Paprika Samples Research Articles

Study of chili peppers and paprika contamination with alternaria toxins as health risk factors

At present, researchers show considerable interest in unregulated toxins of widespread fungi in nature, in particular, metabolites of microfungi of Alternaria genus. These toxins are potentially hazardous for human health and, under unfavorable conditions, capable of producing toxic metabolites, Alternaria toxins (AT), which have shown genotoxicity, mutagenicity and acute toxic effects. They are frequently detected not only in cereals and oilseeds, fruits, nuts, vegetables, but also in spices, especially dried red peppers. The aim of the study was to investigate the occurrence of Alternaria toxins in paprika and chili peppers sold on the domestic market as well as to assess their intakes by humans through their consumption. Concentration of 5 Alternaria toxins (alternatiol (AOH), alternariol monomethyl ether (AME), altenuene (ALT), tentoxin (TEN), tenuazonic acid (TeA)) was detected in 37 samples of dried red peppers marketed in Moscow and Moscow region in 2024 year including paprika (20 samples) and chili pepper (17 samples). The analysis of Alternaria toxins contamination was carried out by high-performance liquid chromatography coupled to tandem mass-spectrometric detection (HPLC-MS/MS). TeA was detected in 84 % of red pepper samples in concentration from 43 to 3295 µg/kg and TEN – in 40 % cases, in low levels ranging from 1.0 to 11 µg/kg. The occurrence of AT in paprika was higher than in chili pepper. Combined (2 or more toxins) contamination with Alternaria toxins was found only in paprika samples (65 %; the predominant combination is TeA and TEN). Intakes of Alternaria toxins associated with consumption of chili and paprika did not exceed the reference values and ranged from 0.0003 % (for TEN) to 0.24 % (for TeA) of the threshold of toxicological concern (TTC).

Результаты оценки контаминации перца чили и паприки альтернариатоксинами как факторы риска здоровью

At present, researchers show considerable interest in unregulated toxins of widespread fungi in nature, in particular, metabolites of microfungi of Alternaria genus. These toxins are potentially hazardous for human health and, under unfavorable conditions, capable of producing toxic metabolites, Alternaria toxins (AT), which have shown genotoxicity, mutagenicity and acute toxic effects. They are frequently detected not only in cereals and oilseeds, fruits, nuts, vegetables, but also in spices, especially dried red peppers. The aim of the study was to investigate the occurrence of Alternaria toxins in paprika and chili peppers sold on the domestic market as well as to assess their intakes by humans through their consumption. Concentration of 5 Alternaria toxins (alternatiol (AOH), alternariol monomethyl ether (AME), altenuene (ALT), tentoxin (TEN), tenuazonic acid (TeA)) was detected in 37 samples of dried red peppers marketed in Moscow and Moscow region in 2024 year including paprika (20 samples) and chili pepper (17 samples). The analysis of Alternaria toxins contamination was carried out by high-performance liquid chromatography coupled to tandem mass-spectrometric detection (HPLC-MS/MS). TeA was detected in 84 % of red pepper samples in concentration from 43 to 3295 µg/kg and TEN – in 40 % cases, in low levels ranging from 1.0 to 11 µg/kg. The occurrence of AT in paprika was higher than in chili pepper. Combined (2 or more toxins) contamination with Alternaria toxins was found only in paprika samples (65 %; the predominant combination is TeA and TEN). Intakes of Alternaria toxins associated with consumption of chili and paprika did not exceed the reference values and ranged from 0.0003 % (for TEN) to 0.24 % (for TeA) of the threshold of toxicological concern (TTC).

