Monitoring of 49 Pesticides and 17 Mycotoxins in Wine by QuEChERS and UHPLC–MS/MS Analysis

Abstract

An effective method for the determination of 49 pesticide residues and 17 mycotoxins in wine by a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method and ultrahigh‐performance liquid chromatography–tandem mass spectrometry was developed. The target compounds were extracted with 1% (v/v) formic acid–acetonitrile, and no cleanup steps were required. The extracts were separated on a C18 chromatographic column (2.1 mm × 50 mm, 1.7 µm) with acetonitrile and water with 0.2% formic acid solution and ammonium acetate (10 mM) as the mobile phases under gradient elution at a flow rate of 0.2 mL/min. The determination was conducted using electrospray ionization in positive ion mode with multiple reaction monitoring. The analytes were quantified by comparison with matrix‐matched standard solutions. The good linearities were obtained in the range of 0.05 to 500.0 µg/kg, and the correlation coefficients were all greater than 0.9935. The average recoveries of the 66 target compounds ranged from 69% to 119%, and the RSDs were in the range of 1% to 10%. The limits of detection were in the range of 0.05 to 20.0 µg/kg. The method was proved to be rapid, selective, sensitive, and stable, and it has been applied to analysis of 64 wine samples.

An overview of chemical contaminants and other undesirable chemicals in alcoholic beverages and strategies for analysis

“…Solvent extraction and SPE are common, having been used for mycotoxins and pesticides in wine (Čuš et al., 2010; Nistor et al., 2017), for mycotoxins and imidazoles in beer (Inoue et al., 2013b; Klejdus, Moravcová, Lojková, Vacek, & Kubáň, 2006), and for the monitoring of PAHs in various wines and spirits (García‐Falcón & Simal‐Gándara, 2005). QuEChERS or modified QuEChERS are also employed for analyzing agricultural contaminants and acrylamide in beer and wine (Bogdanova et al., 2018; He et al., 2019), as well as techniques such as dispersive liquid–liquid microextraction (DLLME) for phthalates in wine (Fan, Liu, & Xie, 2014). Direct injection or injection after minimal preparation is also possible and has been done in beer, wine, and liquors, for multiple contaminant types (Akıllıoglu et al., 2011; Barbaste, Medina, & Perez‐Trujillo, 2003; Masson et al., 2012; Nagatomi et al., 2012; Pereira et al., 2011; Rejczak & Tuzimski, 2017; Shimizu et al., 2001; Stachova et al., 2016; Stärker & Welle, 2019; Xie et al., 2015).…”

“…LC is often coupled with MS (He et al., 2019; Klejdus et al., 2006; Sagratini et al., 2008), but may also utilize other detectors such as diode array detectors (DAD) (Fan et al., 2014; Stachova et al., 2016) or fluorescence detectors (García‐Falcón & Simal‐Gándara, 2005); this has largely been seen for mycotoxin analysis in beer and wines (Bryła et al., 2018; Di Stefano et al., 2015; Mably et al., 2005; Nigussie et al., 2018; Nistor et al., 2017), and has also been used for HMF and related compounds (Akıllıoglu et al., 2011; Masson et al., 2012; Pereira et al., 2011; Shimizu et al., 2001), migration contaminants (Fan et al., 2014; Xie et al., 2015), and colorants (Rejczak & Tuzimski, 2017; Stachova et al., 2016). For pesticides, nitrogen–phosphorus detectors (NPD) can be used, which has been demonstrated in wine (Cabras et al., 1999; Słowik‐Borowiec & Szpyrka, 2018).…”

“…Agricultural practices often involve the usage of agrochemicals; residues of glyphosate, a popular herbicide, have been detected in beer (Pflaum et al., 2016), and arsenic and copper residues, possibly stemming from fungicides or bactericides (EFSA, 2018; Moreira et al., 2011), have also been detected in wine and spirits, as well as traces of multiple vineyard fungicides and other pesticides in wine (IARC, 2010). Wine, in particular, has been a popular subject of research concerning pesticide residues; though the processing methods involved in winemaking can significantly reduce pesticide residue content, multiple studies have indicated remaining residues in wine samples produced experimentally or currently in the market (Cabras & Angioni, 2000; Čuš, Česnik, Bolta, & Gregorčič, 2010; González‐Rodríguez, Cancho‐Grande, & Simal‐Gándara, 2009; He et al., 2019). Azoxystrobin, dimethoate, and pyrimethanil show little reduction through the vinification process.…”

“…Wine is also a possible source of fungal toxins stemming from grapes. Ochratoxin, aflatoxins, deoxynivalenol, fumonisin B1, HT2 toxin, and patulin residues have been found in wines (He et al., 2019; IARC, 2010; Pang et al., 2017; Pflaum et al., 2016), with OTA being the most common problem, particularly in sweet red wines (Gil‐Serna, Vázquez, González‐Jaén, & Patiño, 2018). Similar to pesticides, the fermentation, clarification, and filtration steps are expected to effectively reduce the mycotoxin content, though evidently there are cases where the final level is still above detectable levels (Gil‐Serna et al., 2018).…”

Rapid Determination of 17 Phthalate Esters in Capsanthin by QuEChERS Coupled with Gas Chromatography-Mass Spectrometry

“…Therefore, it is very necessary to study the detection method of PAEs in plant extracts. In addition, the traditional pre-processing method is time-consuming and laborious, but the QuEChERS method is a "quick, easy, cheap, effective, rugged, safe" extraction method [9][10][11][12][13] . The method is first proposed by Anastassiades and others at the EPRW meeting in 2002, and in 2003 officially published a pre-treatment method for multi-pesticide residue analysis in agricultural products.…”