Authentication of Argentinean extra-virgin olive oils using three-way fluorescence and two-way near-infrared data fused with multi-block DD-SIMCA.

A trending problem of Extra Virgin Olive Oil (EVOO) adulteration is investigated using two analytical platforms, involving: (1) Near Infrared (NIR) spectroscopy, resulting in a two-way data set, and (2) Fluorescence Excitation-Emission Matrix (EEFM) spectroscopy, producing three-way data. The related instruments were employed to study genuine and adulterated samples. Each data set was first separately analyzed using the Data Driven-Soft Independent Modeling of Class Analogies (DD-SIMCA) method, based on Principal Component Analysis (for the two-way NIR data) and PARallel FACtor analysis (for the three-way EEFM data). The data sets were then processed together using the multi-block fusion method, based on the concept of Cumulative Analytical Signal (CAS). A comparison of the data processing methods in terms of sensitivity, specificity and selectivity showed the following order of excellence: NIR < EEFM < NIR + EEFM. This finding confirms the effectiveness of multi-block data fusion, which cumulatively improves the model performance.

Dataset of Raman spectroscopy responses for over-the-counter drugs in Paraguay, including acetylsalicylic acid, paracetamol, and ibuprofen.

This dataset includes spectra obtained through Raman spectroscopy of acetylsalicylic acid, paracetamol, and ibuprofen commercialized in San Lorenzo, Central Department of Paraguay. The pharmaceuticals were randomly purchased from pharmacies, official sales points, and street vendors, simulating purchases for self-consumption. These drugs were selected due to their high demand and consumption by the population, aiming to document and facilitate the identification of adulterations or alterations in their original structures caused by poor storage conditions. Additionally, this database will support multivariate studies for clustering using various techniques, both supervised and unsupervised, and will allow for signal processing and spectroscopic data handling.

Lead content in cinnamon and its health risk assessment for Ecuadorian consumers.

Lead (Pb) is a poisonous metal that affects organs and the nervous system. Its presence in spices such as cinnamon has been identified as a potential human exposure pathway. In late October 2023, a safety alert was issued in the United States regarding four children with elevated Pb levels in their blood after consuming apple-cinnamon fruit puree manufactured and exported by an Ecuadorian company. Thus, this study aimed to determine the Pb content in 61 ground and stick cinnamon samples, from different commercial brands and lots sold in Ecuador. Results showed that ground cinnamon samples had almost twice the level of Pb (0.80 ± 0.75 mg/kg) than stick samples (0.36 ± 0.28 mg/kg). Three ground samples had Pb content above the maximum level established by Ecuadorian and European Union regulations (2.0 mg/kg). A Kruskal-Wallis test showed significant differences in Pb content between ground and stick cinnamon (p < 0.05). The HQ values showed negligible non-carcinogenic effects for children and adults, even at the highest Pb content. However, the carcinogenic risk of ground cinnamon at maximum and mean Pb concentrations was found for the population. Our study highlights the deficiencies in current surveillance systems and the lack of effective national regulations for exposure to foodborne metals.

Investigation of fraud in the production of butter: a forensic case study of criminal association.

Butter is among the most popular and commercially valuable dairy products. Its high commercial value makes it a major target for adulteration, which aims to reduce production costs by using lower-quality fats and oils from other sources. The annual global market is around USD 30 billion (2023), expected to reach USD 36 billion in 2028, which also justifies the enormous interest in adulteration. In this work, a confirmed case of butter adulteration was studied by Nuclear Magnetic Resonance (NMR) and Stable Carbon Isotopic Ratio Analysis (SCIRA) techniques, employed to detect the inclusion in butter production of vegetable oils, such as soybean and palm oils. A total of 21 samples seized by the Brazilian Federal Police were analysed by NMR and SCIR, and compared to original butter obtained from commercial sources. The composition of all the seized samples was a mixture of butter (dairy fat of animal origin) with fat of vegetable origin (soybean and palm oil) and did not contain milk as a major component. While NMR was an unequivocal choice to discriminate the chemical composition of food samples, identifying the short-chain saturated fatty acids present in milk fat, including the butyryl alkyl chain, SCIRA was able to discriminate the origin of fat present in the butter samples as C3 sources, such as palm vegetable oils.