Photothermal pasteurization of paprika powder by ultra-high irradiance blue (405 nm) light: Impact on Salmonella inactivation and quality attributes

This study aimed to evaluate the inactivation efficacy of ultra-high irradiance blue (405 nm) LED treatments against Salmonella spp. in paprika powder and develop an alternative Weibull model to describe the inactivation kinetics. Paprika samples were inoculated with a Salmonella cocktail at a ratio of 1 mL/100 g (∼8.7 log CFU/g), acclimated for 7 days at 22 °C, and irradiated with blue LED at a fixed distance (5 cm) using different irradiances (548, 697, and 842 mW/cm2) and exposure times (60, 120, 180, and 240 s). Sterilization-like temperatures of up to 131.7 °C were observed in paprika after 240 s at 842 mW/cm2. Reduction levels in Salmonella counts ranged from 2.1 to 7.8 logs after 240 s. A modified Weibull model satisfactorily described the Salmonella inactivation kinetics (Radj2 > 0.98). Compared to control samples, a significant decrease in redness (a* values) and higher DPPH scavenging activity were observed in treated paprika powders.Industrial relevance: The obtained results indicated that UHI LED technology could serve as an alternative dry pasteurization method to improve the microbiological safety of spices. This would open further possibilities, including the use of this technology to disinfect food-contact surfaces in dry operations. These findings are thus important in supporting the development and optimization of LED technology for food safety applications in the food industry. Blue light has a shorter penetration depth, which may limit the size and shape of products that can be pasteurized with UHI blue LED technology.

Authentication strategy for paprika analysis according to geographical origin and study of adulteration using near infrared spectroscopy and chemometric approaches

Paprika is a spice whose composition and characteristics vary with its geographical origin and additionally is illegally adulterated with dyes to improve its appearance. This work proposes a strategy based on Fourier-transform near infrared (FT-NIR) analysis and chemometric tools for its authentication and detection of fraud. A total of 115 paprika samples were analyzed, including paprika with protected designation of origin (PDO) labels from Spain, France and Hungary, and samples from China and Zambia. The proposed orthogonal partial least squares-discriminant analysis (OPLS-DA) models allow to distinguish paprika according to its PDO and variety, as well as to identify adulteration with Sudan dyes or Congo red. Partial least squares regressions allow to quantify the adulterant in paprika from 0.1 to 5 %. Chemometric models achieved high classification success rates and suitable linearities. The proposed strategy is presented as a comprehensive and effective tool to ensure paprika quality and authenticity, including the detection and quantification of adulteration with commercial dyes.

Uncertainty and associated risks in the analysis of pesticides in homogeneous paprika samples.

In this study, risk estimation based on sampling and subsampling uncertainty was performed for pesticide analysis in homogeneous spice products such as paprika. The results of the subsampling were also used to estimate the minimum weight necessary in subsampling to minimize overall uncertainty. The results show that subsampling has more uncertainty than sampling in the product due to high homogeneity in the manufacturer's batch. On the other hand, results using the Monte Carlo (MC) simulation on the size of the subsample indicate that uncertainty is lower for weights between 20 and 30g and increases for sample sizes of 100g. A sample size of 30g was used for saffron, and the values simulated with the MC method were confirmed.

THE USE OF TARGETED ANALYSIS TO VERIFY THE GEOGRAPHICAL ORIGIN OF GROUND PAPRIKA

This study investigated the use of targeted analysis to verify the geographic origin of ground paprika samples. In total, 36 samples were analyzed from all over the world (17 from Europe, 17 from Asia, one from North America, and one from Africa). Deliberately chosen methods that use equipment commonly available in control laboratories were used for the analysis. The samples were examined for total fat content, total protein content, sugar concentration, the concentration of selected elements, ASTA coloring, ash content, and pH of the extract. The results were processed using multivariate analysis, which showed that, based on these investigated parameters, it is possible to differentiate ground paprika samples from different regions. In addition to being able to separate samples originating from Asia from those originating from Europe, it was also possible to distinguish samples from Europe with protected geographical indications, such as paprika from Hungary, Spain, and Slovakia.

Carbon based electrodes for the voltammetric determination of capsaicin in spicy samples

A voltammetric sensor based on the modification of a screen-printed carbon electrode with reduced graphene oxide (rGO-SPCE) is presented for the cyclic voltammetric determination of capsaicin in a wide range of concentrations. Special attention was given to factors affecting sensitivity and repeatability in order to overcome common reported issues related to the voltammetric determination of capsaicin. Fouling associated to the adsorption of capsaicin was minimized using a simple and effective washing step, allowing sensors to be reused for at least 10 measurements with a repeatable signal. The developed rGO-SPCE presented two well-defined linear ranges (from 1.1 to 25.0 and from 25.0 to 150.3 µmol L−1) and provided an increased sensitivity as compared to the unmodified electrode as well as to other modified electrodes based on carbon nanomaterials commercially available. Furthermore, a low limit of detection of 0.3 µmol L−1 was achieved and the accuracy of the method was demonstrated for the determination of capsaicin in chilli pepper, paprika samples and Tabasco sauce, obtaining comparable results to those achieved by liquid chromatography with UV–vis detection.

