Probabilistic risk assessment of exposure to multiple mycotoxins in consumers of packaged and unpackaged spices in Iran.

The current study assessed the risk posed to Iranian consumers by oral exposure to a mixture of ten mycotoxins in 138 packaged and unpackaged spices collected from the Iran market. Concentrations of mycotoxins in samples were quantified by liquid chromatography, tandem mass spectrometry with triple quadrupole, and ion trap. Probabilistic health risks of oral exposure to these mycotoxins for Iranians were assessed under percent tolerable daily intake (TDI) and cancer risk scenarios. Mean concentrations of mycotoxins in both packaged and unpackaged spice samples showed statistically significant variation among different spice samples. Based on a Monte Carlo simulation model, at the 50th, 80th, and 95th centiles, oral consumption of the analyzed samples poses no carcinogenic risk for exposure to aflatoxin. Moreover, in both packaged and unpackaged samples, while the percent TDIs for ochratoxin A, deoxynivalenol, zearalenone, patulin, fumonisin B1, and fumonisin B2 were below 1.0 at the 50th, 80th, and 95th centiles, the value was above 1.0 for aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2 at each of these centiles.

Seasonal Variation of Aflatoxin Levels in Selected Spices Available in Retail Markets: Estimation of Exposure and Risk Assessment.

A total of 603 samples of selected spices from different seasons (winter and summer) were analyzed for the occurrence of aflatoxin B1 (AFB1), total AFs, and tocopherols. The findings revealed that 120 (38.7%) samples from the summer and 136 (46.4%) samples from the winter season were observed to be infected with AFB1 and a large amount of AFs. The highest means of both AFB1 and total Afs were observed in red pepper, i.e., 15.5 ± 3.90 µg/kg and 22.90 ± 4.10 µg/kg, respectively. The minimum averages of AFB1 and total AFs were observed in cloves of 6.32 ± 1.8 and 8.40 ± 1.60 µg/kg, respectively (from the winter season). The seasonal variations in the levels of the total AFs in selected spices were observed to be nonsignificant (p ≥ 0.05), except for the levels in red pepper and ginger samples, which showed significant differences (p ≤ 0.05). The maximum average of the dietary intake of Afs, 4.80 µg/day/kg, was found in ginger from the winter season in individual females. Furthermore, the findings document that the maximum level of total tocopherol, i.e., 44.8 ± 9.3 mg/100 g, was observed in black pepper from the winter season. A significant difference in the concentration of total tocopherols was observed in selected spices from the summer and the winter seasons (p ≤ 0.05).

Determination of Some Chemical Elements of Common Spices Used by Algerians and Possible Health Risk Assessment.

Spices in general owned a very important reputation in the herbal plantae Kingdom; they have been used for food flavoring, preservation, aroma, and coloring for more than 2000 years. Moreover, spices are classified as all natural, and for this reason, they attracted a large scale of consumers worldwide; however, since most of spices are consumed in their natural form (without grounded them), it is necessary to monitor their consumed quantities. Hence, the aim of this work was to quantify major and trace elements contained in some Algerian kitchen frequently used spices (Piper nigrum L., Nigella sativa L., and Pimpinella anisum L.). Spice materials were washed well then pass through an instrumental neutron activation analysis (INAA). Results revealed the existence of twenty-six elements among them: K, Ca, Fe, and Na which showed significant concentrations, consecutively, while Ce, Eu, Lu, Sm, and Tb were presented at low concentrations. Furthermore, these spices consumption assessment results were found to be well below the tolerance limits compared with the recommended values (RDA) suggested by the FAO association.

A Novel FTIR-Based Chemometric Solution for the Assessment of Saffron Adulteration with Non-Fresh Stigmas.

