[en] Virgin olive oil quality assessment is critical for consumer protection and industry regulation. Fraudulent activities involving virgin olive oil are common worldwide. In Brazil, recent nationwide inspections have revealed recurrent cases of fraud, including the sale of adulterated or mislabeled olive oils. As a result, the Brazilian federal agency has suspended the commercialization of numerous brands and seized large quantities of products that failed to meet the official quality requirements. This study presents an automated analytical workflow for classifying Brazilian virgin olive oils based on their volatile organic compound (VOC) profiles. Headspace solid-phase microextraction (HS-SPME) and comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS) were used to analyze 215 certified virgin olive oil samples, categorized as either defective (VOO, virgin and LVOO, lampante virgin) or non-defective (EVOO, extra virgin), and 21 undisclosed oils (UNKN). Chemometric modeling using partial least squares-discriminant analysis (PLS-DA) was applied to the resulting data, which comprised 108 recurring VOCs. The PLS-DA model successfully differentiated between the two quality classes (defective and non-defective) with a predictive accuracy of 91% based on the external validation set. Key chemical markers driving the classification were identified. Non-defective oils were characterized by higher levels of C5 and C6 aldehydes and alcohols from the lipoxygenase (LOX) pathway, such as (E)-2-hexenal, associated with positive green and fruity notes. Conversely, defective oils showed higher levels of compounds such as nonanal and acetic acid, linked to rancidity and other off-flavors. Finally, the model was used to predict the quality of 21 previously undisclosed samples. This instrumental approach demonstrates a powerful and reliable alternative for forensic analysis of olive oils, generating models that can be interpreted in sensory terms.
Disciplines :
Food science
Author, co-author :
Cunha Paiva, Andre; Instituto de Química (IQ), Universidade Estadual de Campinas, Rua Monteiro Lobato, 270, Campinas, SP, 13083-862, Brazil ; Instituto Nacional de Ciência e Tecnologia (INCTBio), Campinas, SP, Brazil
Passos de Resende, Glaucimar Alex ; Université de Liège - ULiège > Molecular Systems (MolSys) ; Instituto de Química (IQ), Universidade Estadual de Campinas, Rua Monteiro Lobato, 270, Campinas, SP, 13083-862, Brazil ; Instituto Nacional de Ciência e Tecnologia (INCTBio), Campinas, SP, Brazil
Barbosa, Luidy Darllan; Instituto de Química (IQ), Universidade Estadual de Campinas, Rua Monteiro Lobato, 270, Campinas, SP, 13083-862, Brazil
Dantas Freitas, Daniel Lucas; OpenScience, Campinas, SP, Brazil
Sabin, Guilherme Post; OpenScience, Campinas, SP, Brazil
Hantao, Leandro Wang ; Instituto de Química (IQ), Universidade Estadual de Campinas, Rua Monteiro Lobato, 270, Campinas, SP, 13083-862, Brazil. wang@unicamp.br ; Instituto Nacional de Ciência e Tecnologia (INCTBio), Campinas, SP, Brazil. wang@unicamp.br ; Núcleo Interdisciplinar de Planejamento Energético (NIPE), Campinas, SP, Brazil. wang@unicamp.br
Language :
English
Title :
Quality assessment of Brazilian olive oils by GC×GC-MS and chemometrics.
Publication date :
May 2026
Journal title :
Analytical and Bioanalytical Chemistry
ISSN :
1618-2642
eISSN :
1618-2650
Publisher :
Springer Science and Business Media Deutschland GmbH, Germany
CAPES - Coordenação de Aperfeicoamento de Pessoal de Nível Superior FAPESP - Fundação de Amparo à Pesquisa do Estado de São Paulo CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
Funding text :
The Article Processing Charge (APC) for the publication of this research was funded by the Coordena\u00E7\u00E3o de Aperfei\u00E7oamento de Pessoal de N\u00EDvel Superior - Brasil (CAPES) (ROR identifier: 00x0ma614). This study received funding from the National Council for Scientific and Technological Development (CNPq) (Grants 302748/2018\u20130, 316202/2021\u20135, 408338/2024\u20135, and 306108/2025\u20139), the S\u00E3o Paulo Research Foundation (FAPESP) (Grant 2022/07406\u20131), and the Coordination for the Improvement of Higher Education Personnel (CAPES) (Finance Code 001). Additionally, the instruments used in this study were provided through funding from ANP/PETROBRAS (Grants 2019/00209\u20133 and 2019/00210\u20131).
