LDPE and PLA Active Food Packaging Incorporated with Lemon by-Products Extract: Preparation, Characterization and Effectiveness to Delay Lipid Oxidation in Almonds and Beef Meat.

Low-density polyethylene-based packaging with 4% lemon extract (LDPE/4LE) and two polylactic-based (PLA) packaging materials with 4% and 6% lemon extract (PLA/PEG/4LE and PLA/6LE) were produced. O2 and water permeability tests were performed, the total and individual phenolic compounds content were measured, and the films' antioxidant activities were determined. The films' ability to delay lipid oxidation was tested in two model foods: almonds, packaged with LDPE/4LE, PLA/4LE and PLA/6LE for a maximum period of 60 days at 40 °C (accelerated assay); and beef meat, packaged with the PLA/6LE for a maximum period of 11 days at 4 °C. The LE improved the WVP in all of the active films by 33%, 20% and 60% for the LDPE/4LE, PLA/4LE and PLA/6LE films, respectively. At the end of 10 days, the migration of phenolic compounds through the PLA films was measured to be 142.27 and 114.9 µg/dm2 for the PLA/4LE and PLA/6LE films, respectively, and was significantly higher than phenolic compounds migration measured for the LDPE/4LE (15.97 µg/dm2). Naringenin, apigenin, ferulic acid, eriocitrin, hesperidin and 4-hydroxybenzoic acid were the main identified compounds in the PLA, but only 4-hydroxybenzoic acid, naringenin and p-coumaric acid were identified in the LDPE films. Regarding the films' ability to delay lipid oxidation, LDPE/4LE presented the best results, showing a capacity to delay lipid oxidation in almonds for 30 days. When applied to raw beef meat, the PLA/6LE packaging was able to significantly inhibit lipid oxidation for 6 days, and successfully inhibited total microorganisms' growth until the 8th day of storage.

Migration of Dihydroxy Alkylamines and Their Possible Impurities from Packaging into Foods and Food Simulants: Analysis and Safety Evaluation.

Alkyl diethanolamines are a group of compounds commonly used as antistatic agents in plastic food packaging materials. These additives and their possible impurities have the ability to transfer into the food; hence, the consumer may be exposed to these chemicals. Recently, scientific evidence of unknown adverse effects associated with these compounds was reported. N,N-bis(2-hydroxyethyl)alkyl (C8-C18) amines as well as other related compounds and their possible impurities were analyzed in different plastic packaging materials and coffee capsules using target and non-target LC-MS methods. N,N-bis(2-hydroxyethyl)alkyl amines, precisely, C12, C13, C14, C15, C16, C17 and C18, 2-(octadecylamino)ethanol and octadecylamine, among others, were identified in most of the analyzed samples. It should be emphasized that the latter compounds are not listed in the European Regulation 10/2011 and 2-(octadecylamino)ethanol was classified as high toxicity according to Cramer rules. Migration tests were carried out in foods and in the food simulants Tenax and 20% ethanol (v/v). The results showed that stearyldiethanolamine migrated into the tomato, salty biscuits, salad and Tenax. Lastly, as a crucial step in the risk assessment process, the dietary exposure to stearyldiethanolamine transferred from the food packaging into the food was determined. The estimated values ranged from 0.0005 to 0.0026 µg/kg bw/day.

Towards the Sustainable Exploitation of Salt-Tolerant Plants: Nutritional Characterisation, Phenolics Composition, and Potential Contaminants Analysis of Salicornia ramosissima and Sarcocornia perennis alpini.

Increasing soil salinisation represents a serious threat to food security, and therefore the exploitation of high-yielding halophytes, such as Salicornia and Sarcocornia, needs to be considered not merely in arid regions but worldwide. In this study, Salicornia ramosissima and Sarcocornia perennis alpini were evaluated for nutrients, bioactive compounds, antioxidant capacity, and contaminants. Both were shown to be nutritionally relevant, exhibiting notable levels of crude fibre and ash, i.e., 11.26-15.34 and 39.46-40.41% dry weight (dw), respectively, and the major minerals were Na, K, and Mg. Total phenolics thereof were 67.05 and 38.20 mg of gallic acid equivalents/g extract dw, respectively, mainly p-coumaric acid and quercetin. Both species displayed antioxidant capacity, but S. ramossima was prominent in both the DPPH and ß-carotene bleaching assays. Aflatoxin B1 was detected in S. ramosissima, at 5.21 µg/Kg dw, which may pose a health threat. The Cd and Pb levels in both were low, but the 0.01 mg/Kg Hg in S. perennis alpini met the maximum legal limit established for marine species including algae. Both species exhibit high potential for use in the agro-food, cosmetics, and pharmaceutical sectors, but specific regulations and careful cultivation strategies need to be implemented, in order to minimise contamination risks by mycotoxins and heavy metals.