The development of fast, non-destructive, and green methods with adequate sensitivity for saffron authentication has important implications in the quality control of the entire production chain of this precious spice. In this context, the highly suitable sensitivity of a spectroscopic method coupled with chemometrics was verified. A total number of 334 samples were analyzed using attenuated-total-reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy; the collected spectra were processed by partial-least-squares discriminant analysis (PLS-DA) to evaluate the feasibility of this study for the discrimination between compliant saffron (fresh samples produced in 2020) and saffron samples adulterated with non-fresh stigmas produced in 2018 and 2016. PLS-DA was able to classify the saffron samples in accordance with the aging time and to discriminate fresh samples from the samples adulterated with non-fresh (legally expired) stigmas, achieving 100% of both sensitivity and specificity in external prediction. Moreover, PLS regression was able to predict the adulteration level with sufficient accuracy (the root-mean-square error of prediction was approximately 3-5%). In summary, ATR-FTIR and chemometrics can be employed to highlight the illegal blending of fresh saffron with unsold stocks of expired saffron, which may be a common fraudulent practice not yet considered in the scientific literature.

Assessment of Citrinin in Spices and Infant Cereals Using Immunoaffinity Column Clean-Up with HPLC-Fluorescence Detection.

Historically, the analysis of citrinin has mainly been performed on cereals such as red yeast rice; however, in recent years, more complex and abnormal commodities such as spices and infant foods are becoming more widely assessed. The aim of this study was to develop and validate clean-up methods for spices and cereal-based infant foods using a citrinin immunoaffinity column before HPLC analysis with fluorescence detection. Each method developed was validated with a representative matrix, spiked at various citrinin concentrations, based around European Union (EU) regulations set for ochratoxin A (OTA), with recoveries >80% and % RSD < 9% in all cases. The limit of detection (LOD) and the limit of quantification (LOQ) were established at 1 and 3 µg/kg for spices and 0.1 and 0.25 µg/kg for infant cereals, respectively. These methods were then tested across a variety of spices and infant food products to establish efficacy with high recoveries >75% and % RSD < 5% across all matrices assessed. Therefore, these methods proved suitable for providing effective clean-up of spices and infant cereals, enabling reliable quantification of citrinin detected. Samples such as nutmeg and infant multigrain porridge had higher levels of citrinin contamination than anticipated, indicating that citrinin could be a concern for public health. This highlighted the need for close monitoring of citrinin contamination in these commodities, which may become regulated in the future.

The Safety Assessment of Toxic Metals in Commonly Used Herbs, Spices, Tea, and Coffee in Poland.

The presented study was aimed at the determination of the level of contamination with heavy metals (Cd, Pb, As, and Hg) in 240 samples of plant materials, i.e., herbal raw materials, spices, tea, and coffee. Moreover, a probabilistic risk assessment (noncarcinogenic and carcinogenic risks) was estimated by models including target hazard quotient (THQ) and cancer risk (CR). The samples were subjected to microwave mineralisation with the use of HNO3 (65%), while the determination of the content of the elements was performed with the use of inductively coupled plasma mass spectrometer (ICP-MS) and a mercury analyser. The element which was characterised by the highest level of accumulation in the analysed samples was lead (from 0.010 to 5.680 mg/kg). Among the heavy metals under analysis, the lowest concentration was noted in the case of mercury (from 0.005 to 0.030 mg/kg). A notably higher level of contamination with heavy metals was noted in the analysed samples of herbs and spices (0.005-5.680 mg/kg), compared to samples of tea and coffee (0.005-0.791 mg/kg). According to the guidelines of the World Health Organisation (WHO) concerning the limits of contamination of samples of herbal raw materials with heavy metals, lead levels exceeding the limits were only noted in 24 samples of herbs (18%). In all of the analysed samples of spices, tea, and coffee, no instances of exceeded limits were noted for any of the analysed heavy metals. The values of TTHQmax (in relation to the consumption of the analysed products) were as follows: up to 4.23 × 10-2 for spices, up to 2.51 × 10-1 for herbs, up to 4.03 × 10-2 for China tea, and up to 1.25 × 10-1 for roasted coffee beans. As the value of THQ ≤1, there is no probability of the appearance of undesirable effects related to the consumption of the analysed group of raw materials and products of plant origin. The CR value for As (max. value) was 1.29 × 10-5, which is lower than the maximum acceptable level of 1 × 10-4 suggested by United States Environmental Protection Agency (USEPA).