Genovese A Caporaso N Leone T Paduano A Mena C Perez-Jimenez MA Sacchi R Use of odorant series for extra virgin olive oil aroma characterisation J Sci Food Agric 2019 99 1215 1224 10.1002/jsfa.9293 30066487
Veloso ACA Silva LM Rodrigues N Rebello LPG Dias LG Pereira JA Peres AM Perception of olive oils sensory defects using a potentiometric taste device Talanta 2018 176 610 618 10.1016/j.talanta.2017.08.066 28917798
UNESCO (2010) Decision of the intergovernmental committee: 5.COM 6.41. https://ich.unesco.org/en/decisions/5.COM/6.41. Accessed 27 Sep 2025
Cecchi L Migliorini M Giambanelli E Cane A Zanoni B Canuti V Mulinacci N Melani F Is the volatile compounds profile a suitable tool for authentication of virgin olive oils (Olea europaea L.) according to cultivars? A study by using HS-SPME-GC-MS and chemometrics Food Control 2022 139 10.1016/j.foodcont.2022.109092 109092
Marín X Grau-Noguer E Gervilla-Cantero G Ripolles-Avila C Castillo M Emerging technologies for detecting food fraud: a review of the current landscape in the 2020s Trends Food Sci Technol 2025 165 10.1016/j.tifs.2025.105313 105313
Ministério da Agricultura, Pecuária e Abastecimento (2012) Instrução Normativa no. 1/2012. https://sistemasweb.agricultura.gov.br/sislegis/action/detalhaAto.do?method=visualizarAtoPortalMapa&chave=629707739. Accessed 25 Aug 2025.
Grigoletto I Cevoli C Koidis A Gallina Toschi T Valli E Infrared spectroscopy and chemometrics for predicting commercial categories of virgin olive oils and supporting the panel test Food Res Int 2025 199 10.1016/j.foodres.2024.115347 39658151 115347
Brilhante NS Bizzo HR Caratti A Squara S Cordero C Artificial intelligence tools and concepts give access to authenticity and quality information in Brazilian olive oil volatilome J Food Compos Anal 2024 136 10.1016/j.jfca.2024.106826 106826
Kalogiouri NP Aalizadeh R Dasenaki ME Thomaidis NS Application of high-resolution mass spectrometric methods coupled with chemometric techniques in olive oil authenticity studies: a review Anal Chim Acta 2020 1134 150 173 10.1016/j.aca.2020.07.029 33059861
Melucci D Bendini A Tesini F Barbieri S Zappi A Vichi S Conte L Gallina Toschi T Rapid direct analysis to discriminate geographic origin of extra virgin olive oils by flash gas chromatography electronic nose and chemometrics Food Chem 2016 204 263 273 10.1016/j.foodchem.2016.02.131 26988501
Bortolomeazzi R Berno P Pizzale L Conte LS Sesquiterpene, alkene, and alkane hydrocarbons in virgin olive oils of different varieties and geographical origins J Agric Food Chem 2001 49 3278 3283 10.1021/jf001271w 11453763
Kritioti A Menexes G Drouza C Chemometric characterization of virgin olive oils of the two major Cypriot cultivars based on their fatty acid composition Food Res Int 2018 103 426 437 10.1016/j.foodres.2017.10.064 29389633
Lozano VA Jiménez-Carvelo AM Olivieri AC Kucheryavskiy SV Rodionova OY Pomerantsev AL Authentication of Argentinean extra-virgin olive oils using three-way fluorescence and two-way near-infrared data fused with multi-block DD-SIMCA Food Chem 2025 463 141127 10.1016/j.foodchem.2024.141127 39243625
Quintanilla-Casas B Rinnan Å Romero A Guardiola F Tres A Vichi S Bro R Using fluorescence excitation–emission matrices to predict bitterness and pungency of virgin olive oil: a feasibility study Food Chem 2022 395 10.1016/j.foodchem.2022.133602 35809549 133602
Lozano-Castellón J López-Yerena A Domínguez-López I Siscart-Serra A Fraga N Sámano S López-Sabater C Lamuela-Raventós RM Vallverdú-Queralt A Pérez M Extra virgin olive oil: a comprehensive review of efforts to ensure its authenticity, traceability, and safety Compr Rev Food Sci Food Saf 2022 21 2639 2664 10.1111/1541-4337.12949 35368142