An integrative review of analytical techniques used in food authentication: A detailed description for milk and dairy products.

The use of suitable analytical techniques for the detection of adulteration, falsification, deliberate substitution, and mislabeling of foods has great importance in the industrial, scientific, legislative, and public health contexts. This way, this work reports an integrative review with a current analytical approach for food authentication, indicating the main analytical techniques to identify adulteration and perform the traceability of chemical components in processed and non-processed foods, evaluating the authenticity and geographic origin. This work presents results from a systematic search in Science Direct® and Scopus® databases using the keywords "authentication" AND "food", "authentication," AND "beverage", from published papers from 2013 to, 2024. All research and reviews published were employed in the bibliometric analysis, evaluating the advantages and disadvantages of analytical techniques, indicating the perspectives for direct, quick, and simple analysis, guaranteeing the application of quality standards, and ensuring food safety for consumers. Furthermore, this work reports the analysis of natural foods to evaluate the origin (traceability), and industrialized foods to detect adulterations and fraud. A focus on research to detect adulteration in milk and dairy products is presented due to the importance of these products in the nutrition of the world population. All analytical tools discussed have advantages and drawbacks, including sample preparation steps, the need for reference materials, and mathematical treatments. So, the main advances in modern analytical techniques for the identification and quantification of food adulterations, mainly milk and dairy products, were discussed, indicating trends and perspectives on food authentication.

Microscopy, HPTLC, and LC-DAD-Q-ToF validation of nut-based weight-loss dietary supplements, Aleurites moluccanus (candlenut) and Bertholletia excelsa (Brazil nut).

Aleurites moluccanus (candlenut) and Bertholletia excelsa (Brazil nut) are marketed as dietary supplements for weight loss. These dietary supplements have been found to sometimes be adulterated with toxic nuts/seeds from Cascabela thevetia, commonly known as yellow oleander or lucky nut. This study emphasizes the key identification parameters to differentiate the genuine and adulterated nuts. Samples were obtained from authenticated sources of the nuts and from commercial sources of dietary supplements. This study examined 38 samples, including voucher and commercial samples. All eight commercial candlenut dietary supplement samples were adulterated. Additionally, two samples sold as Brazil nuts were also found to be adulterated. Other nuts were screened for the presence of Cardiac Glycosides, but none were found to be positive. The presence of yellow oleander was confirmed in all commercial dietary supplement samples marketed as candlenut as well as in commercial samples of Brazil nut. This study provides simple key identification characters using micro-morphology and histochemical localization of cardiac glycosides in the commercial nuts, HPTLC fingerprints, and LC-DAD-Q-ToF analytical parameters to detect and identify adulteration in commercial products.

The presence of doping agents in dietary supplements: A glimpse into the Brazilian situation.

Dietary supplements (DS) are intended for healthy people to maintain or improve their overall health. Its consumption is widespread in large part of the general population and at all levels of athletes. Nevertheless, DS use can also pose health risks to individuals and, in the case of athletes, may lead to adverse analytical findings (AAFs) due to the possibility of DS contamination or adulteration with doping agents banned by the World Anti-Doping Agency. Although educational initiatives are being performed in Brazil to warn the sports community about inadvertent doping cases, AAFs connected to the DS administration have been increasingly growing. The findings of DS analyzed by the Brazilian Doping Control Laboratory (LBCD), between 2017 and 2022, after Testing Authorities (TAs) analysis requests, showed an alarming number of tainted samples. Diuretics were the most common adulterants found in all supplement types. However, the profile of prohibited substances in manufactured and compounded dietary supplements (MDS and CDS, respectively) were distinct, with stimulants being most prevalent in MDS and anabolic agents in CDS products. Additionally, MDS samples generally presented higher estimated concentrations of banned substances (mg/g) than CDS samples (µg/g). The common practice of DS intake by athletes continues to be of great concern for a doping-free sport, given the high prevalence of prohibited substances detected in the analyzed samples by the LBCD. The current Brazilian scenario reinforces the importance of raising awareness in the sports community of the possible consequences of an unintentional doping case linked to DS use.

Characterisation of Sclerocarya birrea (marula) seed oil and investigation of the geographical origin by applying similarity calculations, differential NMR and hierarchical cluster analysis.

