Rapid Sensing: Hand-Held and Portable FTIR Applications for On-Site Food Quality Control from Farm to Fork.

Today, one of the world's biggest problems is the assurance of food integrity from farm to fork. Economically motivated food adulteration and food authenticity problems are increasing daily with considerable health and economic effects. Early detection and prevention of food integrity-related problems could be provided by the application of effective on-site food analysis technologies. FTIR spectroscopy coupled with chemometrics can be used for the rapid quality control of a wide variety of food products with fast, high-throughput, accurate and nondestructive analysis advantages. In particular, hand-held and portable FTIR instruments have the potential to surveil food quality and food safety in various critical segments of the food supply chain. In this review, we explore the abilities of hand-held and portable FTIR spectrometers combined with multivariate statistics to conduct a quality evaluation of various food products in terms of food adulteration and authenticity issues. An examination of the literature showed that comparable results were obtained based on detection limits, correlation coefficient (R2) values, standard error values and discrimination power by using both portable/hand-held FTIR spectrometers and benchtop FTIR spectrometers. In conclusion, this review highlights the potential usefulness of portable and hand-held FTIR spectrometers combined with chemometrics for maintaining the food quality through the presentation of various applications that may shed light for on-site food control at any point of the food supply chain.

Food metabolomics: Latest hardware-developments for nontargeted food authenticity and food safety testing.

The analytical requirements for food testing have increased significantly in recent years. On the one hand, because food fraud is becoming an ever-greater challenge worldwide, and on the other hand because food safety is often difficult to monitor due to the far-reaching trade chains. In addition, the expectations of consumers on the quality of food have increased, and they are demanding extensive information. Cutting-edge analytical methods are required to meet these demands. In this context, non-targeted metabolomics strategies using mass and nuclear magnetic resonance spectrometers (mass spectrometry [MS]) have proven to be very suitable. MS-based approaches are of particular importance as they provide a comparatively high analytical coverage of the metabolome. Accordingly, the efficiency to address even challenging issues is high. A variety of hardware developments, which are explained in this review, have contributed to these advances. In addition, the potential of future developments is highlighted, some of which are currently not yet commercially available or only used to a comparatively small extent but are expected to gain in importance in the coming years.

Characterization of vanillin carbon isotope delta reference materials.

Stable carbon isotope ratio measurements are used to investigate the provenance of vanillin. In this study, a variety of commercial vanillin samples and vanilla products were analyzed to provide a frame of reference for the variability of carbon isotope delta values in various vanillin samples, with the results ranging from -20.6 to -36.7‰ relative to the Vienna Peedee Belemnite (VPDB). We present information on the development of two synthetic vanillin reference materials, VANA-1 and VANB-1, prepared in 0.75 g units in glass vials, to be used for the calibration of carbon isotope delta measurements of vanillin and other easily combustible organic materials. Characterization of 40 vials each of VANA-1 and VANB-1 was performed by three laboratories over several measurement sequences. The certified carbon isotope delta values are -31.30 ± 0.06‰ (VANA-1) and -25.85 ± 0.05‰ (VANB-1). These uncertainties, for the 95% confidence level, include considerations for measurement uncertainty, coherence of the reference materials used for calibration, batch homogeneity, and stability during storage and transportation. The results are traceable to the VPDB through a set of nine reference materials (IAEA-CH-6, USGS65, IAEA-600, NBS22, USGS61, IAEA-603, IAEA-610, IAEA-611, and IAEA-612). For up to date certified values, users should refer to doi.org/10.4224/crm.2022.vana-1 and doi.org/10.4224/crm.2022.vanb-1.

NMR internal standard signal shifts due to cyclodextrin inclusion complexes.

Nuclear magnetic resonance (NMR)-based screening of materials is a powerful tool for quality control, authenticity testing, and purity testing of compounds. However, reliance on 3-(trimethylsilyl)-propane-1-sulfonate (DSS) and 3-(trimethylsilyl)propanoic acid (TMSP) for referencing the spectra of aqueous samples is not without hazard, particularly with automated analyses. The assumption that these reference signals always represent 0 ppm is ubiquitous in NMR spectroscopy and is routinely used for spectral alignment. However, it has been found that cyclodextrins readily generate inclusion complexes with DSS and TMSP with the effect of rendering this assumption incorrect. These inclusion complexes alter the electronic shielding of the trimethylsilane functional groups on DSS and TMSP yielding a small, but significant, shift to a higher frequency in the signal relied upon for spectral referencing. As a result, samples containing traces of these compounds may be incorrectly declared fraudulent, inconsistent with standards, or adulterated. In order to maintain the viability of this screening method, vigilance and/or improved referencing of spectra is needed.