Almond Hull as a Functional Ingredient of Bread: Effects on Physico-Chemical, Nutritional, and Consumer Acceptability Properties.

Hulls are the principal almond by-products and are rich in bioactive compounds, such as polyphenols and fibre. Generally, hulls are used as animal feed; however, because of their valuable chemical composition, alternative applications as a natural food ingredient and dietary supplement should be evaluated. The aim of this study was to assess the physico-chemical and nutritional characteristics and the consumer acceptability of bread produced by replacing 4% and 8% of wheat flour with almond hulls (AHs) obtained from six almond varieties at two ripening stages (green and mature). The use of AHs in bread production increased fibre content, polyphenol content, and antioxidant activity. In particular, bread containing mature AHs showed the highest quantities of fibre and sugars, mainly glucose, whereas bread containing green AHs showed the highest polyphenol content. The polyphenol content and antioxidant activity in bread containing green AHs were 272.88 mg GAE/100 g dry weight and 1145.32 µmol TE/100 g dry weight, respectively, of which 60.5% and 52% were bioaccessible after in vitro digestion. Bread containing AH powder showed slightly lower specific volume, darker crumb colour, and lower hardness than those of the control. Consumer evaluation indicated that breads with 8% AH powder were those with the most overall liking.

Study on the chemical behaviour of Bisphenol S during the in vitro gastrointestinal digestion and its bioaccessibility.

This study evaluated the chemical behaviour of Bisphenol S (BPS) and determined its bioaccessibility after human ingestion using a standardised in vitro gastrointestinal digestion protocol and an analytical method based on high-pressure liquid chromatography coupled with a photodiode array and tandem mass spectrometry. The effects of different factors such as gastric pH, enzymes, and food matrix on the solubility and chemical stability of BPS were studied to evaluate their contribution to its bioaccessibility. The results highlighted that BPS was available at the end of the digestion process in the range of 50-80%, and was susceptible to absorption at the intestinal level. The effect of pH was not significant as a single factor. The presence of enzymes slightly decreased the bioaccessibility of BPS in the intestinal phase with gastric pH increase. Additionally, a soy drink reduced BPS bioaccessibility by up to 5% after oral intake. Finally, a few BPS degradation products were found in non-bioaccessible fractions at different pH values.

Chemometric Classification of Cocoa Bean Shells Based on Their Polyphenolic Profile Determined by RP-HPLC-PDA Analysis and Spectrophotometric Assays.

The cocoa bean shell (CBS), a byproduct from the cocoa industry, was recently proposed as a functional and low-cost ingredient, mainly because of its content in polyphenols. However, vegetal food products could significantly differ in their chemical composition depending on different factors such as their geographical provenience. This work is aimed to determine the polyphenolic and methylxanthine profile of different CBS samples and utilize it for achieving their differentiation according to their geographical origin and variety. RP-HPLC-PDA was used to determine the CBS polyphenolic profile. Spectrophotometric assays were used to obtain the total phenolic, flavonoid, and tannin contents, as well as to evaluate their radical scavenging activity. The results obtained from both methods were then compared and used for the CBS differentiation according to their origin and varieties through chemometric analysis. RP-HPLC-PDA allowed to determine 25 polyphenolic compounds, as well as the methylxanthines theobromine and caffeine. Polyphenolic profile results highlighted significant differences among the analyzed samples, allowing for their differentiation based on their geographical provenience. Similar results were achieved with the results of the spectrophotometric assays, considered as screening methods. Differentiation based on CBS variety was instead obtained based on the HPLC-determined methylxanthine profile.

Characterization and Classification of Cocoa Bean Shells from Different Regions of Venezuela Using HPLC-PDA-MS/MS and Spectrophotometric Techniques Coupled to Chemometric Analysis.