INTRODUCTION: The marula fruit is an important indigenous African fruit since various commercial products are produced from the pulp and the seed oil. The increased demand requires methods for authentication, quality control and determination of geographical origin. OBJECTIVE: The study aimed to establish a fast and reliable method for characterisation and authentication of marula seed oil. Furthermore, to identify marker compounds that can distinguish marula seed oils from other commercial oils and indicate regional differences. MATERIALS AND METHODS: Metabolic profiling of 44 commercial marula seed oils was performed using proton nuclear magnetic resonance (1 H NMR). For rapid classification similarity calculations were compared with principal component analysis. Differential NMR was used to determine marker compounds. RESULTS: Marula seed oil was found to be similar to macadamia and olive oils and was distinguished from these oils by the detection of minor components. Marula seed oil is differentiated from the other two oils by the absence of α-linolenic acid, relatively high levels of monoglycerides and diglycerides, and an approximately 1:1 ratio of 1,2- and 1,3-diglycerides. When comparing marula seed oils from various regions using hierarchical cluster analysis, clustering of the marula seed oils from Namibia and Zimbabwe was observed and was related to the quantities of linoleic acid and monoglycerides and diglycerides. Some samples displayed deviations in their composition which might indicate adulteration or contamination during the production process. CONCLUSION: The study demonstrates the potential of NMR as a tool in the quality control of marula seed oil. This technique requires very little sample preparation, circumvents derivatisation of the oil components with fast run-times. In addition, samples with chemical profiles that differ from the general signature profile can easily be identified.

Nutritional lipidomics for the characterization of lipids in food.

Lipids represent one out of three major macronutrient classes in the human diet. It is estimated to account for about 15-20% of the total dietary intake. Triacylglycerides comprise the majority of them, estimated 90-95%. Other lipid classes include free fatty acids, phospholipids, cholesterol, and plant sterols as minor components. Various methods are used for the characterization of nutritional lipids, however, lipidomics approaches become increasingly attractive for this purpose due to their wide coverage, comprehensiveness and holistic view on composition. In this chapter, analytical methodologies and workflows utilized for lipidomics profiling of food samples are outlined with focus on mass spectrometry-based assays. The chapter describes common lipid extraction protocols, the distinct instrumental mass-spectrometry based analytical platforms for data acquisition, chromatographic and ion-mobility spectrometry methods for lipid separation, briefly mentions alternative methods such as gas chromatography for fatty acid profiling and mass spectrometry imaging. Critical issues of important steps of lipidomics workflows such as structural annotation and identification, quantification and quality assurance are discussed as well. Applications reported over the period of the last 5years are summarized covering the discovery of new lipids in foodstuff, differential profiling approaches for comparing samples from different origin, species, varieties, cultivars and breeds, and for food processing quality control. Lipidomics as a powerful tool for personalized nutrition and nutritional intervention studies is briefly discussed as well. It is expected that this field is significantly growing in the near future and this chapter gives a short insight into the power of nutritional lipidomics approaches.

Biogenic amines and stable isotopes in the quality and authenticity of honeys from Brazil.

The identification of biogenic amines and some precursor amino acids and the adulteration through stable isotopes was carried out in 114 honey from different geographic regions in Brazil (states of São Paulo (SP) and Santa Catarina (SC)) as support for evaluating quality control and food safety. Serotonin was detected in all samples, while melatonin was quantified in 92.2% of honey from SP and in 94% of SC. l-Dopa, dopamine and histamine appeared at higher levels in honey from SP. Cadaverine, putrescine, spermidine and spermine, varied little according to botanical source. Three honey from the metropolitan region of SP were considered adulterated (C4SUGARS > 7%), 92 were authentic samples (C4SUGARS - 7 to 7%) and 19 unadulterated (C4SUGARS less than - 7%), with isotopic values of δ13CH and δ13CP > 7%. The data were important for differentiating quality as a function of biogenic amines and stable isotope technique was important in detecting honey adulteration.

Amphetamine-type Stimulants: Novel Insights into their Actions and use Patterns.