Dispersive Magnetic Solid-Phase Extraction as a Novelty Sample Treatment for the Determination of the Main Aflatoxins in Paprika.

Dispersive magnetic solid-phase extraction (DMSPE) technique is proposed as a new sensitive and effective sample treatment method for the determination of aflatoxins in paprika samples. DMSPE was followed by ultrahigh-performance liquid chromatography and high-resolution mass spectrometry detection (UHPLC-HRMS) using a non-targeted acquisition mode for the detection of main aflatoxins (aflatoxin G1, G2, B1 and B2) and derivatives. DMSPE was based on the use of magnetic nanocomposite coated with polypyrrole (PPy) polymer and the main experimental parameters influencing the extraction efficiency in adsorption and desorption steps have been studied and optimized. Analyses were performed using 250 µL magnetic PPy nanocomposite into the sample solution, adsorbing the analytes in 30 min and desorbing them with ethyl acetate (2 mL) in 15 min. The method has been validated, obtaining quantification limits between 3.5 and 4.7 µg kg-1 and recoveries between 89.5-97.7%. The high recovery rate, wide detection range and the use for the first time of the reusable Fe3O4@PPy nanomaterial in suspension for solid food matrices, guarantee the usefulness of the method developed for adequate control of aflatoxins levels in paprika. The proposed methodology was applied for the analysis of 31 samples (conventional and organic) revealing the absence of aflatoxins in the samples.

Deep Genotypic Species Delimitation of Aspergillus Section Flavi Isolated from Brazilian Foodstuffs and the Description of Aspergillus annui sp. nov. and Aspergillus saccharicola sp. nov.

Aspergillus section Flavi is a fungal group that is important in food because it contains spoilage and potentially aflatoxigenic species. Aflatoxins are metabolites that are harmful to human and animal health and have been recognized as the primary natural contaminant in food. Therefore, recognizing the biodiversity of this group in food is necessary to reduce risks to public health. Our study aimed to investigate the diversity of Aspergillus section Flavi isolated from Brazilian foodstuffs such as cassava, sugarcane, black pepper, paprika, Brazil nuts, yerba-mate, peanuts, rice, and corn. A polyphasic approach integrating phenotypic data and multilocus genotypic analyses (CaM, BenA, and RPB2) was performed for 396 strains. Two new species in the Aspergillus subgenus Circumdati section Flavi are proposed using maximum-likelihood analysis, Bayesian inference, and coalescence-based methods: Aspergillus saccharicola sp. nov. and Aspergillus annui sp. nov. A. saccharicola sp. nov. belongs to the series Flavi, is a potentially aflatoxigenic species (B1, B2, G1, and G2), closely related to Aspergillus arachidicola, and was found mostly in sugarcane. A. annui sp. nov. was isolated from samples of sweet paprika. To accommodate A. annui sp. nov., a new series Annuorum was proposed.

Detection and Quantitation of Adulterated Paprika Samples Using Second-Order HPLC-FLD Fingerprints and Chemometrics.

Paprika is a widely consumed spice in the world and its authentication has gained interest considering the increase in adulteration cases in recent years. In this study, second-order fingerprints acquired by liquid chromatography with fluorescence detection (HPLC-FLD) were first used to detect and quantify adulteration levels of Chinese paprika samples. Six different adulteration cases, involving paprika production region, cultivar, or both, were investigated by pairs. Two strategies were employed to reduce the data matrices: (1) chromatographic fingerprints collected at specific wavelengths and (2) fusion of the mean data profiles in both spectral and time dimensions. Afterward, the fingerprint data with different data orders were analyzed using partial least squares (PLS) and n-way partial least squares (N-PLS) regression models, respectively. For most adulteration cases, N-PLS based on second-order fingerprints provided the overall best quantitation results with cross-validation and prediction errors lower than 2.27% and 20.28%, respectively, for external validation sets with 15–85% adulteration levels. To conclude, second-order HPLC-FLD fingerprints coupled with chemometrics can be a promising screening technique to assess paprika quality and authenticity in the control and prevention of food frauds.