The cocoa bean shell (CBS) is one of the main cocoa byproducts with a prospective to be used as a functional food ingredient due to its nutritional and sensory properties. This study aims to define the chemical fingerprint of CBSs obtained from cocoa beans of diverse cultivars and collected in different geographical areas of Venezuela assessed using high-performance liquid chromatography coupled to photodiodes array and mass spectrometry (HPLC-PDA-MS/MS) and spectrophotometric assays combined with multivariate analysis for classification purposes. The study provides a comprehensive fingerprint and quantitative data for 39 compounds, including methylxanthines and several polyphenols, such as flavan-3-ols, procyanidins, and N-phenylpropenoyl amino acids. Several key cocoa markers, such as theobromine, epicatechin, quercetin-3-O-glucoside, procyanidin_A pentoside_3, and N-coumaroyl-l-aspartate_2, were found suitable for the classification of CBS according to their cultivar and origin. Despite the screening methods required a previous purification of the sample, both methodologies appear to be suitable for the classification of CBS with a high correlation between datasets. Finally, preliminary findings on the identification of potential contributors for the radical scavenging activity of CBS were also accomplished to support the valorization of this byproduct as a bioactive ingredient in the production of functional foods.

Presence of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in Food Contact Materials (FCM) and Its Migration to Food.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are synthetic chemical compounds widely used in different industry fields including food contact materials (FCM), providing resistance to fat and humidity, and non-stick properties. PFAS enter into the food chain directly from the intake of contaminated food or indirectly from the migration of the FCM into the food. This exposure published in different research highlights a public health concern. Therefore, it is necessary to perform analysis of the content of different FCM and evaluate the migration from the FCM under normal conditions of use and storage. This bibliographical review proves that different perfluoroalkyl and polyfluoroalkyl compounds are detected in fast food packaging, microwave popcorn bags, and frying pans, among others. Furthermore, it shows the conditions or factors that favor the migration of the PFAS from the FCM into the food.

Evaluation of Cocoa Bean Shell Antimicrobial Activity: A Tentative Assay Using a Metabolomic Approach for Active Compound Identification.

Cocoa bean shell is one of the main by-products of chocolate manufacturing and possesses several compounds with biofunctionalities. It can function as an antibacterial agent, and its action is mostly reported against Streptococcus mutans. However, only a few studies have investigated the cocoa bean shell compounds responsible for this activity. This study aimed to evaluate several extracts of cocoa bean shells from different geographical origins and cocoa varieties and estimate their antimicrobial properties against different fungal and bacterial strains by determining their minimal inhibitory concentration. The results demonstrated antimicrobial activity of cocoa bean shell against one of the tested strains, S. mutans. Cocoa bean shell extracts were further analysed via LC-HRMS for untargeted metabolomic analysis. LC-HRMS data were analysed (preprocessing and statistical analyses) using the Workflow4Metabolomics platform. The latter enabled us to identify possible compounds responsible for the detected antimicrobial activity by comparing the more and less active extracts. Active extracts were not the most abundant in polyphenols but contained higher concentrations of two metabolites. After tentative annotation of these metabolites, one of them was identified and confirmed to be 7-methylxanthine. When tested alone, 7-methylxanthine did not display antibacterial activity. However, a possible cocktail effect due to the synergistic activity of this molecule along with other compounds in the cocoa bean shell extracts cannot be neglected. In conclusion, cocoa bean shell could be a functional ingredient with benefits for human health as it exhibited antibacterial activity against S. mutans. However, the antimicrobial mechanisms still need to be confirmed.

Development and Characterization of Inhaled Ethanol as a Novel Pharmacological Strategy Currently Evaluated in a Phase II Clinical Trial for Early-Stage SARS-CoV-2 Infection.

Inhaled administration of ethanol in the early stages of COVID-19 would favor its location on the initial replication sites, being able to reduce the progression of the disease and improving its prognosis. Before evaluating the efficacy and safety of this novel therapeutic strategy in humans, its characterization is required. The developed 65° ethanol formulation is stable at room temperature and protected from light for 15 days, maintaining its physicochemical and microbiological properties. Two oxygen flows have been tested for its administration (2 and 3 L/min) using an automated headspace gas chromatographic analysis technique (HS-GC-MS), with that of 2 L/min being the most appropriate one, ensuring the inhalation of an ethanol daily dose of 33.6 ± 3.6 mg/min and achieving more stable concentrations during the entire treatment (45 min). Under these conditions of administration, the formulation has proven to be safe, based on histological studies of the respiratory tracts and lungs of rats. On the other hand, these results are accompanied by the first preclinical molecular imaging study with radiolabeled ethanol administered by this route. The current ethanol formulation has received approval from the Spanish Agency of Medicines and Medical Devices for a phase II clinical trial for early-stage COVID-19 patients, which is currently in the recruitment phase (ALCOVID-19; EudraCT number: 2020-001760-29).