Food inauthenticity: Authority activities, guidance for food operators, and mitigation tools.

Historically, food fraud was a major public health concern which helped drive the development of early food regulations in many markets including the US and EU market. In the past 10 years, the integrity of food chains with respect to food fraud has again been questioned due to high profile food fraud cases. We provide an overview of the resulting numerous authoritative activities underway within different regions to counter food fraud, and we describe the guidance available to the industry to understand how to assess the vulnerability of their businesses and implement appropriate mitigation. We describe how such controls should be an extension of those already in place to manage wider aspects of food authenticity, and we provide an overview of relevant analytical tools available to food operators and authorities to protect supply chains. Practical Application: Practical Application of the provided information by the food industry in selecting resources (guidance document, analytical methods etc.).

Capillary electromigration methods for fatty acids determination in vegetable and marine oils: A review.

Fatty acids determination is of paramount importance for quality control and suitable labeling of edible oils, required by regulatory agencies in several countries, and fast methods for this determination are worldly desired. This review article aimed to explore the available analytical methods for vegetable and marine oils analyses employing CE, which can be a straightforward and faster alternative than GC methods for fatty acid determination, considering some purposes. CE usually offers the possibility of a rapid analysis with a simple preparation of the sample, without requiring specific columns, which are inherent advantages of the technique. Instrumental conditions and the key points about fatty acids determination employing the technique are highlighted, and the main challenges and perspectives are also approached. Potential use of CE for edible oil analyses has been demonstrated for research and routine, which can be of interest for industries, regulatory agencies, and edible oil researchers. Therefore, we have explored the analytical approaches described in the last decades, intending to spread the interest of CE methods for fatty acid monitoring, label accuracy assessment, and food authenticity evaluation of edible oils.

Detection of bovine milk adulteration in caprine milk with N-acetyl carbohydrate biomarkers by using 1H nuclear magnetic resonance spectroscopy.

In a return to tradition, the popularity of caprine milk is on the rise. However, particularly in countries with developed dairy industries based on bovine milk, there is the risk of adulteration with bovine milk, which is a cheaper alternative. Thus, a rapid, robust, and simple method for the detection of bovine milk added to caprine milk is necessary, and 1H nuclear magnetic resonance spectroscopy appears to provide a solution. A matrix of 115 pure and artificially adulterated pasteurized milk samples was prepared and used to discover biomarkers of bovine milk that are independent of chemical and biological variation caused by factors such as genetics, diet, or seasonality. Principal component analysis and orthogonal projections to latent structures discriminant analysis of pure bovine milk and pure caprine milk revealed spectral features that were assigned to the resonances of 4 molecules. Of these, the peaks corresponding to protons in the N-acetylglucosamine and N-acetylgalactosamine acetyl moieties showed significant applicability for our method. Receiver operating characteristic curve analysis was used to evaluate the performance of the peak integrals as biomarkers of adulteration. This approach was able to distinguish caprine milk adulterated with 5% of bovine milk with 84.78% accuracy and with 10% of bovine milk an excellent 95.65% accuracy. This study demonstrates that N-acetyl carbohydrates could be used as biomarkers for the detection of bovine milk in caprine milk and could help in protecting caprine milk authenticity.

Short communication: Detection of undeclared presence of bovine milk in buffalo yogurt.

The authenticity of buffalo (Bubalus bubalis) dairy products is a focal issue, considering the increasing demand for buffalo milk products. Therefore, the aim of this study was to investigate the undeclared presence of bovine (Bos taurus) milk in buffalo yogurt, to understand which risk factors might make the product vulnerable to fraud. Real-time PCR assay showed the undeclared presence of bovine DNA in addition to buffalo DNA in 18 of 72 samples. Given the widespread lack of data on the presence of undeclared milk species in buffalo dairy products, the study provides a significant insight into the incidence of fraud in the buffalo dairy field. The data from this study could help improve the analysis of food safety risks along the buffalo milk supply chain and in the dairy processing industry, perceived as being highly vulnerable to food fraud, and prioritize target areas for food policy making to steer and enforce European food fraud regulations.

Application of the Metabolomics Approach in Food Authentication.