Differential mobility spectrometry coupled to mass spectrometry (DMS–MS) for the classification of Spanish PDO paprika

Ion mobility spectrometry (IMS) has proved its huge potential in many research areas, especially when hyphenated with chromatographic techniques or mass spectrometry (MS). However, focusing on food analysis, and particularly in classification and authentication issues, very few applications have been reported. In this study, differential mobility spectrometry coupled to mass spectrometry (DMS–MS) is presented for the first time as an alternative and high-throughput technique for food classification and authentication purposes using a fingerprinting strategy. As a study case, 70 Spanish paprika samples (from La Vera, Murcia, and Mallorca) were analyzed by DMS–MS to address their classification —using partial least squares regression-discriminant analysis (PLS-DA)— and authentication —through soft independent modeling of class analogy (SIMCA). As a result, after external validation, complete sample classification according to their geographical origin and excellent La Vera and Mallorca sample authentication were reached.

Fe3O4 Nanorods‐RGO‐ionic Liquid Nanocomposite Based Electrochemical Sensor for Aflatoxin B1 in Ground Paprika

AbstractA novel and sensitive method for the determination of aflatoxin B1 (AFA−B1) in ground paprika using a methyltrioctylammonium chloride ionic liquid (IL), iron oxide nanorods (Fe3O4 nanorods) and reduced graphene oxide (RGO) fabricated glassy carbon electrode (GCE) was developed. The synthesized nanoparticles, nanocomposites and modified electrode surfaces were characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA/DSC) and x‐ray diffraction (XRD) analyses. Moreover, the electrochemical performance of the developed sensor was determined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The obtained results demonstrate that the sensitivity of AFA−B1 is significantly enhanced on RGO‐Fe3O4 nanorods‐IL‐GCE in comparison with bare GCE, RGO‐GCE and RGO‐Fe3O4 nanorods‐GCE. The redox peak currents of AFA−B1 exhibited good linear relationship with its concentration in the range from 0.02 to 0.33 ng mL−1 with detection limit of (LOD) 0.03 ng mL−1 and limit of quantification (LOQ) 0.36 ng mL−1 respectively (S/N=3). In addition, the fabricated electrode showed good stability and reproducibility. The proposed technique was effectively applied to identify the AFA−B1 in real ground paprika samples with acceptable results.

Occurrence and Determination of Carotenoids and Polyphenols in Different Paprika Powders from Organic and Conventional Production.

Paprika powder is a good source of different carotenoids and polyphenols, which play a key role in preventing certain diseases (some kinds of cancer and cardiovascular diseases). They can also be used as natural food colorants. Organic production is characterized by strict rules, but products obtained in this way contain more bioactive compounds, such as carotenoids and polyphenols. The aim of this study was to measure and identify carotenoids and polyphenols in different paprika samples (sweet, hot, smoked, and chili) obtained by organic and conventional production. Quantitative and qualitative carotenoid and polyphenols analysis showed that the experimental samples contained different concentrations of these compounds.

Estudo microscópico de páprica (Capsicum annuum L.): detecção de fraudes e matérias estranhas

