L-1, respectively. The herein discussed results suggest that the proposed method could be a practical option for identifying pesticides in beverages. (AU)