The authentication of food products is essential for food quality and safety. Authenticity assessments are important to ensure that the ingredients or contents of food products are legitimate and safe to consume. The metabolomics approach is an essential technique that can be utilized for authentication purposes. This study aimed to summarize food authentication through the metabolomics approach, to study the existing analytical methods, instruments, and statistical methods applied in food authentication, and to review some selected food commodities authenticated using metabolomics-based methods. Various databases, including Google Scholar, PubMed, Scopus, etc., were used to obtain previous research works relevant to the objectives. The review highlights the role of the metabolomics approach in food authenticity. The approach is technically implemented to ensure consumer protection through the strict inspection and enforcement of food labeling. Studies have shown that the study of metabolomics can ultimately detect adulterant(s) or ingredients that are added deliberately, thus compromising the authenticity or quality of food products. Overall, this review will provide information on the usefulness of metabolomics and the techniques associated with it in successful food authentication processes, which is currently a gap in research that can be further explored and improved.

A New Method for Olive Oil Screening Using Multivariate Analysis of Proton NMR Spectra.

A new NMR-based method for the discrimination of olive oils of any grade from seed oils and mixtures thereof was developed with the aim of allowing the verification of olive oil authenticity. Ten seed oils and seven monovarietal and blended extra virgin olive oils were utilized to develop a principal component analysis (PCA) based analysis of 1H NMR spectra to rapidly and accurately determine the authenticity of olive oils. Another twenty-eight olive oils were utilized to test the principal component analysis (PCA) based analysis. Detection of seed oil adulteration levels as low as 5% v/v has been shown using simple one-dimensional proton spectra obtained using a 400 MHz NMR spectrometer equipped with a room temperature inverse probe. The combination of simple sample preparation, rapid sample analysis, novel processing parameters, and easily interpreted results, makes this method an easily accessible tool for olive oil fraud detection by substitution or dilution compared to other methods already published.

Multispecies Identification of Oilseed- and Meat-Specific Proteins and Heat-Stable Peptide Markers in Food Products.

Consumer demand for both plant products and meat products enriched with plant raw materials is constantly increasing. Therefore, new versatile and reliable methods are needed to find and combat fraudulent practices in processed foods. The objective of this study was to identify oilseed species-specific peptide markers and meat-specific markers that were resistant to processing, for multispecies authentication of different meat and vegan food products using the proteomic LC-MS/MS method. To assess the limit of detection (LOD) for hemp proteins, cooked meatballs consisting of three meat species and hemp cake at a final concentration of up to 7.4% were examined. Hemp addition at a low concentration of below 1% was detected. The LOD for edestin subunits and albumin was 0.9% (w/w), whereas for 7S vicilin-like protein it was 4.2% (w/w). Specific heat-stable peptides unique to hemp seeds, flaxseed, nigella, pumpkin, sesame, and sunflower seeds, as well as guinea fowl, rabbit, pork, and chicken meat, were detected in different meat and vegan foods. Most of the oilseed-specific peptides were identified as processing-resistant markers belonging to 11S globulin subunits, namely conlinin, edestin, helianthinin, pumpkin vicilin-like or late embryogenesis proteins, and sesame legumin-like as well as 2S albumins and oleosin isoforms or selected enzymic proteins.

Determination of geographical origin of concentrated apple juice through analysis of stable isotopic and mineral elemental fingerprints: preliminary results.

BACKGROUND: With increasing attention being paid to food authenticity, the geographic origin of food has become a topic of interest for both consumers and producers. As far as we know, there are relatively few studies on the origin traceability of concentrated apple juice. The most commonly used methods of origin tracing research is by using stable isotopes and mineral elements technology, because these indicators are directly related to local geographical environment. RESULTS: In this study, a discriminant model was established by determining the content of the stable isotopes (δ13 C, δ18 O) and 13 mineral elements (B, Mn, Co, Ni, Cu, Sr, V, Ba, Fe, Mg, Na, Ca and Cr) in concentrated apple juice. Linear discriminant analysis (LDA), principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were employed for regional classification of samples. After data conversion and correlation analysis, spatial and quantitative prediction models were established using multiple linear regressions. Finally, the experimental results showed that the eight key variables(δ 13 C, δ 18 O, B, Ca, Mg, Cu, Sr and Na) selected by the analysis can be used to further characterize the production area. CONCLUSION: The results showed that the carbon and oxygen isotopes combined with certain mineral elements can be used to indicate the origin of concentrated apple juice. © 2020 Society of Chemical Industry.

Proteomic analysis of oilseed cake: a comparative study of species-specific proteins and peptides extracted from ten seed species.