Introdução: A páprica (Capsicum annuum L.) é um condimento utilizado mundialmente, produzido a partir de diversas variedades de pimentão maduro, seco e moído e está sujeita a adulterações e fraudes, além de contaminações decorrentes de falhas nas boas práticasde produção, armazenamento ou na comercialização. Objetivo: Avaliar a autenticidade e a presença de matérias estranhas em pápricas comercializadas no estado de São Paulo, assim como verificar a sua conformidade em relação à legislação nos parâmetros microscópicos. Método: Foram analisadas 43 amostras de páprica para verificação da autenticidade e para a pesquisa de matérias estranhas, utilizando método preconizado nos Métodos Oficiais da Association of Official Analytical Collaboration International. Resultados: A avaliação da autenticidade evidenciou fraude em 30,0% das amostras. O ingrediente adicionado com maior frequência foi o amido de Zea mays L. (milho), acompanhado principalmente de Bixa orellana L. (urucum). Entre as matérias estranhas detectadas, os fragmentos de pelo de roedor e os fragmentos de insetos foram os mais frequentes, presentes em 91,0% e 79,0% das amostras, respectivamente. As amostras puras apresentaram maior quantidade de fragmentos de pelo de roedor, enquanto as amostras adulteradas, maior quantidade de fragmentos de insetos. Em relação à legislação sanitária, 88,0% das amostras foram consideradas insatisfatórias, destas, 30,0% por estarem adulteradas e 77,0% por apresentarem quantidade de matérias estranhas acima do limite tolerado. Conclusões: Os resultados deste trabalho revelaram fraude e falhas nas boas práticas na cadeia produtiva da páprica, ressaltando a necessidade de intensificação da vigilância desse tipo de produto com vistas à garantia de sua oferta à população de forma fidedigna e segura.

Determination of capsaicinoids and carotenoids for the characterization and geographical origin authentication of paprika by UHPLC–APCI–HRMS

The production area mislabeling of a food product is considered a fraudulent practice worldwide. In this work, a method that uses ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry using atmospheric pressure chemical ionization (UHPLC–APCI–HRMS) was used for the geographical origin authentication of paprika based on the determination of capsaicinoids and carotenoids. Satisfactory instrumental method performance was obtained, providing good linearity (R2 > 0.998), run-to-run and day-to-day precisions (%RSD < 15 and 10%, respectively), and trueness (relative errors < 10%), while method limits of quantification were between 0.21 and 51 mg kg−1. Capsaicinoids and carotenoids were determined in 136 paprika samples, from different origins (La Vera, Murcia, Hungary, and the Czech Republic) and types (hot, sweet, and bittersweet). The composition of capsaicinoids and carotenoids was used as chemical descriptors to achieve paprika authentication through a classification decision tree built by partial least squares regression−discriminant analysis (PLS−DA) models and reaching a rate of 80.9%.

Dry pasteurization of paprika (Capsicum annuum L.) by short time intensive microwave-infrared radiation: Inactivation of Salmonella Typhimurium and Aspergillus flavus considering quality degradation kinetics

The inactivation of S. Typhimurium and A. flavus along with quality degradation kinetics was studied during combined microwave-infrared (MW-IR) heating of paprika. The spatial changes in the distribution of temperature and variation in water activity (aw) of the paprika samples resulted in a 7.389 log reduction in S. Typhimurium, and 6.182 log reduction in A. flavus. During heating, the deterioration of red pigments was more pronounced compared to that of the yellow pigments. The alteration of color was observed to be due to the increase in a large number of brown pigments. The inhibition of DPPH radicals accelerated with an increase in the power level of MW-IR radiation; the inhibition rate increased from 0.0859 to 0.1485 s−1. Also, the pungency of dried paprika was found to increase due to moisture reduction, inactivation of peroxidase, and the short-duration of heating.

Polycyclic aromatic hydrocarbons in smoked and non‐smoked paprika samples

The aim of our work is to investigate and compare the polycyclic aromatic hydrocarbons (PAHs) content of smoked paprika produced with different technologies and originated from different locations. A new sample preparation method was developed for the determination of 16 PAHs, eight low molecular weight, and eight high molecular weight (PAH8) compounds, from different smoked and non-smoked Hungarian and imported ground paprika (Capsicum spp.) samples, adapting and validating the HPLC/DAD-FLD measuring technique to accomplish this. The validation parameters were in accordance with performance criteria described in EU regulations. Four non-smoked, three smoke flavored, and eight smoked paprika samples were analyzed for their PAHs contaminations. Benzo[a]pyrene was detected in all samples and ranged in non-smoked samples from <LOQ to 6.3 µg/kg, in flavored samples from 6.3 to 7.0 µg/kg, and in smoked samples from 5.8 to 97 µg/kg. Amounts of ΣPAH were from 190 to 1,686 µg/kg, from 213 to 352 µg/kg, and from 801 to 48,042 µg/kg, respectively. Particularly, contributions of the light PAHs values to ΣPAH were significant in the case of smoked paprika samples regarding which, percentages of the PAH4 and PAH8 levels showed 4%–15% and 5%–24%, respectively. Using discriminant analysis, more than 96% of the samples were correctly classified based on the measurement data. Practical applications The issue of food safety is extremely important nowadays, as the risk of contamination has increased with the increase in transport and storage time, the range of food, and the place of origin. Anti-nutritive components, contaminants such as for example, PAHs are present in different amounts in foods from different locations or produced by technology. It is also important for manufacturers, researchers, and dietitians to be aware of these data, as these compounds can accumulate in the body and cause serious health problems.