This review focuses on the effects and mechanisms of action of amphetamine-type stimulants (ATS) and their adverse effects on the cardiovascular, nervous, and immune systems. ATS include amphetamine (AMPH), methamphetamine (METH, "crystalmeth," or "ice"), methylenedioxymethamphetamine (MDMA, "ecstasy," or "Molly"), MDMA derivatives (e.g., methylenedioxyamphetamine [MDA] and methylenedioxy-N-ethylamphetamine [MDEA]), khat, and synthetic cathinones. The first section of this paper presents an overview of the historical aspects of ATS use, their initial clinical use, and regulations. The second part reviews the acute and chronic impact and the most salient clinical effects of ATS on the central nervous and cardiovascular systems, skin, and mouth. The chemical structure, pharmacokinetics, and classic and non-canonical pharmacological actions are covered in the third section, briefly explaining the mechanisms involved. In addition, the interactions of ATS with the central and peripheral immune systems are reviewed. The last section presents data about the syndemic of ATS and opioid use in the North American region, focusing on the increasing adulteration of METH with fentanyl.

Amphetamine-type Stimulants: Novel Insights into their Actions and use Patterns

ABSTRACT This review focuses on the effects and mechanisms of action of amphetamine-type stimulants (ATS) and their adverse effects on the cardiovascular, nervous, and immune systems. ATS include amphetamine (AMPH), methamphetamine (METH, "crystalmeth," or "ice"), methylenedioxymethamphetamine (MDMA, "ecstasy," or "Molly"), MDMA derivatives (e.g., methylenedioxyamphetamine [MDA] and methylenedioxy-N-ethylamphetamine [MDEA]), khat, and synthetic cathinones. The first section of this paper presents an overview of the historical aspects of ATS use, their initial clinical use, and regulations. The second part reviews the acute and chronic impact and the most salient clinical effects of ATS on the central nervous and cardiovascular systems, skin, and mouth. The chemical structure, pharmacokinetics, and classic and non-canonical pharmacological actions are covered in the third section, briefly explaining the mechanisms involved. In addition, the interactions of ATS with the central and peripheral immune systems are reviewed. The last section presents data about the syndemic of ATS and opioid use in the North American region, focusing on the increasing adulteration of METH with fentanyl.

Fraude alimentario: Pasado, presente y futuro

La adulteración y el fraude de productos alimenticios son tan antiguos como los sistemas de procesamiento y producción de alimentos, sin embargo, en la actualidad son cada vez más frecuentes. Con la globalización y los sistemas de producción y distribución de alimentos cada día más complejos, la adulteración puede ocurrir en distintos puntos de la cadena alimentaria y tener un impacto de gran alcance, e incluso, consecuencias adversas para la salud de las personas. Los enfoques regulatorios de la comunidad internacional para enfrentar y resolver el fraude alimentario están dispersos y en constantes ajustes. Se necesita un enfoque colectivo y coordinado para identificar a todos los interesados en la cadena de suministro de alimentos, calificarlos y certificarlos, excluir a aquellos que no cumplan con los estándares adecuados y rastrear los alimentos en tiempo real. Este artículo de actualización revisará conceptos claves asociados a la integridad alimentaria, historia del fraude alimentario y episodios de fraude alimentario de connotación pública en el mundo y en Chile, herramientas analíticas y alimentos más vulnerables al fraude, reglamentos y nuevas acciones en el mundo y en Chile para enfrentar la inocuidad y el riesgo de fraude alimentario.

Food adulteration and food fraud is as old as food production and processing however, it is increasingly prevalent today. With globalization and increasingly complex food production and distribution systems, adulteration can occur at different points in the food chain and may have far-reaching impacts and even adverse consequences for human health. The international community's regulatory approaches to confronting and resolving food fraud are scattered and in constant adjustment. A collective and coordinated approach is needed to identify all stakeholders in the food supply chain, certify and qualify them, exclude those who do not meet applicable standards, and trace food in real time. This update provides definitions and background on key concepts associated with food integrity, episodes of food fraud in Chile and the world, main foods vulnerable to food fraud, common fraud practices and analytical techniques, regulations and new actions in Chile and the world to face food safety and the risk of food fraud.

First report on quality and purity assessment of sweet almond oil in Brazilian body oils by gas chromatography and mass spectrometry.

