Determination of type B fumonisin mycotoxins in maize and maize‐based products by liquid chromatography/tandem mass spectrometry using a QqQ_{linear ion trap} mass spectrometer

Abstract

A sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for determining the type B fumonisin mycotoxins in corn-based foodstuffs is described. Fumonisins FB1 and FB2 were extracted from a 1 g sample by homogenization with acetonitrile/water (75:25, v/v, 50 mmol/L formic acid, 25 mL final volume) and the extract was defatted on C18 phase. Volumes of 5 mL of crude extracts were cleaned up on Carbograph-4 cartridges. The final solution was analyzed by HPLC with electrospray ionization mass spectrometry in positive ion mode using multiple reaction monitoring with a QqQ linear ion trap mass spectrometer. Recoveries for spiked corn-based foodstuffs ranged from 91-105% (RSD% < or =8%), and method detection limits were < or =2 ng/g for FB1 and < or =1 ng/g for FB2. Two different spiking levels were tested (5000 and 100 ng/g for FB1, 1000 and 20 ng/g for FB2). Quantitation was achieved by an external calibration procedure using matrix-matched standards, with diclofenac added post-cleanup as internal standard for the LC/MS/MS analyses. Calibration curves showed linearity in the concentration range 0.005-5 ng/microL of final extract (0.992 < or = R2< or =0.995). Two other fumonisins, FB3 and FB4, were identified in naturally contaminated samples of corn meal using an information-dependent acquisition protocol that looped three experiments, including neutral loss scan, enhanced resolution scan, and enhanced product ion scan. FB3 and FB4 quantitation was estimated as peak area ratios relative to the FB2 response in view of the lack of both standards. This work also includes an application of the present LC/MS/MS method to some maize and maize-based product samples (corn meal, cornflakes and popcorn) collected from Italian stores. FB1 and FB2 contamination levels exceeding the European Union recommendation were found in 8 out of 15 corn meal samples.

Ultra-high-performance liquid chromatography-tandem mass spectrometry for the analysis of free and conjugated natural estrogens in cow milk without deconjugation

“…As already reported, molecular structures containing aromatic rings as estrogens are strongly retained by the GCB surface [31,32] and were not eluted by methanol (non acidic compounds) or acidified methanol (acidic compounds). Therefore, 10 mL of methanol acidified with 50 mmol L −1 formic acid and 5 mL of methanol could be passed through the cartridge to eliminate some interfering compounds without any analyte loss.…”

“…As formerly reported, this sorbent can behave both as RP and as anion-exchanger sorbent, retaining from aqueous samples acidic compounds. Moreover, these characteristics make it suitable for isolating acidic substances from neutral and basic ones [25,31], and therefore, it could be a suitable adsorbent for our purpose to isolate from milk free estrogens (neutral) and the conjugated metabolites (acidic) in two separated fractions, but in a single loading step.…”

Simple and high-throughput method for the multimycotoxin analysis in cereals and related foods by ultra-high performance liquid chromatography/tandem mass spectrometry

“…Due to scarce volatility of mycotoxins, GC-MS determination (Krska, Baumgartner, & Josephs, 2001;Melchert & Pabel, 2004;Schollenberger et al, 2008) is possible after a suitable derivatisation step. In consequence, LC based methods, using several analysers such as single quadrupole (Garon et al, 2006;Silva et al, 2009), time of flight (TOF) (Tanaka, Takino, Sugita-Konishi, & Tanaka, 2006), and mainly tandem mass spectrometry (MS/MS) (Berthiller, Schuhmacher, Buttinger, & Krska, 2005;Cavalieri, Foglia, Pastorini, Samperi, & Laganà, 2005;Cervino, Asam, Knopp, Rycillik, & Niessner, 2008;D'Arco, Fernández-Franzón, Font, Damiani & Mañes, 2008;Faberi, Foglia, Pastorini, Samperi, & Laganà, 2005;Lattanzio, Solfrizzo, Powers, & Visconti, 2007;Silva et al, 2009;Spanjer, Rensen, & Scholten, 2008;Sulyok, Berthiller, Krska, & Schuhmacher, 2006), are more frequently applied. Most of these chromatographic methods are based on the determination of a single mycotoxin or multiple mycotoxins belonging to the same group (Berthiller et al, 2005;Cervino et al, 2008;D'Arco et al, 2008;Faberi et al, 2005;Silva et al, 2009), whereas the number of methods for the simultaneous determination of more than one group of mycotoxin is still limited (Cavalieri et al, 2005;Lattanzio et al, 2007;Sulyok et al, 2006).…”