A Fast GC-MS-Based Method for Efficacy Assessment of Natural Anti-Oxidants for Inhibiting Lipid Oxidation.

BACKGROUND: For health reasons it is preferred to prepare food products with edible fats and oils that are high in unsaturated fatty acids. Unfortunately, these unsaturated acids are susceptible to lipid oxidation and the addition of natural antioxidants, e.g., rosemary extracts, etc. is needed. OBJECTIVE: To assess the efficacy of natural oxidation inhibition strategies, fast, yet realistic, and objective methods are needed to study oxidation inhibition. METHODS: A model system consisting of salt and sunflower oil is proposed as a model for dry soups and sauces. Hexanal formation is studied using fast GC-MS as a quantitative indicator for lipid oxidation. RESULTS: A fast GC-MS method using a short, 6-m 150 µm inner-diameter column was developed that allowed elution of hexanal within approximately 20 s, with a total run time of 2 min. The GC method has quantification limits below 1 ppm and is hence much more sensitive than the human nose. CONCLUSIONS: The new accelerated method with hexanal read-out was successfully applied in a study to identify spices and herbs mixtures that can act as natural inhibitors of lipid oxidation. The fast GC-MS method is extremely stable and allowed the analysis of thousands of samples with very little maintenance. HIGHLIGHTS: With the right mixture of spices and herbs, lipid oxidation can be delayed more than 100 times as compared to non-stabilized systems.

Occurrence and Risk Assessment of Pyrrolizidine Alkaloids in Spices and Culinary Herbs from Various Geographical Origins.

Pyrrolizidine alkaloids (PA) and their N­oxides (PANO) are a group of toxic secondary plant metabolites occurring predominantly as contaminants in (herbal) teas, honeys and food supplements, as well as in spices and culinary herbs. Depending on the botanical origin of the contaminating plant, the pattern of PA/PANO can strongly vary within a sample. The current study aimed to broaden the existing data on the occurrence of PA/PANO in spices and culinary herbs. For this, 305 authentic samples covering 15 different matrices mainly harvested in 2016 or 2017 and originating from 36 countries were investigated for the presence of 44 PA/PANO. Fifty-eight percent of the samples contained at least one PA/PANO. The average sum content over all samples was 323 µg/kg (median of 0.9 µg/kg, 95% percentile of 665 µg/kg). The highest amount of 24.6 mg/kg was detected in an oregano sample. Additionally, conspicuous analyte patterns were discovered in samples from similar cultivation regions, indicating related botanical sources of PA/PANO contaminations. Particularly, oregano and cumin from Turkey often contained high amounts of PA/PANO. The results were used to assess the acute and chronic health risks related to PA/PANO intake via spices and culinary herbs, indicating a potential health risk in particular for adults and children with high consumption or when considering worst­case contamination scenarios of a sum content of 5500 µg/kg.

A Rapid Non-Targeted Method for Detecting the Adulteration of Black Pepper with a Broad Range of Endogenous and Exogenous Material at Economically Motivating Levels Using Micro-ATR-FT-MIR Imaging.

Infrared spectroscopy is often used as a simple, fast, and green method to screen for economically motivated adulteration in spices. However, conventional microscopy remains the reference method. In this research, the combination of microscopy and Fourier-transform infrared spectroscopy in mapping mode, namely, micro-FTIR imaging, along with Principle Component Analysis were used to develop a non-targeted method for detecting a broad range of organic and mineral bulking agents that could potentially be used to adulterate black pepper. This method, based on the spatial distribution of black pepper chemical composition, has been thoroughly validated as a one-class, non-targeted classification method. Results are categorized as Typical or Atypical, where an Atypical result indicates a high probability of adulteration. For an Atypical outcome, a multitool investigational approach is then used for the detection and identification of the potential adulterant.

Assessment of Occupational Health Hazards Due to Particulate Matter Originated from Spices.