BACKGROUND: In recent years there has been a visible trend among consumers to move away from consuming meat in favor of plant products. Meat producers have therefore been trying to meet the expectations of consumers by introducing new products to the food market with a greater proportion of plant ingredients. Meat products are enriched not only by the addition of vegetable oils but also by ground or whole oilseeds or their preparation. In this study, we present in-solution tryptic digestion and an ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS/MS)-based proteomics approach to investigate specific proteins and peptides of ten oilseed cakes, by-products of cold pressing oil from coconut, evening primrose, hemp, flax, milk thistle, nigella, pumpkin, rapeseed, sesame, and sunflower seeds, for authentication purposes. RESULTS: We identified a total of 229 unique oilseed proteins. The number of specific proteins varied depending on the sample, from 4 to 48 in evening primrose and sesame. Moreover, we identified approximately 440 oilseed unique peptides in the cakes of all the analyzed oilseeds; the largest amounts were found in sesame (107 peptides), sunflower (100), pumpkin, hemp (42), rapeseed (36), and flax cake (35 peptides). CONCLUSIONS: We provide novel information on unique / species-specific peptide markers that will extend the scope of testing the authenticity of a wide range of foods. The results of this peptide discovery experiment may further contribute to the development of targeted methods for the detection and quantification of oilseed proteins in processed foods, and thus to the improvement of food quality. © 2020 Society of Chemical Industry.

Determining the presence of undeclared animal species using Real-time PCR in canned and ready-to-eat meat products in South Africa.

DNA based PCR is the most widely used technique for the detection of animal species in processed meat products. However, the detection of animal species in highly processed meat products, specifically, canned meat, has been reported to be challenging due to the presence of highly degraded DNA and/or the inability to extract sufficient amount of amplifiable DNA. The aim of this study was to evaluate the use of Real-time PCR to detect animal species in ready-to-eat meat products which represent highly processed complex food matrices. DNA was extracted from a total of 44 ready-to-eat meat products purchased from supermarkets in South Africa. The extracted DNA was screened for the presence of commonly reported undeclared animal species using Real-time PCR. Real-time PCR successfully detected the animal species declared on the product label, thus demonstrating its suitability for highly processed complex food matrices. Undeclared animal species was detected in 27% of the meat products tested in this study. Surprisingly, four products marketed with a specific "no-pork" claim tested positive for pork. An additional eight products tested positive for undeclared chicken, beef and/or sheep. The presence of undeclared animal species indicates a need for food authenticity monitoring. In cases where it may not be practically feasible to prevent the adventitious presence of unintended animal species despite adhering to the highest standards of production, it may be advisable for manufacturers to implement precautionary labelling. The use of precautionary labelling for animal species in processed meat products is a new concept that requires further consideration.

Food authentication in real life: How to link nontargeted approaches with routine analytics?

In times of increasing globalization and the resulting complexity of trade flows, securing food quality is an increasing challenge. The development of analytical methods for checking the integrity and, thus, the safety of food is one of the central questions for actors from science, politics, and industry. Targeted methods, for the detection of a few selected analytes, still play the most important role in routine analysis. In the past 5 years, nontargeted methods that do not aim at individual analytes but on analyte profiles that are as comprehensive as possible have increasingly come into focus. Instead of investigating individual chemical structures, data patterns are collected, evaluated and, depending on the problem, fed into databases that can be used for further nontargeted approaches. Alternatively, individual markers can be extracted and transferred to targeted methods. Such an approach requires (i) the availability of authentic reference material, (ii) the corresponding high-resolution laboratory infrastructure, and (iii) extensive expertise in processing and storing very large amounts of data. Probably due to the requirements mentioned above, only a few methods have really established themselves in routine analysis. This review article focuses on the establishment of nontargeted methods in routine laboratories. Challenges are summarized and possible solutions are presented.

Investigating aroma diversity combining purge-and-trap, comprehensive two-dimensional gas chromatography, and mass spectrometry.

Headspace gas chromatography is frequently used for aroma profiling thanks to its ability to naturally exploit the volatility of aroma compounds, and also to provide chemical information on sample composition. Its main advantages rely on simplicity, no use of solvent, amenability to automation, and the cleanliness of the extract. In the present contribution, the most effective sampling (dynamic extraction), separation (multidimensional gas chromatography), and detection (mass spectrometry) techniques for untargeted analysis are exploited in combination, showing their potential in unraveling aroma profiles in fruit beers. To complete the overall analytical process, a neat workflow for data analysis is discussed and used for the successful characterization and identification of five different beer flavors (berries, cherry, banana, apple, and peach). From the technical viewpoint, the coupling of purge-and-trap, comprehensive two-dimensional gas chromatography, and mass spectrometry makes the global methodology unique, and it is for the first time discussed. A (low-)flow modulation approach allowed for the full transfer into the second dimension with mass-spectrometry compatible flow (< 7 mL/min), avoiding the need of splitting before detection and making the overall method sensitive (1.2-5.2-fold higher signal to noise ratio compared to unmodulated gas chromatography conditions) and selective.

