Extending Calibration Anchors Resolves Low-m/z Shifts in Negative-Mode Orbitrap Workflows Francisco José Díaz-Galiano, Bruno Le Bizec Journal of the American Society for Mass Spectrometry, 2026 Reliable mass accuracy is essential for the confident identification of diagnostic fragment ions in high-resolution mass spectrometry. During the analysis of perfluoroalkyl sulfonic acids (PFSAs) with a Q Exactive Orbitrap, we consistently observed the characteristic O 3 Ṡ – fragment, expected at a mass-to-charge ratio ( m / z ) of 79.9574, reported at m / z 79.9568, a systematic deviation of approximately −6 parts per million (ppm). Similar errors affected other ions below m / z 100, while precursors and higher- m / z fragments remained within the specification. Comparison with an Exploris 120 instrument, calibrated with anchors down to m / z 59, confirmed that the deviation is not intrinsic to the ion but originates from the limited calibration range of the Q Exactive standard calibration solution. We demonstrate that extending calibration to include additional low- m / z anchors generated in situ by in-source fragmentation fully corrects the error without affecting the accuracy at a higher m / z . This adjustment resolves systematic deviations for ions below m / z 100 in the Q Exactive instruments.
Assess farming production models in tomato crops using a metabolomic approach based on high-resolution mass spectrometry Adrián Rosa García, Francisco José Díaz-Galiano, María Jesús Martínez Bueno, Amadeo R. Fernández-Alba Microchemical Journal, 2025 The lack of reliable chemical markers to distinguish agricultural practices leaves the organic market vulnerable to food fraud. Metabolomic approaches using ultrahigh-performance liquid chromatography coupled with high-resolution-mass-spectrometry (UHPLC-HRMS) and multivariate statistical analysis can identify differences between crops from conventional and organic farming. This approach also helps detect fraudulent organic practices, such as the minimal use of synthetic fertilisers or phytosanitary products, which alter crop metabolism, as shown in this study on tomatoes. The principal component analysis (PCA) of the HRMS compound profiles revealed distinct groups based on the type and amount of fertilisation applied. A negative correlation was observed between the levels of synthetic fertilisers and the abundance of certain markers. Thirteen bioactive compounds, including carotenoids, sterols, and vitamins, were identified as potential markers to differentiate production methods. Taken together, these findings lay an important foundation for differentiating agricultural practices and for developing future classification models to support the integrity of organic products. • The methodology allowed the tentative identification of 13 bioactive compounds. • Seven of them have been reported for the first time in tomato. • The approach differentiated tomatoes grown under different agronomic conditions. • The more fertiliser, the lower the relative abundance of biochemical markers.
Evaluation of the honeybee exposome in European apiaries by combining passive samplers and liquid chromatography with Zeno trap-time-of-flight mass spectrometry María del Mar Gómez-Ramos, María José Gómez-Ramos, Francisco José Díaz-Galiano, María Murcia-Morales, José Luis Oller-Serrano, Maritta Martikkala, Preben Kristiansen, Flemming Vejsnæs, Amadeo R. Fernández-Alba Environmental Pollution, 2025 This study introduces an analytical methodology that combines passive sampling with ultra-high pressure liquid chromatography coupled with a high-end quadrupole-time-of-flight mass spectrometer (UHPLC-QTOF-MS) for monitoring the honeybee ( Apis mellifera L .) exposome across various European regions and seasons. The sampling methodology employs the recently developed adsorb pesticide in-hive strips (APIStrip) passive samplers, which use TENAX® TA adsorbent, to collect a wide range of chemicals when placed inside beehives. Following acetonitrile-based desorption, extracts were analyzed by UHPLC-QTOF-MS, equipped with an advanced ion trap –the Zeno trap– that enhances tandem-mass spectrometry (MS/MS) signals and improves mass accuracy, facilitating efficient feature annotation. A non-targeted analysis (NTA) approach, combined with multivariate analysis, was used to simultaneously identify exposure analytes (e.g.natural products) and effect-related metabolites associated with honeybee health and condition (e.g. pheromones and other compounds emitted by bees). This methodology revealed geographical and seasonal variations in the chemical profiles of honeybee hives. In the evaluated Nordic countries, natural products from plants and pollen, along with bee-emitted substances such us neurotransmitters and pheromones, were prevalent. Seasonal analysis in Denmark revealed distinct chemical profiles associated with blooming flowers and peak brood rearing activity in April. This integrated, non-invasive methodology has proven highly effective in assessing the honeybee exposome, providing valuable insights into how environmental factors influence the chemical profiles emitted by bees. • Assessment of honeybee exposome to evaluate environmental impact or bee health. • Combined passive sampling and UHPLC-QTOF-MS to monitor in-hive chemical exposure. • APIStrip and UHPLC-QTOF-MS with ion trap to improve chemical analysis. • Identified geographical and seasonal variations in -hive chemical profiles. • This approach provides a comprehensive view of bee colonies' chemical environment.
