The fate of mycotoxins during secondary food processing of maize for human consumption.

Mycotoxins are naturally occurring fungal metabolites that are associated with health hazards and are widespread in cereals including maize. The most common mycotoxins in maize that occur at relatively high levels are fumonisins (FBs), zearalenone, and aflatoxins; furthermore, other mycotoxins such as deoxynivalenol and ochratoxin A are frequently present in maize. For these toxins, maximum levels are laid down in the European Union (EU) for maize raw materials and maize-based foods. The current review article gives a comprehensive overview on the different mycotoxins (including mycotoxins not regulated by EU law) and their fate during secondary processing of maize, based on the data published in the scientific literature. Furthermore, potential compliance with the EU maximum levels is discussed where appropriate. In general, secondary processing can impact mycotoxins in various ways. Besides changes in mycotoxin levels due to fractionation, dilution, and/or concentration, mycotoxins can be affected in their chemical structure (causing degradation or modification) or be released from or bound to matrix components. In the current review, a special focus is set on the effect on mycotoxins caused by different heat treatments, namely, baking, roasting, frying, (pressure) cooking, and extrusion cooking. Production processes involving multiple heat treatments are exemplified with the cornflakes production. For that, potential compliance with FB maximum levels was assessed. Moreover, effects of fermentation of maize matrices and production of maize germ oil are covered by this review.

NMR spectroscopy in wine authentication: An official control perspective.

Wine authentication is vital in identifying malpractice and fraud, and various physical and chemical analytical techniques have been employed for this purpose. Besides wet chemistry, these include chromatography, isotopic ratio mass spectrometry, optical spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy, which have been applied in recent years in combination with chemometric approaches. For many years, 2 H NMR spectroscopy was the method of choice and achieved official recognition in the detection of sugar addition to grape products. Recently, 1 H NMR spectroscopy, a simpler and faster method (in terms of sample preparation), has gathered more and more attention in wine analysis, even if it still lacks official recognition. This technique makes targeted quantitative determination of wine ingredients and nontargeted detection of the metabolomic fingerprint of a wine sample possible. This review summarizes the possibilities and limitations of 1 H NMR spectroscopy in analytical wine authentication, by reviewing its applications as reported in the literature. Examples of commercial and open-source solutions combining NMR spectroscopy and chemometrics are also examined herein, together with its opportunities of becoming an official method.

The Fate of Mycotoxins During the Processing of Wheat for Human Consumption.

Mycotoxins are a potential health threat in cereals including wheat. In the European Union (EU), mycotoxin maximum levels are laid down for cereal raw materials and final food products. For wheat and wheat-based products, the EU maximum levels apply to deoxynivalenol (DON), zearalenone, aflatoxins, and ochratoxin A. This review provides a comprehensive overview on the different mycotoxins and their legal limits and on how processing of wheat can affect such contaminants, from raw material to highly processed final products, based on relevant scientific studies published in the literature. The potential compliance with EU maximum levels is discussed. Of the four mycotoxins regulated in wheat-based foods in the EU, most data are available for DON, whereas aflatoxins were rarely studied in the processing of wheat. Furthermore, available data on the effect of processing are outlined for mycotoxins not regulated by EU law-including modified and emerging mycotoxins-and which cover DON derivatives (DON-3-glucoside, mono-acetyl-DONs, norDONs, deepoxy-DON), nivalenol, T-2 and HT-2 toxins, enniatins, beauvericin, moniliformin, and fumonisins. The processing steps addressed in this review cover primary processing (premilling and milling operations) and secondary processing procedures (such as fermentation and thermal treatments). A special focus is on the production of baked goods, and processing factors for DON in wheat bread production were estimated. For wheat milling products derived from the endosperm and for white bread, compliance with legal requirements seems to be mostly achievable when applying good practices. In the case of wholemeal products, bran-enriched products, or high-cereal low-moisture bakery products, this appears to be challenging and improved technology and/or selection of high-quality raw materials would be required.

Origin authentication of distillers' dried grains and solubles (DDGS)--application and comparison of different analytical strategies.