Purcaro G Cordero C Liberto E Bicchi C Conte LS Toward a definition of blueprint of virgin olive oil by comprehensive two-dimensional gas chromatography J Chromatogr A 2014 1334 101 111 10.1016/j.chroma.2014.01.067 24556172
Stilo F Liberto E Reichenbach SE Tao Q Bicchi C Cordero C Untargeted and targeted fingerprinting of extra virgin olive oil volatiles by comprehensive two-dimensional gas chromatography–mass spectrometry: challenges in long-term studies J Agric Food Chem 2019 67 5289 5302 10.1021/acs.jafc.9b01661 30994349
Stilo F Liberto E Reichenbach SE Tao Q Bicchi C Cordero C Exploring the extra-virgin olive oil volatilome by adding extra dimensions to comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry featuring tandem ionization J AOAC Int 2021 104 274 287 10.1093/jaoacint/qsaa095 34020455
Granvogl M Schieberle P Turan NB Engin GO Bilgili MS The sensomics approach: a useful tool to unravel the genuine aroma blueprint of foods and aroma changes during food processing Comprehensive analytical chemistry 2022 Amsterdam Elsevier 41 68 99
Gerhardt N Schwolow S Rohn S Pérez-Cacho PR Galán-Soldevilla H Arce L Weller P Quality assessment of olive oils based on temperature-ramped HS-GC-IMS and sensory evaluation Food Chem 2019 278 720 728 10.1016/j.foodchem.2018.11.095 30583434
Ríos-Reina R Salatti-Dorado JÁ Ortiz-Romero C Cardador MJ Arce L Callejón R Comparative study of fluorescence and Raman spectroscopy for discrimination of virgin olive oil categories Food Control 2024 158 10.1016/j.foodcont.2023.110250 110250
Quintanilla-Casas B Torres-Cobos B Guardiola F Servili M Alonso-Salces RM Valli E Bendini A Toschi TG Vichi S Tres A Geographical authentication of virgin olive oil by GC–MS sesquiterpene hydrocarbon fingerprint Food Chem 2022 378 132104 10.1016/j.foodchem.2022.132104 35078099
Cecchi L Migliorini M Digiglio I Ugolini T Trapani S Zanoni B Mulinacci N Melani F Robust application of a chemometric model to support the panel test in virgin olive oil quality classification J Food Compos Anal 2025 141 10.1016/j.jfca.2025.107362 107362
Caratti A Fina A Trapani F Liberto E Jiménez-Herrera B Arce L Callejón RM Cordero C Beyond current quality indices: quantitative volatilomics and aroma blueprint of extra-virgin olive oils J Food Compos Anal 2025 137 106975 10.1016/j.jfca.2024.106975
Stilo F Jiménez-Carvelo AM Liberto E Bicchi C Reichenbach SE Cuadros-Rodríguez L Cordero C Chromatographic fingerprinting enables effective discrimination and identification of high-quality Italian extra-virgin olive oils J Agric Food Chem 2021 69 8874 8889 10.1021/acs.jafc.1c02981 34319731 8389832
Quintanilla-Casas B Bertin S Leik K Bustamante J Guardiola F Valli E Bendini A Toschi TG Tres A Vichi S Profiling versus fingerprinting analysis of sesquiterpene hydrocarbons Food Chem 2020 307 125556 10.1016/j.foodchem.2019.125556 31648180
van den Dool H Kratz PD A generalization of the retention index system including linear temperature programmed gas–liquid partition chromatography J Chromatogr A 1963 11 463 471 10.1016/S0021-9673(01)80947-X
Magagna F Valverde-Som L Ruíz-Samblás C Cuadros-Rodríguez L Reichenbach SE Bicchi C Cordero C Combined untargeted and targeted fingerprinting by comprehensive two-dimensional chromatography Anal Chim Acta 2016 936 245 258 10.1016/j.aca.2016.07.005 27566362
Stilo F Alladio E Squara S Bicchi C Vincenti M Reichenbach SE Cordero C Bizzo HR Quantitative 2D-fingerprinting of Brazilian and Italian extra-virgin olive oils J Food Compos Anal 2023 115 10.1016/j.jfca.2022.104899 104899