Spices have been known for their various health activities; however, they also possess the allergic potential for the respiratory system and the skin as they are fine particulate matter. Persons involved in spice agriculture and food industries are at greater risk since they are exposed to a considerable amount of combustible dust, which may be the cause of fire and explosion and adversely affect the health. These workers may experience allergy, long-term and short-term respiratory issues including occupational asthma, dermatitis, etc. Some spices induce T cell-based inflammatory reaction upon contact recognition of the antigen. Antigen Presenting Cells (APC) on binding to the causative metabolite results in activation of macrophages by allergen cytokine interleukin (IL)-12 and tumor necrosis factor-beta (TNF). Cross-reactivity for protein allergens is another factor which seems to be a significant trigger for the stimulation of allergic reactions. Thus, it was imperative to perform a systematic review along with bioinformatics based representation of some evident allergens has been done to identify the overall conservation of epitopes. In the present manuscript, we have covered a multifold approach, i.e., to categorize the spice particles based on a clear understanding about nature, origin, mechanisms; to assess metabolic reactions of the particles after exposure as well as knowledge on the conditions of exposure along with associated potential health effects. Another aim of this study is to provide some suggestions to prevent and to control the exposure up to some extent.

Analysis of unauthorized Sudan dyes in food by high-performance thin-layer chromatography.

Food authenticity and food safety are of high importance to organizations as well as to the food industry to ensure an accurate labeling of food products. Respective analytical methods should provide a fast screening and a reliable cost-efficient quantitation. HPTLC was pointed out as key analytical technique in this field. A new HPTLC method applying caffeine-impregnated silica gel plates was developed for eight most frequently found fat-soluble azo dyes unauthorizedly added to spices, spice mixtures, pastes, sauces, and palm oils. A simple post-chromatographic UV irradiation provided an effective sample cleanup, which took 4 min for up to 46 samples in parallel. The method was trimmed to enable 23 simultaneous separations within 20 min for quantitation or 46 separations within 5 min for screening. Linear (4-40 ng/band) or polynomial (10-200 ng/band) calibrations of the eight azo dyes revealed high correlation coefficients and low standard deviations. Limits of detection and quantification were determined to be 2-3 and 6-9 ng/zone, respectively. After an easy sample extraction, recoveries of 70-120% were obtained from chili, paprika, and curcuma powder as well as from chili sauce, curry paste, and palm oil spiked at low (mainly 25-50 mg/kg) and high levels (150-300 mg/kg). For unequivocal identification, the compound in a suspect zone was eluted via a column into the mass spectrometer. This resulted in the hyphenation HPTLC-vis-HPLC-DAD-ESI-MS. Graphical abstract Simplified clean-up by UV irradiation for Sudan dye analysis in food by HPTLC-vis-HPLC-DAD-ESI-MS.

Chemometric brand differentiation of commercial spices using direct analysis in real time mass spectrometry.

RATIONALE: Commercial spices represent an emerging class of fuels for improvised explosives. Being able to classify such spices not only by type but also by brand would represent an important step in developing methods to analytically investigate these explosive compositions. Therefore, a combined ambient mass spectrometric/chemometric approach was developed to quickly and accurately classify commercial spices by brand. METHODS: Direct analysis in real time mass spectrometry (DART-MS) was used to generate mass spectra for samples of black pepper, cayenne pepper, and turmeric, along with four different brands of cinnamon, all dissolved in methanol. Unsupervised learning techniques showed that the cinnamon samples clustered according to brand. Then, we used supervised machine learning algorithms to build chemometric models with a known training set and classified the brands of an unknown testing set of cinnamon samples. RESULTS: Ten independent runs of five-fold cross-validation showed that the training set error for the best-performing models (i.e., the linear discriminant and neural network models) was lower than 2%. The false-positive percentages for these models were 3% or lower, and the false-negative percentages were lower than 10%. In particular, the linear discriminant model perfectly classified the testing set with 0% error. Repeated iterations of training and testing gave similar results, demonstrating the reproducibility of these models. CONCLUSIONS: Chemometric models were able to classify the DART mass spectra of commercial cinnamon samples according to brand, with high specificity and low classification error. This method could easily be generalized to other classes of spices, and it could be applied to authenticating questioned commercial samples of spices or to examining evidence from improvised explosives.