In the context of products from certain regions or countries being banned because of an identified or non-identified hazard, proof of geographical origin is essential with regard to feed and food safety issues. Usually, the product labeling of an affected feed lot shows origin, and the paper documentation shows traceability. Incorrect product labeling is common in embargo situations, however, and alternative analytical strategies for controlling feed authenticity are therefore needed. In this study, distillers' dried grains and solubles (DDGS) were chosen as the product on which to base a comparison of analytical strategies aimed at identifying the most appropriate one. Various analytical techniques were investigated for their ability to authenticate DDGS, including spectroscopic and spectrometric techniques combined with multivariate data analysis, as well as proven techniques for authenticating food, such as DNA analysis and stable isotope ratio analysis. An external validation procedure (called the system challenge) was used to analyze sample sets blind and to compare analytical techniques. All the techniques were adapted so as to be applicable to the DDGS matrix. They produced positive results in determining the botanical origin of DDGS (corn vs. wheat), and several of them were able to determine the geographical origin of the DDGS in the sample set. The maintenance and extension of the databanks generated in this study through the analysis of new authentic samples from a single location are essential in order to monitor developments and processing that could affect authentication.

Metabolic fingerprinting based on high-resolution tandem mass spectrometry: a reliable tool for wine authentication?

Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (MS) and an alternative technology represented by direct analysis in real time coupled with quadrupole time-of-flight MS were investigated for metabolic fingerprinting of 343 red and white wine samples. Direct injection of pure wine and an extraction procedure optimized for isolation of polyphenols were used to compare different analytical and data handling strategies. After data processing and data pretreatment, principal component analysis was initially used to explore the data structure. Initially, the unsupervised models revealed a notable clustering according to the grape varieties, and therefore supervised orthogonal partial least squares discriminant analysis models were created and validated for separation of red and white wines according to the grape variety. The validated orthogonal partial least squares discriminant analysis models based on data (ions) recorded in positive ionization mode were able to classify correctly 95% of samples. In parallel, authentication parameters, such as origin and vintage, were evaluated, and they are discussed. A tentative identification of markers was performed using accurate mass measurement of MS and MS/MS spectra, different software packages and different online libraries. In this way, different flavonol glucosides and polyphenols were identified as wine markers according to the grape varieties.

Non-volatile molecular composition and discrimination of single grape white of chardonnay, riesling, sauvignon blanc and silvaner using untargeted GC-MS analysis.

This study developed and applied a GC-MS method aiming at molecular fingerprinting of 120 commercial single grape white wines (Chardonnay, Riesling, Sauvignon Blanc and Silvaner) for possible authentication according to grape variety. The method allowed detection of 372 peaks and tentative identification of 146 metabolites including alcohols, organic acids, esters, amino acids and sugars. The grape variety effect explained 8.3% of the total metabolite variation. Univariate tests showed two-thirds of the metabolites being different between grape varieties. Partial least squares-discriminant analysis based classification models were developed for each grape variety and a panel of classifiers (42 metabolites) was established. All the classification models for grape variety showed a high certainty (>91%) for an independent test set. Riesling contained the highest relative concentrations of sugars and organic acids, while concentrations of hydroxytyrosol and gallic acid, common antioxidants in wine, decreased in the order of Chardonnay > Riesling > Sauvignon Blanc > Silvaner.

Factors during Production of Cereal-Derived Feed That Influence Mycotoxin Contents.