Improved efficiency of ion trapping time-of-flight mass spectrometry for the analysis of pesticide residues and mycotoxins at trace levels in baby food Lorena Manzano-Sánchez, Francisco José Díaz-Galiano, José Antonio Martínez, Carmen Ferrer, Amadeo Rodríguez Fernández-Alba Talanta, 2024 The analysis of pesticide residues and mycotoxins in baby food demands exceptionally low limits of quantitation, necessitating the use of highly sensitive instruments capable of conducting trace analyses. High-resolution instruments typically fail to detect such low levels. However, the latest advancements in liquid time-of-flight technology, when coupled with ion trapping, enable ion enrichment, thereby improving detection levels. This allows for the analysis of these substances at low concentration levels, benefiting from enhanced mass accuracy. Additionally, the use of mass accuracy data helped eliminate matrix interferences, thereby enabling high-confidence identification. We developed a multi-residue method to analyse 219 pesticide residues and 9 mycotoxin residues in baby food matrices. Utilizing a QuEChERS-based extraction method, the samples were then analysed using an LC-ZenoTOF 7600 system with mass window screening acquisition. For pesticides, the limit of quantitation was 0.001-0.003 mg/kg for 81 % of the evaluated compounds, 0.005 mg/kg for 13 %, 0.010 mg/kg for 4 % and 0.020-0.030 for 2 %; good linearities were obtained at these levels. Apparent recoveries were evaluated at 0.003, 0.005, and 0.010 mg/kg. At the lowest recovery level, 93 % of compounds showed recoveries between 70 and 120 %. The rest of the compounds were in the range of 63-129 %, with relative standard deviation values below 20 %. For mycotoxins, the limits of quantitation ranged from 0.0001 to 0.100 mg/kg, with matrix-matched concentrations assessed within this range. Recoveries were evaluated at low concentration range (0.001-0.003 mg/kg) and high range (0.020-0.050) with apparent recoveries values between 92 and 140 %. Finally, a total of 31 commercial baby food samples were analysed using this method. The results indicated that 16 samples contained pesticide residues, while two samples were found to have mycotoxins.
Alfred Otto Carl Nier: On the Shoulders of a Mass Spectrometry Giant Francisco José Díaz-Galiano Journal of the American Society for Mass Spectrometry, 2024 This Perspective pays homage to Alfred Otto Carl Nier, whose substantial contributions were fundamental in shaping the mass spectrometry field into a key technology in research and industry. On the 30th anniversary of his passing, on May 16, 1994, this paper explores Nier's role in the field of mass spectrometry through an overview of his published works, key interviews, and archival material. Nier, originally an electrical engineer turned physicist, spent most of his scientific career at the University of Minnesota. His many innovations, both instrumental and methodological, encompassed advanced fields such as isotopic research, tracer studies, geochronology, or space research. Nier improved sector mass spectrometers, participated in the development of the isotope-ratio mass spectrometry field, developed a double-focusing sector mass spectrometer, and was a relevant member of the Manhattan Project. Today, Nier's influence persists, inspiring new generations of scientists engaged in cutting-edge research, from environmental studies to planetary exploration. His legacy thrives as current technologies and scientific strategies still echo his innovations and foresight.
Ions on the move: The combination of ion mobility and food metabolomics Francisco José Díaz-Galiano, María Murcia-Morales, Víctor Cutillas, Amadeo R. Fernández-Alba Trends in Food Science and Technology, 2024 The application of ion mobility coupled with mass spectrometry in food metabolomics has become increasingly popular since 2014, although it is still a niche combination in the field of food metabolomics and authentication. This growth can be attributed to its unique capability of offering detailed molecular analysis, which is crucial for accurate identification and quantification of compounds in complex food matrices. The review focuses on ion mobility spectrometry techniques such as drift tube ion mobility spectrometry, travelling wave ion mobility spectrometry, and other specialised techniques. We look at their ability to distinguish molecular species, especially isomers, which enhances the accuracy and depth of food metabolomic studies. Practical examples in which ion mobility significantly improved metabolite identification are described. The findings show that ion mobility significantly improves (i) the number of metabolites characterised and (ii) the reliability of the structure assignation. Moreover, they show the reproducibility of ion mobility measurements in natural products, providing enhanced identification capabilities that are crucial in food authentication processes. The review concludes that the use of ion mobility mass spectrometry offers significant advancements in the field of food metabolomics, leading to a more accurate and comprehensive understanding of food composition.