“…In consequence, LC based methods, using several analysers such as single quadrupole (Garon et al, 2006;Silva et al, 2009), time of flight (TOF) (Tanaka, Takino, Sugita-Konishi, & Tanaka, 2006), and mainly tandem mass spectrometry (MS/MS) (Berthiller, Schuhmacher, Buttinger, & Krska, 2005;Cavalieri, Foglia, Pastorini, Samperi, & Laganà, 2005;Cervino, Asam, Knopp, Rycillik, & Niessner, 2008;D'Arco, Fernández-Franzón, Font, Damiani & Mañes, 2008;Faberi, Foglia, Pastorini, Samperi, & Laganà, 2005;Lattanzio, Solfrizzo, Powers, & Visconti, 2007;Silva et al, 2009;Spanjer, Rensen, & Scholten, 2008;Sulyok, Berthiller, Krska, & Schuhmacher, 2006), are more frequently applied. Most of these chromatographic methods are based on the determination of a single mycotoxin or multiple mycotoxins belonging to the same group (Berthiller et al, 2005;Cervino et al, 2008;D'Arco et al, 2008;Faberi et al, 2005;Silva et al, 2009), whereas the number of methods for the simultaneous determination of more than one group of mycotoxin is still limited (Cavalieri et al, 2005;Lattanzio et al, 2007;Sulyok et al, 2006). In general, these methods require considerable analysis time (higher than 20 min) (Cavalieri et al, 2005;Lattanzio et al 2007;Spanjer et al, 2008;Tanaka et al, 2006), and in some cases, two injections are required (Sulyok et al, 2006), as well as the application of a clean-up step (Cavalieri et al, 2005;Lattanzio et al, 2007;Tanaka et al, 2006 ).…”

Mycotoxins in breakfast cereals from the Canadian retail market: A 3-year survey

“…They have been determined in corn-based breakfast cereals in Canada (Scott and Lawrence 1994;Kuiper-Goodman et al 1996;Lawrence et al 2000;Kim et al 2003;Park et al 2004), the USA (Stack andEppley 1992;Pohland 1996;Castelo et al 1998), Brazil (Machinski andSoares 2000;Scaff and Scussel 2004), Uruguay (Piñ eiro et al 1997), Argentina (Solovey et al 1999), Czech Republic (Ostrý and Ruprich 1998), Spain (Sanchis et al 1994;Velluti et al 2001), Denmark (Petersen and Thorup 2001), Germany (Schneider et al 1995;Bresch et al 1998;Usleber and Märtlbauer 1998;Meister 1999;SCOOP 2003), Italy (Doko and Visconti 1994;Solfrizzo et al 2001;Cirillo et al 2003;SCOOP 2003;Faberi et al 2005), Switzerland (Pittet et al 1992), Belgium (Paepens et al 2005), France (Leblanc et al 2005, Molinié et al 2005, the Netherlands (De Nijs et al 1998), Sweden (SCOOP 2003, the UK (Patel et al 1997;Candlish et al 2000), Taiwan (Tseng and Liu 1997), and Korea (Kim et al 2002). In previous Canadian surveys FB 1 was frequently detected in corn-based breakfast cereals.…”