Untargeted classification for paprika powder authentication using visible – Near infrared spectroscopy (VIS-NIRS)

This paper describes a non-destructive screening method for authentication of paprika belonging to the Spanish Protected Designation of Origin (PDO) “Pimentón de La Vera”. Different multivariate classification models were developed in order to differentiate PDO and non-PDO samples, using visible-near infrared spectra as fingerprint for each paprika sample. Sample treatment was not required. Principal component analysis (PCA) was applied in different spectral ranges: 400–2500, 400–800 and 800–2500 nm. In all spectral ranges, PCA was largely able to differentiate PDO from non-PDO samples. Partial least-squares - discriminant analysis (PLS-DA), PCA-linear discriminant analysis (LDA) and PCA-quadratic discriminant analysis (QDA) were used as classification methods in the different spectral ranges. All methods were able to differentiate PDO from non-PDO samples, with error rates (ER) lower than 0.15. The best models were those obtained with PLS-DA in the NIR range (800–2500 nm), showing ERs lower than 0.07 and error indexes (IERROR) (false positives) lower than 0.05.

Authentication of PDO paprika powder (Pimentón de la Vera) by multivariate analysis of the elemental fingerprint determined by ED-XRF. A feasibility study

Products with a Protected Denomination of Origin (PDO) are vulnerable to misdescription of their true geographical origin. In this work a method has been developed that allows the authentication of La Vera paprika powder (Pimentón de la Vera), a PDO product from the central-west Spanish region, Extremadura. The mass fractions of Br, Ca, Cr, Cl, Cu, Fe, K, Mn, Ni, P, Rb, S, Sr and Zn determined by energy dispersive X-ray fluorescence (ED-XRF) are used for classification purposes by multivariate analysis using Soft Independent Modelling of Class Analogy (SIMCA) (PCA-Class) and Partial Least Square-Discriminant Analysis (PLS-DA). Sixty-seven paprika samples purchased in supermarkets around Europe and on-line via the official web-site of Pimentón de La Vera, were used to build up the models for prediction purposes. The PCA-class model of La Vera paprika powder had a sensitivity of 82%, a specificity of 100% and an accuracy of 91%, whereas the PLS-DA model had a sensitivity of 100%, a specificity of 91% and an accuracy of 96%.

Classification and Authentication of Paprika by UHPLC-HRMS Fingerprinting and Multivariate Calibration Methods (PCA and PLS-DA).

In this study, the feasibility of non-targeted UHPLC-HRMS fingerprints as chemical descriptors to address the classification and authentication of paprika samples was evaluated. Non-targeted UHPLC-HRMS fingerprints were obtained after a simple sample extraction method and C18 reversed-phase separation. Fingerprinting data based on signal intensities as a function of m/z values and retention times were registered in negative ion mode using a q-Orbitrap high-resolution mass analyzer, and the obtained non-targeted UHPLC-HRMS fingerprints subjected to unsupervised principal component analysis (PCA) and supervised partial least squares regression-discriminant analysis (PLS-DA) to study sample discrimination and classification. A total of 105 paprika samples produced in three different regions, La Vera PDO and Murcia PDO, in Spain, and the Czech Republic, and all of them composed of samples of at least two different taste varieties, were analyzed. Non-targeted UHPLC-HRMS fingerprints demonstrated to be excellent sample chemical descriptors to achieve the authentication of paprika production regions with 100% sample classification rates by PLS-DA. Besides, the obtained fingerprints were also able to perfectly discriminate among the different paprika taste varieties in all the studied cases, even in the case of the different La Vera PDO paprika tastes (sweet, bittersweet, and spicy) which are produced in a very small region.