The Detection of Substitution Adulteration of Paprika with Spent Paprika by the Application of Molecular Spectroscopy Tools.

The spice paprika (Capsicum annuum and frutescens) is used in a wide variety of cooking methods as well as seasonings and sauces. The oil, paprika oleoresin, is a valuable product; however, once removed from paprika, the remaining spent product can be used to adulterate paprika. Near-infrared (NIR) and Fourier transform infrared (FTIR) were the platforms selected for the development of methods to detect paprika adulteration in conjunction with chemometrics. Orthogonal partial least squares discriminant analysis (OPLS-DA), a supervised technique, was used to develop the chemometric models, and the measurement of fit (R2) and measurement of prediction (Q2) values were 0.853 and 0.819, respectively, for the NIR method and 0.943 and 0.898 respectively for the FTIR method. An external validation set was tested against the model, and a receiver operating curve (ROC) was created. The area under the curve (AUC) for both methods was highly accurate at 0.951 (NIR) and 0.907 (FTIR). The levels of adulteration with 100% correct classification were 50-90% (NIR) and 40-90% (FTIR). Sudan I dye is a commonly used adulterant in paprika; however, in this study it was found that this dye had no effect on the outcome of the result for spent material adulteration.

The Rapid Detection of Sage Adulteration Using Fourier Transform Infra-Red (FTIR) Spectroscopy and Chemometrics.

Background: Sage, a common term for the various species of the genus Salvia L., is an herb that is mainly used as a seasoning, or for medicinal purposes. Valuable herbs such as sage, are under constant threat from criminals dealing in economically motivated adulteration. Objective: In this study, the development of a rapid screening technique to detect adulteration in sage was developed using FTIR and chemometrics. Method: A range of sage samples were collected, along with possible known adulterants, olive leaves, myrtle leaves, sumac, hazelnut leaves, cistus and phlomis, strawberry tree leaves and sandalwood. The samples were analyzed on the Thermo Nicolet iS5 FTIR with iD7 attenuated total reflectance accessory and diamond crystal. Chemometric techniques were applied to convert this raw spectral data obtained from the instrument into qualitative models. The qualitative chemometric models for adulteration detection were obtained using principal component analysis and orthogonal partial least squares-discriminant analysis following preprocessing of the spectra. Results: The orthogonal partial least squares-discriminant analysis models had a measurement of fit of 0.978 and 0.952 and a measurement of prediction of 0.975 and 0.936 for binary and multiclass models, respectively. The receiver operating curves following external validation had an area under the curve of 1, indicating excellent method performance. Conclusions: The use of FTIR and chemometrics can potentially screen unknown sage samples for adulteration and can be used in the fight against fraud in the herb and spice industry.

Development of a comprehensive analytical platform for the detection and quantitation of food fraud using a biomarker approach. The oregano adulteration case study.

Due to increasing number of food fraud incidents, there is an inherent need for the development and implementation of analytical platforms enabling detection and quantitation of adulteration. In this study a set of unique biomarkers of commonly found oregano adulterants became the targets in the development of a LC-MS/MS method which underwent a rigorous in-house validation. The method presented very high selectivity and specificity, excellent linearity (R2>0.988) low decision limits and detection capabilities (<2%), acceptable accuracy (intra-assay 92-113%, inter-assay 69-138%) and precision (CV<20%). The method was compared with an established FTIR screening assay and revealed a good correlation of quali- and quantitative results (R2>0.81). An assessment of 54 suspected adulterated oregano samples revealed that almost 90% of them contained at least one bulking agent, with a median level of adulteration of 50%. Such innovative methodologies need to be established as routine testing procedures to detect and ultimately deter food fraud.

A comprehensive strategy to detect the fraudulent adulteration of herbs: The oregano approach.

Fraud in the global food supply chain is becoming increasingly common due to the huge profits associated with this type of criminal activity. Food commodities and ingredients that are expensive and are part of complex supply chains are particularly vulnerable. Both herbs and spices fit these criteria perfectly and yet strategies to detect fraudulent adulteration are still far from robust. An FT-IR screening method coupled to data analysis using chemometrics and a second method using LC-HRMS were developed, with the latter detecting commonly used adulterants by biomarker identification. The two tier testing strategy was applied to 78 samples obtained from a variety of retail and on-line sources. There was 100% agreement between the two tests that over 24% of all samples tested had some form of adulterants present. The innovative strategy devised could potentially be used for testing the global supply chains for fraud in many different forms of herbs.

Determination of the Mycotoxin Content in Distiller's Dried Grain with Solubles Using a Multianalyte UHPLC-MS/MS Method.

There are more than 300 potential mycotoxins that can contaminate food and feed and cause adverse effects in humans and animals. The data on the co-occurrence of mycotoxins in novel animal feed materials, such as distiller's dried grain with solubles (DDGS), are limited. Thus, a UHPLC-MS/MS method for the quantitation of 77 mycotoxins and other fungal metabolites was used to analyze 169 DDGS samples produced from wheat, maize, and barley and 61 grain samples. All DDGS samples analyzed were contaminated with 13-34 different mycotoxins. Fumonisins were present in all 52 maize DDGS samples (81.0-6890 µg/kg for fumonisin B1), and deoxynivalenol was present in all 99 wheat DDGS samples (39.3-1120 µg/kg). A number of co-occurring mycotoxins were also identified. Due to the high co-occurrence of mycotoxins, routine screening of the animal feed ingredients is highly recommended to allow the highlighted risks to be effectively managed.

Classification the geographical origin of corn distillers dried grains with solubles by near infrared reflectance spectroscopy combined with chemometrics: A feasibility study.

In this study, 137 corn distillers dried grains with solubles (DDGS) samples from a range of different geographical origins (Jilin Province of China, Heilongjiang Province of China, USA and Europe) were collected and analysed. Different near infrared spectrometers combined with different chemometric packages were used in two independent laboratories to investigate the feasibility of classifying geographical origin of DDGS. Base on the same dataset, one laboratory developed a partial least square discriminant analysis model and another laboratory developed an orthogonal partial least square discriminant analysis model. Results showed that both models could perfectly classify DDGS samples from different geographical origins. These promising results encourage the development of larger scale efforts to produce datasets which can be used to differentiate the geographical origin of DDGS and such efforts are required to provide higher level food security measures on a global scale.