Novel multiresidue method for determination of pesticides in red wine using gas chromatography–mass spectrometry and solid phase extraction Maja Pelajic ´ a,⇑ , Gorana Pec ˇek b , Dragana Mutavdz ˇic ´ Pavlovic ´ c , Dubravka Vitali C ˇ epo d a Croatian Centre for Agriculture, Food and Rural Affairs, Institute for Plant Protection, Rim 98, 10000 Zagreb, Croatia b Ministry of Agriculture, Phytosanitary Sector, Department of Plant Protection Products, Grada Vukovara 68, 10000 Zagreb, Croatia c Department of Analytical Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, Marulic ´ev trg 19, 10000 Zagreb, Croatia d Faculty of Pharmacy and Biochemistry, University of Zagreb, A. Kovac ˇic ´a 1, 10000 Zagreb, Croatia article info Article history: Received 1 July 2015 Received in revised form 28 December 2015 Accepted 6 January 2016 Available online 7 January 2016 Keywords: Multiresidue method GC–MS Pesticide residues Red wine Solid phase extraction abstract A new multiresidue method was developed for determination of 25 pesticide residues in red wine by gas chromatography coupled to mass spectrometry with a single run of 23.63 min. Samples were extracted from wine with solid phase extraction using Oasis HLB. Mixture of methanol and water was used for rins- ing, while acetonitrile and n-hexane were used as elution solvents. Method was validated according to SANCO/12571/2013 criteria in wide linearity range (limit of quantification – 400 lgL À1 ). Limits of quan- tification (LOQ) were well below 10 lgL À1 for most pesticides and recoveries at 2 Â LOQ and 10 Â LOQ concentration levels were in range 70–120%. Precision, expressed as a relative standard deviation, was always under 14%. The method was applied to 32 red wine samples from Croatia. Pesticides were detected in 30 samples with a total of 15 pesticides found, 7 of which were at a high concentration. Ó 2016 Elsevier Ltd. All rights reserved. 1. Introduction The use of agrochemicals is important part of harvest quality and food protection (Herrero-Hernández et al., 2013). Vineyards are one of the most widespread crops with inevitable usage of pes- ticides. Conventional cultivation of wine is characterized by signif- icant use of number of different groups of pesticides. The most common group is fungicides, which are applied to the vine grape. Many of these products are resistant to fermentation process which results in their presence in the final product affecting the wine quality and consumer health (Jiménez, Bernal, del Nozal, Bernal, & Toribio, 2007). The European Union has set maximum residue levels (MRLs) for pesticides in vine grapes. However, MRLs for wine are still scarcely established. The approach in wine prod- ucts is the same as in other processed food products. MRLs of raw products are applicable to processed food products taking into account product processing. Although technological processing of wine and fermentation result in a decrease in pesticide concentra- tions, in recent years a number of studies indicate wine contamina- tion with pesticides concentration above MRLs (Economou, Botitsi, Antoniou, & Tsipi, 2009). Therefore, with growing popularity of wine and estimated worldwide wine consumption of 240 million hectoliters (OIV (International Organization of Vine, 2012), contin- uous monitoring of pesticide levels in wine is essential not only for consumers’ health protection, but also for establishing legislations for wine contamination. Frequent application of various pesticides simultaneously requires a determination of as many compounds as possible in a single analysis. One way to approach the problem of pesticides determination is the development of multiresidue methods (Wilkowska & Biziuk, 2011). The most common determination techniques include liquid (LC) or gas chromatography (GC) coupled to different detectors. Mass spectrometry (MS) represents power- ful detection characteristics because of its sensitivity and confir- mation power (Camino-Sánchez et al., 2011). GC–MS is probably the most common determination technique for multiresidue pesti- cides analysis in food and environmental products (Jiménez et al., 2007; Lesueur, Knittl, Gartner, Mentler, & Fuerhacker, 2008; Maštovska & Lehotay, 2004; Park et al., 2011; Soleas, Yan, Hom, & Goldberg, 2000; Wong et al., 2003; Yang et al., 2011). Recently, a number of techniques such as liquid chromatography coupled with tandem mass spectrometry (MS/MS) have been developed (Camino-Sánchez et al., 2011; Carpinteiro, Ramil, Rodríquez, & Cela, 2010; Economou et al., 2009; Fontana, Rodríquez, Ramil, http://dx.doi.org/10.1016/j.foodchem.2016.01.018 0308-8146/Ó 2016 Elsevier Ltd. All rights reserved. ⇑ Corresponding author. E-mail address: maja.pelajic@hcphs.hr (M. Pelajic ´). Food Chemistry 200 (2016) 98–106 Contents lists available at ScienceDirect Food Chemistry journal homepage: www.elsevier.com/locate/foodchem