Ion-Mobility-Derived Collision Cross Section as an Additional Identification Point for Multiresidue Screening of Pesticides in Fish Feed

Abstract

Ion mobility spectrometry allows for the measurement of the collision cross section (CCS), which provides information about the shape of an ionic molecule in the gas phase. Although the hyphenation of traveling-wave ion mobility spectrometry (TWIMS) with high-resolution quadrupole time-of-flight mass spectrometry (QTOFMS) has been mainly used for structural elucidation purposes, its potential for fast screening of small molecules in complex samples has not yet been thoroughly evaluated. The current work explores the capabilities of ultrahigh-performance liquid chromatography (UHPLC) coupled to a new design TWIMS-QTOFMS for the screening and identification of a large set of pesticides in complex salmon feed matrices. A database containing TWIMS-derived CCS values for more than 200 pesticides is hereby presented. CCS measurements showed high intra- and interday repeatability (RSD < 1%), and they were not affected by the complexity of the investigated matrices (ΔCCS ≤ 1.8%). The use of TWIMS in combination with QTOFMS was demonstrated to provide an extra-dimension, which resulted in increased peak capacity and selectivity in real samples. Thus, many false-positive detections could be straightforwardly discarded just by applying a maximum ΔCCS tolerance of ±2%. CCS was proposed as a valuable additional identification point in the pesticides screening workflow. Several commercial fish feed samples were finally analyzed to demonstrate the applicability of the proposed approach. Ethoxyquin and pirimiphos-methyl were identified in most of the analyzed samples, whereas tebuconazole and piperonil butoxide were identified for the first time in fish feed samples.

Towards the use of ion mobility mass spectrometry derived collision cross section as a screening approach for unambiguous identification of targeted pesticides in food

“…Introductory work using these new features confirmed the higher degree of selectivity of the screening method when using ion mobility . Since then, the approach has been successfully tested and validated . Nonetheless, the reported travelling wave CCS ( TW CCS) screening workflows utilized IM at the ultimate step after closing down the retention time and mass accuracy windows.…”

Comprehensive overview of feed‐to‐fillet transfer of new and traditional contaminants in Atlantic salmon and gilthead sea bream fed plant‐based diets

“…In particular, AQUAMAX (2006–2010) and ARRAINA (2012–2016) EU projects have highly contributed on this, providing valuable samples but also adequate analytical methods and approaches to assess the presence of potential contaminant residues in the aquaculture food chain (Justino et al., ; Nácher‐Mestre, Ibáñez, Serrano, Pérez‐Sánchez, & Hernández, ; Nácher‐Mestre, Serrano, Hernández, Benedito‐Palos, & Pérez‐Sánchez, ; Nácher‐Mestre, Serrano, Benedito‐Palos, et al., ; Nácher‐Mestre, Serrano, Portolés, et al., ; Nácher‐Mestre, Serrano, Benedito‐Palos, et al., ; Nácher‐Mestre et al., , ; Portolés, Garlito, Nácher‐Mestre, Berntssen, & Pérez‐Sánchez, ; Portolés, Ibáñez, et al., ; Regueiro, Negreira, & Berntssen, ). Advanced analytical methodologies based on the use of both gas chromatography (GC) and liquid chromatography (LC) coupled with low‐ and high‐resolution mass spectrometry (MS and HRMS, respectively) make feasible to analyse large lists of organic compounds (Portolés, Ibáñez, et al., ; Regueiro et al., ). Traditional target methods are usually focused on a reduced list of organic compounds, generally with quantitative purposes and using tandem MS techniques (Nácher‐Mestre, Serrano, Portolés, et al., ; Nácher‐Mestre, Serrano, Hernández, et al., ; Saera‐Vila et al., ; Serrano, Barreda, Pitarch, & Hernández, ).…”

“…Besides, these specific contaminants, other nontarget (non‐pre‐selected) unknown and/or nonexpected undesirables, can potentially contribute to food safety of farmed fish. This is an analytical challenge that requires, among others, the application of wide‐scope analytical methodologies able to detect and identify a large number of very different potential undesirables in the aquaculture food chain as reported elsewhere (Hernández et al., ; Justino et al., ; Nácher‐Mestre et al., , , ; Portolés, Ibáñez, et al., ; Regueiro et al., ).…”

Recent Advances and Future Challenges in Modified Mycotoxin Analysis: Why HRMS Has Become a Key Instrument in Food Contaminant Research

“…Hence, the overall peak capacity of the method is increased [81,82] making IM-MS highly suitable for food safety control analysis. In this frame, a broad range of food contaminants such as herbicides [83], pesticides [75,84], mycotoxins [71,77,78], and veterinary drug residues [85] have been successfully detected by IMS.…”

“…Therefore, the CCS tolerance of ±2% in combination with the traditional confirmation threshold filters of m / z (±5/10 ppm) and retention time (±2.5%) will lead to a more definitive identification of the species of interest. A further dataset providing CCS values for 200 pesticides has been recently reported by Regueiro et al [84]. …”