Mycotoxins are naturally present in cereal-based feed materials; however, due to adverse effects on animal health, their presence in derived animal feed should be minimized. A systematic literature search was conducted to obtain an overview of all factors from harvest onwards influencing the presence and concentration of mycotoxins in cereal-based feeds. The feed production processes covered included the harvest time, post-harvest practices (drying, cleaning, storage), and processing (milling, mixing with mycotoxin binders, extrusion cooking, ensiling). Delayed harvest supports the production of multiple mycotoxins. The way feed materials are dried after harvest influences the concentration of mycotoxins therein. Applying fungicides on the feed materials after harvest as well as cleaning and sorting can lower the concentration of mycotoxins. During milling, mycotoxins might be redistributed in cereal feed materials and fractions thereof. It is important to know which parts of the cereals are used for feed production and whether or not mycotoxins predominantly accumulate in these fractions. For feed production, mostly the milling fractions with outer parts of cereals, such as bran and shorts, are used, in which mycotoxins concentrate during processing. Wet-milling of grains can lower the mycotoxin content in these parts of the grain. However, this is typically accompanied by translocation of mycotoxins to the liquid fractions, which might be added to by-products used as feed. Mycotoxin binders can be added during mixing of feed materials. Although binders do not remove mycotoxins from the feed, the mycotoxins become less bioavailable to the animal and, in the case of food-producing animals, to the consumer, lowering the adverse effects of mycotoxins. The effect of extruding cereal feed materials is dependent on several factors, but in principle, mycotoxin contents are decreased after extrusion cooking. The results on ensiling are not uniform; however, most of the data show that mycotoxin production is supported during ensiling when oxygen can enter this process. Overall, the results of the literature review suggest that factors preventing mycotoxin production have greater impact than factors lowering the mycotoxin contents already present in feed materials.

What's in a wine? - A spot check of the integrity of European wine sold in China based on anthocyanin composition, stable isotope and glycerol impurity analysis.

The international wine market has been repeatedly hit by cases of fraud in recent decades. While several studies attested a special vulnerability of the fast growing wine business in China, reports on chemical analyses of commercial wine samples are rare. We examined 50 predominantly red wines with European labelling, which were purchased on the Chinese market, for fraud-relevant parameters. More than 20% of the tested samples revealed anomalies in relation to the stable isotope ratios of D/H, 18O/16O and 13C/12C, contents of technical glycerol by-products or anthocyanin composition. These results strongly suggested watering of the wines, chaptalisation, glycerol addition or the use of non-Vitis anthocyanin sources, respectively. Some of these samples also showed suspicious spelling errors or other irregularities in the labelling, but the majority appeared genuine to the eye. Hence, this spot check demonstrates the importance of chemical authenticity analysis of market samples in order to detect fraudulent products. Moreover, we used the same sample set for an evaluation of the Chinese standard method for carbon stable isotope determination of wine ethanol in comparison to the current OIV (International Organisation of Vine and Wine) standard method. The results of a Bland-Altman analysis indicated that the methods can be applied interchangeably. As the two methods differ in their workflow and in the requested equipment, this might eventually enable more laboratories to perform 13C/12C analysis of wine and spirits.

Mycotoxins during the Processes of Nixtamalization and Tortilla Production.

Tortillas are a traditional staple food in Mesoamerican cuisine, which have also become popular on a global level, e.g., for wraps or as snacks (tortilla chips). Traditional tortilla production includes alkaline cooking (nixtamalization) of maize kernels. This article summarizes the current knowledge on mycotoxin changes during the nixtamalization of maize and tortilla production. Upon nixtamalization, mycotoxins can be affected in different ways. On the one hand, the toxins can be physically removed during steeping and washing. On the other hand, mycotoxins might be degraded, modified, or released/bound in the matrix by high pH and/or high temperature. This also applies to the subsequent baking of tortillas. Many studies have shown reduced mycotoxin levels in alkali-cooked maize and in tortillas. Most of the available data relate to aflatoxins and fumonisins. The reduction (and detoxification) of aflatoxins during nixtamalization might, however, be partially reversed in acidic conditions. The loss of fumonisin concentrations is to some extent accompanied by hydrolyzation and by lower toxicity. However, some studies have indicated the potential formation of toxicologically relevant modified forms and matrix-associated fumonisins. More data are required to assess the influence of alkaline cooking regarding such modified forms, as well as mycotoxins other than aflatoxins/fumonisins.

Non-targeted detection of paprika adulteration using mid-infrared spectroscopy and one-class classification - Is it data preprocessing that makes the performance?