Stilo F Cordero C Sgorbini B Bicchi C Liberto E Highly informative fingerprinting of extra-virgin olive oil volatiles Separations 2019 6 34 10.3390/separations6030034
Daszykowski M Walczak B Massart DL Representative subset selection Anal Chim Acta 2002 468 91 103 10.1016/S0003-2670(02)00651-7
Snee RD Validation of regression models: methods and examples Technometrics 1977 19 415 428 10.1080/00401706.1977.10489581
Da Ros A Masuero D Riccadonna S Brkić Bubola K Mulinacci N Mattivi F Lukić I Vrhovsek U Complementary metabolomics for differentiation of extra virgin olive oils Molecules 2019 24 10.3390/molecules24162896 31404955 6720806 2896
Sumner LW Amberg A Barrett D Beale MH Beger R Daykin CA Fan TWM Fiehn O Goodacre R Griffin JL Hankemeier T Hardy N Harnly J Higashi R Kopka J Lane AN Lindon JC Marriott P Nicholls AW Reily MD Thaden JJ Viant MR Proposed minimum reporting standards for chemical analysis Metabolomics 2007 3 211 221 10.1007/s11306-007-0082-2 24039616 3772505
Quintanilla-Casas B Bustamante J Guardiola F García-González DL Barbieri S Bendini A Toschi TG Vichi S Tres A Virgin olive oil volatile fingerprint and chemometrics LWT 2020 121 10.1016/j.lwt.2019.108936 108936
Ortiz-Romero C Ríos-Reina R García-González DL Cardador MJ Callejón RM Arce L Comparing IR spectroscopy and GC-IMS for classifying virgin olive oil categories Food Chem X 2023 19 100738 10.1016/j.fochx.2023.100738 37389321 10300311
Paiva AC Teixeira CA Hantao LW Enhancing the understanding of aroma formation during coffee roasting using DHS-GC×GC-TOFMS and chemometrics ACS Omega 2025 9 26871 26883 10.1021/acsomega.5c01783
Luna G Morales MT Aparicio R Characterisation of 39 varietal virgin olive oils by their volatile compositions Food Chem 2006 98 243 252 10.1016/j.foodchem.2005.05.069
Morales MT Luna G Aparicio R Comparative study of virgin olive oil sensory defects Food Chem 2005 91 293 301 10.1016/j.foodchem.2004.06.011
Hachicha Hbaieb R Kotti F Gargouri M Msallem M Vichi S Ripening and storage conditions of Chétoui and Arbequina olives: part I Food Chem 2016 203 548 558 10.1016/j.foodchem.2016.01.089 26948650
Cecchi L Migliorini M Giambanelli E Rossetti A Cane A Melani F Mulinacci N HS-SPME-GC-MS quantification of the volatile profile of more than 1200 virgin olive oils J Agric Food Chem 2019 67 9112 9120 10.1021/acs.jafc.9b03346 31314506
Zunin P Boggia R Salvadeo P Evangelisti F Geographical traceability of West Liguria extra-virgin olive oils J Chromatogr A 2005 1089 243 249 10.1016/j.chroma.2005.07.005 16130793
Vichi S Guadayol JM Caixach J López-Tamames E Buxaderas S Monoterpene and sesquiterpene hydrocarbons of virgin olive oil J Chromatogr A 2006 1125 117 123 10.1016/j.chroma.2006.05.029 16756984
Vichi S Lazzez A Kamoun NG López-Tamames E Buxaderas S Evolution of sesquiterpene hydrocarbons during fruit ripening J Agric Food Chem 2010 58 6972 6976 10.1021/jf100497c 20455560
Damascelli A Palmisano F Sesquiterpene fingerprinting by HS-SPME-GC-MS Food Anal Methods 2013 6 900 905 10.1007/s12161-012-9500-9
Ugolini T Mattagli F Melani F Zanoni B Migliorini M Trapani S Giambanelli E Parenti A Mulinacci N Cecchi L HS-SPME-GC-MS and chemometrics for monovarietal extra virgin olive oil quality control J Agric Food Chem 2024 72 11124 11139 10.1021/acs.jafc.4c00610 38698543
Lukić I Carlin S Horvat I Vrhovsek U Combined targeted and untargeted profiling of volatile aroma compounds Food Chem 2019 270 403 414 10.1016/j.foodchem.2018.07.133 30174064