Protective Effect of Cocoa Bean Shell against Intestinal Damage: An Example of Byproduct Valorization.

BACKGROUND: Cocoa bean shell (CBS), a main byproduct of cocoa processing, represents a source of components such as polyphenols and methylxanthines, which have been associated with a reduced risk of several diseases. Therefore, CBS has potential application as a food ingredient. Intestinal mucosa is exposed to immune and inflammatory responses triggered by dietary agents, such as oxysterols, which derive from cholesterol oxidation and are pro-oxidant compounds able to affect intestinal function. We aimed at investigating the capability of the Forastero cultivar CBS, added or not added to ice cream, to protect against the intestinal barrier damage induced by a dietary oxysterol mixture. METHODS: Composition and antioxidant capacity of in vitro digested CBS and CBS-enriched ice cream were analyzed by high-performance liquid chromatography and 1,1-diphenyl-2-picryl-hydrazyl radical-scavenging assay, respectively. CaCo-2 cells differentiated into enterocyte-like monolayer were incubated with 60 µM oxysterol mixture in the presence of CBS formulations. RESULTS: The oxysterol mixture induced tight junction impairment, interleukin-8 and monocyte chemoattractant protein-1 cell release, and oxidative stress-related nuclear factor erythroid 2 p45-related factor 2 response Nrf2. Both CBSs protected cells from these adverse effects, probably thanks to their high phenolic content. CBS-enriched ice cream showed the highest antioxidant capacity. Theobromine, which is in high concentrations of CBS, was also tested. Although theobromine exerted no effect on Nrf2 expression, its anti-inflammatory cooperating activity in CBS effect cannot be excluded. CONCLUSIONS: Our findings suggest that CBS-enriched ice cream may be effective in the prevention of gut integrity damage associated with oxidative/inflammatory reactions.

Industrial Fruits By-Products and Their Antioxidant Profile: Can They Be Exploited for Industrial Food Applications?

Fruit by-products have a low economic value and have proven biological activities, such as antioxidant capacity due to the presence of active compounds. The main objective of this study was to obtain and determine the antioxidant capacity, through DPPH radical assay and ß-carotene bleaching assay, of three food grade extracts from apple, lemon, and orange industrial by-products. Furthermore, the extracts were characterized by ultra-high performance liquid chromatography coupled to mass spectrometry (UHPLC-MS/MS). LC with diode array detector (LC-DAD) was used for the quantification of the main polyphenols. Lemon extract presented the highest inhibition percentage of DPPH radical (51.7%) and the highest total phenolics content (43.4 mg GAE/g) from the by-products studied. Orange by-product was that with the higher number of polyphenols while lemon extract was that with the highest content of individual phenolics. The by-product obtained from the lemon was that with higher amounts of hydroxycinnamic acids (407 µg/g of by-product), mainly chlorogenic acid (386.7 µg/g), followed by the apple by-product (128.0 µg/g of by-product), which showed higher amounts of rosmarinic and chlorogenic acids. These industrial by-products have great potential as a source of natural antioxidants to be used directly as food additives or to be incorporated in packaging to produce active food packaging.

Polyphenolic and Methylxanthine Bioaccessibility of Cocoa Bean Shell Functional Biscuits: Metabolomics Approach and Intestinal Permeability through Caco-2 Cell Models.

Cocoa bean shell (CBS), a by-product with considerable concentrations of bioactive compounds and proven biofunctional potential, has been demonstrated to be a suitable ingredient for high-fiber functional biscuits adapted to diabetic consumers. In this work, the in vitro bioaccessibility and intestinal absorption of polyphenols and methylxanthines contained in these biscuits were evaluated, and the effect of the food matrix was studied. Biscuits containing CBS and the CBS alone underwent in vitro digestion followed by an intestinal permeability study. The results confirmed that compounds were less bioavailable in the presence of a food matrix, although the digestion contributed to their release from this matrix, increasing the concentrations available at the intestinal level and making them capable of promoting antioxidant and antidiabetic activities. After digestion, CBS biscuits were shown to possess α-glucosidase inhibition capacity comparable to that of acarbose. Moreover, the presence of the food matrix improved the stability of polyphenols throughout the digestion process. Intestinal absorption of flavan-3-ols seemed to be limited to a maximum threshold and was therefore independent of the sample, while procyanidin was not absorbed. Methylxanthine absorption was high and was boosted by the presence of the food matrix. The results confirmed the biofunctional potential of CBS-based biscuits.