A method for the non-targeted detection of paprika adulteration was developed using Fourier transform mid-infrared (FT-MIR) spectroscopy and one-class soft independent modelling of class analogy (OCSIMCA). One-class models based on commercially available paprika powders were developed and optimised to provide >80% sensitivity by external validation. The performances of the established models for adulteration detection were tested by predicting spiked paprika samples with various types of fraudulent material and levels of adulterations including 1% (w/w) Sudan I, 1% (w/w) Sudan IV, 3% (w/w) lead chromate, 3% (w/w) lead oxide, 5% (w/w) silicon dioxide, 10% (w/w) polyvinyl chloride, and 10% (w/w) gum arabic. Further, the influence of data preprocessing on the model performance was investigated. Relationship between classification results and data preprocessing was identified and specificity >80% was achieved for all adulterants by applying different preprocessing methods including standard normal variate (SNV), first and second derivatives, smoothing, and combinations thereof.

Review of validation and reporting of non-targeted fingerprinting approaches for food authentication.

Food fingerprinting approaches are expected to become a very potent tool in authentication processes aiming at a comprehensive characterization of complex food matrices. By non-targeted spectrometric or spectroscopic chemical analysis with a subsequent (multivariate) statistical evaluation of acquired data, food matrices can be investigated in terms of their geographical origin, species variety or possible adulterations. Although many successful research projects have already demonstrated the feasibility of non-targeted fingerprinting approaches, their uptake and implementation into routine analysis and food surveillance is still limited. In many proof-of-principle studies, the prediction ability of only one data set was explored, measured within a limited period of time using one instrument within one laboratory. Thorough validation strategies that guarantee reliability of the respective data basis and that allow conclusion on the applicability of the respective approaches for its fit-for-purpose have not yet been proposed. Within this review, critical steps of the fingerprinting workflow were explored to develop a generic scheme for multivariate model validation. As a result, a proposed scheme for "good practice" shall guide users through validation and reporting of non-targeted fingerprinting results. Furthermore, food fingerprinting studies were selected by a systematic search approach and reviewed with regard to (a) transparency of data processing and (b) validity of study results. Subsequently, the studies were inspected for measures of statistical model validation, analytical method validation and quality assurance measures. In this context, issues and recommendations were found that might be considered as an actual starting point for developing validation standards of non-targeted metabolomics approaches for food authentication in the future. Hence, this review intends to contribute to the harmonization and standardization of food fingerprinting, both required as a prior condition for the authentication of food in routine analysis and official control.

Screening for sulfate in distillers dried grains and solubles by FT-IR spectroscopy.

Distillers Dried Grains and Solubles (DDGS) are an animal feed containing varying levels of sulfur. As ruminants are susceptible to high sulfur diets, sulfur content is of major interest to the parties involved. The variation in levels of sulfur in DDGS is mainly due to sulfate derived from the addition of sulfuric acid during the production. ATR/FT-IR spectroscopy was used to determine sulfate levels in 90 DDGS samples from various origins (Canada, China, EU, and U.S.A.). Specific absorption bands for sulfate at 615 and 1107 cm(-1) enabled the analysis of sulfate in the DDGS matrix. Besides direct quantification (using band at 615 cm(-1)), PLS regression was applied for the prediction of sulfate using FT-IR spectra and calibration with reference values analyzed by capillary electrophoresis. An extended calculation on the total sulfur estimated that 11% of the DDGS samples analyzed in this study featured sulfur contents higher than 0.80%.

Authentication of the botanical and geographical origin of distillers dried grains and solubles (DDGS) by FT-IR spectroscopy.

Distillers dried grains and solubles (DDGS) were investigated with attenuated total reflection FT-IR spectroscopy both directly in their solid state and as the isolated oils (fat fractions). The collected spectra were evaluated in a first step with principal component analysis (PCA) according to the botanical origin (corn, rice, wheat) and the geographical origin (Canada, China, European Union, India, United States) of the DDGS. In a second step, statistical models were constructed for the characterization of the botanical and geographical origin using linear discriminant analysis (LDA) and soft independent modeling of class analogy (SIMCA). For this purpose, the botanical origin was investigated more deeply for corn and wheat as the most important raw materials used for DDGS production. Also, the geographical origin was investigated exemplary for corn DDGS, derived from China and the United States. Models were validated by a randomized batchwise procedure and showed satisfactory classification rates, in most cases better than 80% correct classification.