Sweet almond oil is a raw material with high-added value used in different products. Then, the aim of this study is to evaluate the quality and purity of 10 body oils based on sweet almond oils currently available in the Brazilian market. Fatty acid composition and triacylglycerol (TAG) profile were determined by gas chromatography with flame ionization detector (GC-FID) and atmospheric solids analysis probe mass spectrometry (ASAP-MS), respectively. The authenticity of samples was assessed using an analytical curve equation. Soybean oil was chosen as the adulterant because it is the cheapest vegetable oil commercialized in Brazil. Hierarchical clustering analysis (HCA) in conjunction with ASAP-MS classified product samples according to the type of vegetable oil (soybean and sweet almond oils). The addition of soybean oil (8.79% to 99.70%) was confirmed in samples. However, only two samples stated in their label the presence of soybean oil as an ingredient. These findings highlight the need for better oversight by regulatory bodies to ensure that consumers acquire high quality and authentic products based on equally high quality and purity of sweet almond oils.

Understanding the variations in dielectric properties of mustard (Brassica nigra L.) and argemone (Argemone mexicana) oil blends at different temperatures.

Mustard oil is the most commonly adulterated edible oil, invariably with argemone oil. This study was aimed to develop a parallel plate capacitive sensor for measurement of dielectric properties of pure mustard oil, pure argemone oil and their blends (25, 50 and 75%) at five levels of varying temperature (10 to 50 °C). The effect of blend ratio and temperature on the selected dielectric properties of oil-capacitance (C), dielectric loss tangent (tanδ), dielectric constant ( ε ' ), dielectric loss factor ( ε ″ ) and electrical conductivity (σ) were investigated. It was observed that composition of the individual oils in terms of moisture and fatty acids influenced the physical and dielectric properties. The sensor was used to relate the dielectric properties of oil samples with blend ratio and temperature by means of statistically significant (p < 0.05) and robust (R 2 > 0.8) multiple linear regression model. The effect of temperature on C and ε ' was negative, while it was otherwise for tanδ, ε ″ and σ. Increase in argemone oil content in the blends, increased the dielectric measures due to the associated changes in the physical and chemical properties. The capacitive sensor could distinctly identify mustard oil, argemone oil and its blends on the basis of dielectric properties.

Rapid, reliable and easy-to-perform chemometric-less method for rice syrup adulterated honey detection using FTIR-ATR.

The adulteration of honey (Apis mellifera) is a global problem due to its economic, commercial and health implications. The world's leading beekeeping organisation, APIMONDIA, considers that the detection of adulteration in honey is a problem that has not yet been resolved. This evidence of the importance of the intensive development of analytical techniques that allow the unequivocal detection of adulterants in honey, especially those whose use as honey adulterants has recently emerged. This work aims to develop a fast, easy-to-perform, low-cost analytical method to qualitatively and quantitatively determine rice syrup using the Fourier transform infrared spectroscopy (FTIR) technique with attenuated total reflectance (ATR) mode without complex mathematical procedures and sophisticated sample preparation. This study involved the analysis of 256 intentionally rice-syrup-adulterated honey samples and 92 pure honey samples of bee multifloral honey from Spain. The method, based strictly on the determination of the absorbance directly from the samples, at 1013 cm-1 The methodology used no need for previous treatments or preparations and demonstrated the scope for the unequivocal detection of rice syrup in adulterated honey containing equal to or higher than 3% (m/m) or more of this adulterant. Using the Exponential Plus Linear model (r = 0.998) shows high accuracy and precision, in terms of relative error (0.32%, m/m) and coefficient of variation (1.4%). The results of this study have led to the establishment of a maximum absorbance threshold of 0.670 for honey without rice syrup.

One-class model with two decision thresholds for the rapid detection of cashew nuts adulteration by other nuts.