Physical Properties and Consumer Evaluation of Cocoa Bean Shell-Functionalized Biscuits Adapted for Diabetic Consumers by the Replacement of Sucrose with Tagatose.

The cocoa bean shell (CBS), a by-product of the cocoa industry, has been reported to be rich in fiber and polyphenols, which could contribute to reducing the metabolism of sugars and glucose adsorption. The production of CBS-based biscuits in which sucrose is replaced with tagatose (a low-glycemic sugar with prebiotic properties), benefiting diabetic consumers, is proposed. Six prototype biscuits were produced using sucrose, tagatose, and CBS powder at 0%, 10%, and 20% as a wheat flour replacement. Biscuits were studied in terms of fiber content, and those with 10% and 20% CBS showed to contain 5.66% and 8.70-8.71% of total dietary fiber, respectively. Moreover, the physicochemical and structural properties of the biscuits were studied to evaluate their differences due to the use of sucrose and tagatose combined with CBS. Significant effects mainly caused by the reducing nature and lower solubility of tagatose with respect to sugar, and the water retention capacities of CBS were observed. Finally, the biscuits were evaluated by performing a consumer acceptance evaluation, and their perceptible sensorial differences were studied by performing a Napping® sensory characterization. CBS-based biscuits represent an interesting possibility for cocoa by-product revalorization, although an optimized recipe is recommended, especially when employing tagatose.

In Vitro Bioaccessibility and Functional Properties of Phenolic Compounds from Enriched Beverages Based on Cocoa Bean Shell.

The cocoa bean shell (CBS), a cocoa by-product, contains a significant number of bioactive compounds with functional properties, such as polyphenols and methylxanthines, and is used as an ingredient in beverages and foods. In this work, the bioaccessibility of polyphenols and methylxanthines after In Vitro digestion was evaluated in new flavoured beverages for at-home consumption (capsules and tea bags). In addition, the polyphenolic composition, functional properties (antiradical and α-glucosidase inhibition capacities) and consumer acceptability of these beverages were evaluated. In both capsule and tea bag beverages, the bioaccessibility of methylxanthines was 100% while that of total polyphenols exceeded 50%. The main polyphenols determined using reverse-phase liquid chromatography were type B procyanidins and epicatechin. The antiradical activity in capsule and tea bag beverages was 1.75 and 1.88 mM of Trolox equivalents, respectively, of which 59.50% and 57.09% were recovered after simulated digestion. The percentage of α-glucosidase inhibition before In Vitro digestion (51.64% and 53.82% for capsules and tea bags, respectively) was comparable to that of acarbose at 0.5 mM. All the beverages obtained a high consumer acceptability. Therefore, these results highlight that CBSs can be used as a valid source of bioactive compounds in the preparation of beverages with homemade techniques.

Physico-Chemical Characterization of Tunisian Canary Palm (Phoenix canariensis Hort. Ex Chabaud) Dates and Evaluation of Their Addition in Biscuits.

Phoenix canariensis Hort. Ex Chabaud, also known as the Canary Island palm or ornamental palm, is an endemic species of the Canary Islands and has been widely propagated globally. It has become one of the most important and appreciated ornamental plants, especially in the Mediterranean climate. The fruits are edible but used only for feed as they are bitter. Despite its diffusion, not much data on the composition of these fruits and their application as food are available. The aim of this study was to define the chemical characteristics, especially those of the polyphenolic constituents, of red and yellow varieties of Canary palm dates, and to evaluate their use alone or in different mixes in biscuit production. The yellow variety had higher quantities of fiber (36.88% DW (Dry Weight)) and polyphenolic compounds, while the red variety had a high content of sugars, mainly glucose (22.8% DW). Epicatechin is the most important polyphenol of dates (562 mg/g DW). The use of date palm powder on biscuit production resulted in an increase in hardness, polyphenol and fiber content, and antioxidant activity. Sensory analysis showed that the biscuits obtained with a 25/75 mix of red/yellow date powder had the most overall liking.

Cocoa Bean Shell-A By-Product with Nutritional Properties and Biofunctional Potential.