Historical Evolution and Food Control Achievements of Near Infrared Spectroscopy, Electronic Nose, and Electronic Tongue-Critical Overview.

Amid today's stringent regulations and rising consumer awareness, failing to meet quality standards often results in health and financial compromises. In the lookout for solutions, the food industry has seen a surge in high-performing systems all along the production chain. By virtue of their wide-range designs, speed, and real-time data processing, the electronic tongue (E-tongue), electronic nose (E-nose), and near infrared (NIR) spectroscopy have been at the forefront of quality control technologies. The instruments have been used to fingerprint food properties and to control food production from farm-to-fork. Coupled with advanced chemometric tools, these high-throughput yet cost-effective tools have shifted the focus away from lengthy and laborious conventional methods. This special issue paper focuses on the historical overview of the instruments and their role in food quality measurements based on defined food matrices from the Codex General Standards. The instruments have been used to detect, classify, and predict adulteration of dairy products, sweeteners, beverages, fruits and vegetables, meat, and fish products. Multiple physico-chemical and sensory parameters of these foods have also been predicted with the instruments in combination with chemometrics. Their inherent potential for speedy, affordable, and reliable measurements makes them a perfect choice for food control. The high sensitivity of the instruments can sometimes be generally challenging due to the influence of environmental conditions, but mathematical correction techniques exist to combat these challenges.

Food Phenotyping: Recording and Processing of Non-Targeted Liquid Chromatography Mass Spectrometry Data for Verifying Food Authenticity.

Experiments based on metabolomics represent powerful approaches to the experimental verification of the integrity of food. In particular, high-resolution non-targeted analyses, which are carried out by means of liquid chromatography-mass spectrometry systems (LC-MS), offer a variety of options. However, an enormous amount of data is recorded, which must be processed in a correspondingly complex manner. The evaluation of LC-MS based non-targeted data is not entirely trivial and a wide variety of strategies have been developed that can be used in this regard. In this paper, an overview of the mandatory steps regarding data acquisition is given first, followed by a presentation of the required preprocessing steps for data evaluation. Then some multivariate analysis methods are discussed, which have proven to be particularly suitable in this context in recent years. The publication closes with information on the identification of marker compounds.

The magic angle view to food: magic-angle spinning (MAS) NMR spectroscopy in food science.

Nuclear Magnetic Resonance (NMR) spectroscopy has been used in food science and nutritional studies for decades and is one of the major analytical platforms in metabolomics. Many foods are solid or at least semi-solid, which denotes that the molecular motions are restricted as opposed to in pure liquids. While the majority of NMR spectroscopy is performed on liquid samples and a solid material gives rise to constraints in terms of many chemical analyses, the magic angle thrillingly enables the application of NMR spectroscopy also on semi-solid and solid materials. This paper attempts to review how magic-angle spinning (MAS) NMR is used from 'farm-to-fork' in food science.

Improving Sensitivity in Raman Imaging for Thin Layered and Powdered Food Analysis Utilizing a Reflection Mirror.

Raman imaging has been proven to be a powerful analytical technique for the characterization and visualization of chemical components in a range of products, particularly in the food and pharmaceutical industries. The conventional backscattering Raman imaging technique for the spatial analysis of a deep layer suffers from the presence of intense fluorescent and Raman signals originating from the surface layer which mask the weaker subsurface signals. Here, we demonstrated the application of a new reflection amplifying method using a background mirror as a sample holder to increase the Raman signals from a deep layer. The approach is conceptually demonstrated on enhancing the Raman signals from the subsurface layer. Results show that when bilayer samples are scanned on a reflection mirror, the average signals increase 1.62 times for the intense band at 476 cm-1 of starch powder, and average increases of 2.04 times (for the band at 672 cm-1) for a subsurface layer of high Raman sensitive melamine powder under a 1 mm thick teflon sheet. The method was then applied successfully to detect noninvasively the presence of small polystyrene pieces buried under a 2 mm thick layer of food powder (a case of powdered food adulteration) which otherwise are inaccessible to conventional backscattering Raman imaging. In addition, the increase in the Raman signal to noise ratio when measuring samples on a mirror is an important feature in many applications where high-throughput imaging is of interest. This concept is also applicable in an analogous manner to other disciplines, such as pharmaceutical where the Raman signals from deeper zones are typically, substantially diluted due to the interference from the surface layer.