A green screening method to determine cashew nut adulteration with Brazilian nut, pecan nut, macadamia nut and peanut was proposed. The method was based on the development of a one-class soft independent modelling of class analogy (SIMCA) model for non-adulterated cashew nuts using near-infrared (NIR) spectra obtained with portable equipment. Once the model is established, the assignment of unknown samples depends on the threshold established for the authentic class, which is a key aspect in any screening approach. The authors propose innovatively to define two thresholds: lower model distance limit and upper model distance limit. Samples with distances below the lower threshold are assigned as non-adulterated with a 100% probability; samples with distance values greater than the upper threshold are assigned as adulterated with a 100% probability; and samples with distances within these two thresholds will be considered uncertain and should be submitted to a confirmatory analysis. Thus, the possibility of error in the sample assignment significantly decreases. In the present study, when just one threshold was defined, values greater than 95% for the optimized threshold were obtained for both selectivity and specificity. When two class thresholds were defined, the percentage of samples with uncertain assignment changes according to the adulterant considered, highlighting the case of peanuts, in which 0% of uncertain samples was obtained. Considering all adulterants, the number of samples that were submitted to a confirmatory analysis was quite low, 5 of 224 adulterated samples and 3 of 56 non-adulterated samples.

Buckypaper-Based Nanostructured Sensor for Port Wine Analysis.

The development of electronic gadgets has become of great relevance for the detection of fraud in beverages such as wine, due to the addition of adulterants that bring risks to human health as well as economic impacts. Thus, the present study aims to apply a buckypaper (BP) based on functionalized multiwalled carbon nanotubes (MWCNTs)/cellulose fibers as a sensor for the analysis of Port wine intentionally adulterated with 5 vol.% and 10 vol.% distilled water and ethyl alcohol. The morphology of BP characterized by scanning electron microscopy indicates the formation of agglomerates of random MWCNTs dispersed on the surface and between the fibers of the cellulosic paper. The analysis of the response of the film through the normalized relative resistance change showed a higher response of 0.75 ± 0.16 for adulteration with 10 vol.% of water and a mean response time of 10.0 ± 3.60 s and recovery of approximately 17.2 min for adulteration with 5 vol.% alcohol. Principal component analysis (PCA) was used in data processing to evaluate the ability of BP to recognize and discriminate analytes and adulterating agents, allowing the investigation of its potential application as a low-cost and easy-to-handle multisensor.

Hyperspectral Microscopy Technology to Detect Syrups Adulteration of Endemic Guindo Santo and Quillay Honey Using Machine-Learning Tools.

Honey adulteration is a common practice that affects food quality and sale prices, and certifying the origin of the honey using non-destructive methods is critical. Guindo Santo and Quillay are fundamental for the honey production of Biobío and the Ñuble region in Chile. Furthermore, Guindo Santo only exists in this area of the world. Therefore, certifying honey of this species is crucial for beekeeper communities-mostly natives-to give them advantages and competitiveness in the global market. To solve this necessity, we present a system for detecting adulterated endemic honey that combines different artificial intelligence networks with a confocal optical microscope and a tunable optical filter for hyperspectral data acquisition. Honey samples artificially adulterated with syrups at concentrations undetectable to the naked eye were used for validating different artificial intelligence models. Comparing Linear discriminant analysis (LDA), Support vector machine (SVM), and Neural Network (NN), we reach the best average accuracy value with SVM of 93% for all classes in both kinds of honey. We hope these results will be the starting point of a method for honey certification in Chile in an automated way and with high precision.

A simple method to quantify azo dyes in spices based on flow injection chromatography combined with chemometric tools.

Para Red (PR) and Sudan dyes have been illegally used as colorants to adulterate certain foods by enhancing their red/orange colour. In addition, they are toxic and carcinogenic. This work presents the development of a simple flow injection chromatographic method combined with chemometric tools to perform the determination of PR, Sudan I (SI) and Sudan II (SII) in food samples. The flow chromatographic system consisted of a low-pressure manifold coupled to a reverse phase monolithic column. A Partial Least Square (PLS) model was applied to resolve overlapped absorption spectra registered for each dye at the corresponding retention time. The relative errors of calibration (RMSECV, %) were 0.49, 0.85 and 0.23, and the relative errors of prediction (RMSEP, %) were 1.12, 0.75 and 0.33 for PR, SI and SII, respectively. The residual predictive deviation (RPD) values obtained were higher than 3.00 for all analytes. The method was successfully applied to quantify the dyes in six different commercial spices samples. The results were compared with the HPLC reference method concluding that there were no significant differences at the studied confidence level (α = 0.05). The proposed method can be used to rapidly determine the analytes in a simple, reliable, low-cost and environmentally-friendly manner. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-021-05299-8.