Cocoa bean shells (CBS) are one of the main by-products from the transformation of cocoa beans, representing 10%‒17% of the total cocoa bean weight. Hence, their disposal could lead to environmental and economic issues. As CBS could be a source of nutrients and interesting compounds, such as fiber (around 50% w/w), cocoa volatile compounds, proteins, minerals, vitamins, and a large spectrum of polyphenols, CBS may be a valuable ingredient/additive for innovative and functional foods. In fact, the valorization of food by-products within the frame of a circular economy is becoming crucial due to economic and environmental reasons. The aim of this review is to look over the chemical and nutritional composition of CBS and to revise the several uses that have been proposed in order to valorize this by-product for food, livestock feed, or industrial usages, but also for different medical applications. A special focus will be directed to studies that have reported the biofunctional potential of CBS for human health, such as antibacterial, antiviral, anticarcinogenic, antidiabetic, or neuroprotective activities, benefits for the cardiovascular system, or an anti-inflammatory capacity.

Determination of Xanthohumol in Hops, Food Supplements and Beers by HPLC.

Xanthohumol (XN) is the main prenylated chalcone present in hops (Humulus lupulus) with high biological activity, and it is of great importance for human health because of its antioxidant, anti-inflammatory, immunosuppressive and chemopreventive properties. This polyphenol can be included in the diet through foods in which hops are used, such as beer or food supplements. Because of their health benefits and the increasing interest of using hops as a novel nutraceutical, the aim of this work was the identification and quantification of XN in different types of samples using a method based on high resolution liquid chromatography with a diode array detector (HPLC-DAD). The method was validated in terms of linearity, limits of detection (LOD) and quantification (LOQ), repeatability and recovery. Acceptable linearity (r2 0.9999), adequate recovery (>90% in the most of cases) and good sensitivity (LOD 16 µg/L) were obtained. Furthermore, the presence of XN in all samples was confirmed using liquid chromatography coupled to mass spectrometry (LC-MS/MS) operated in negative ESI (electrospray system ionization) mode. The concentrations of XN determined in hop flowers and food supplements were above the LOQ, in a range between 0.106 and 12.7 mg/g. Beer may also represent an important source of dietary prenylflavonoids, with between 0.028 and 0.062 mg/L of XN. The results showed that the methodology proposed was suitable for the determination of XN in the different types of samples studied, and the amounts of XN varied significantly according to the selected product.

Analytical dataset on volatile compounds of cocoa bean shells from different cultivars and geographical origins.

This data article describes the analysis of volatile organic compounds (VOCs) in 44 samples of cocoa bean shells (CBS) obtained from cocoa beans of diverse cultivars and collected in different geographical origins. The volatile compounds were extracted by headspace solid-phase microextraction (HS-SPME) method and then analyzed by gas chromatography coupled to a quadrupole mass spectrometry GC-qMS. The retention times, identification and semi-quantification of 101 VOCs are reported. Data collected on the volatile profile of CBS samples using E-nose analysis are also available. Additional data related to physicochemical characteristics and color analysis for CBS samples are reported. Further interpretation and discussion on these datasets can be found in the related article entitled "Assessment of volatile fingerprint by HS-SPME/GC-qMS and E-nose for the classification of cocoa bean shells using chemometrics" (Barbosa-Pereira et al., 2019).

Assessment of volatile fingerprint by HS-SPME/GC-qMS and E-nose for the classification of cocoa bean shells using chemometrics.

The cocoa bean shell (CBS) is a main by-product of cocoa processing, with great potential to be used as an ingredient for functional foods because of its nutritional and flavour properties. This study aimed to characterise and classify CBSs obtained from cocoa beans of diverse cultivars and collected in different geographical origins through their volatile profile assessed using headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME/GC-qMS) and E-nose combined with principal component analysis (PCA). The study provides, for the first time in a representative set of samples, a comprehensive fingerprint and semi-quantitative data for >100 volatile organic compounds (VOCs), such as aldehydes, ketones, pyrazines, alcohols, and acids. Through PCA, a clear separation of the Criollo cultivar from the other cultivars was achieved with both GC-qMS and E-nose analytical techniques because of the high content of key-aroma VOCs. Several biomarkers identified by GC-qMS, such as 2-hepanol, 2-methylpropanoic acid, and 2,3,5-trimethylpyrazine, recognized as key-aroma compounds for cocoa beans, were found suitable for the classification of CBSs according to their quality and origin. GC-qMS and E-nose appeared to be suitable analytical approaches to classify CBSs, with a high correlation between both analytical techniques. The volatile fingerprint and classification of CBSs could allow for the selection of samples with a specific flavour profile according to the food application and, therefore, constitute an interesting approach to valorise this by-product as a food ingredient.