Correlation between different markers for the assessment of red chilli pepper powders stability during shelf-life.

Pungency and red colour of Capsicum powders deteriorate during processing and storage, resulting in a decrease in market value. Two varieties of pepper with different pungencies were monitored for capsaicinoids, colour and furosine. Aliquots were stored at room and at low temperature during one year. At low temperature all indicators were stable in both varieties, while at room temperature, redness and capsacinoids decreased significantly, while furosine increased. High correlation was found between those markers. The more pungent variety exhibited higher stability in terms of all parameters. Differences observed suggest a potential protective effect exerted by capsaicinoids on powder stability. The decrease in capsaicinoids and redness accompanied by furosine increase showed a linkage between those markers never reported before. Considering that capsaicinoids and furosine occurrence have strong impact on the nutritional profile, the findings of this work show relevant changes in the nutritional value of chilli pepper powder after storage.

Heavy metals in aromatic spices by inductively coupled plasma-mass spectrometry.

Objective of this study was to determine the content of Cd, Hg, As and Pb in common spices traded in the Italian market, using inductively coupled plasma-mass spectrometry (ICP-MS). The results were compared with the maximum limits established by the national Legislative Decree (LD) no. 107 implementing the Council Directive 88/388/EEC and by international organisations, such as Food and Agriculture Organization (FAO) and World Health Organization (WHO). Food safety for spices was assessed considering the tolerable weekly intake (TWI) and the provisional tolerable weekly intake (PTWI), respectively, for Cd and Hg and the 95% lower confidence limit of the benchmark dose of 1% extra risk (BMDL01) for As and Pb. Investigated elements in all samples were within the maximum limits as set by the national and international normative institutions. Nevertheless, the heavy metal content of some spices exceeded the PTWI, TWI and BMDL01, which needs attention when considering consumer's health.

Pilot-scale radio frequency pasteurisation of chili powder: heating uniformity and heating model.

BACKGROUND: Microbial contamination is a vital obstacle needed to overcome for food safety of condiments. Radio frequency (RF) pasteurisation is a new technology to solve this obstacle. Temperature distribution and heating uniformity of sample, which are influenced by different factors, are the most important things affecting the nutritional ingredients and microbial safety of sample in the process of RF pasteurisation. This study demonstrated the location of cold spot in chili powder by analysing temperature distribution in horizontal and vertical direction. The related models were established and the accuracy was verified. RESULTS: Cold spot located on the centre of sample surface in the process of RF pasteurisation. The averaged temperature of sample increased linearly. The uniformity index decreased as the averaged temperature increased. Both the correlation coefficient of two equations were greater than 0.91. The error value of heating rate and heating uniformity index was 0.54% and 0.75% between the measured value and predicted value. CONCLUSION: Electric field was not uniformly distributed between RF parallel-plate electrodes in the RF pasteurisation of chili powder. The heating models were reliable to predict experiment results with high precision and accuracy. © 2015 Society of Chemical Industry.

Assessment of metal contents in spices and herbs from Saudi Arabia.

In the recent years, there has been a growing interest in monitoring heavy metal contamination of spices/herbs. Spices and herbs are sources of many bioactive compounds that can improve the tastes of food as well as influence digestion and metabolism processes. In the present study, the levels of some essential and toxic elements such as iron (Fe), zinc (Zn), copper (Cu), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), lead (Pb), and cadmium (Cd), present in common spices/herbs that were purchased from the local market in Saudi Arabia, were analyzed by atomic absorption spectroscopy after digestion with nitric acid/hydrogen peroxide mixture. Samples from the following spices/herbs were used: turmeric, cloves, black pepper, red pepper, cumin, legume, cinnamon, abazir, white pepper, ginger, and coriander. The concentration ranges for the studied elements were found as 48.8-231, 4.7-19.4, 2.5-10.5, below detection level (BDL)-1.0, 8.8-490, 1.0-2.6, and BDL-3.7 µg g(-1) for Fe, Zn, Cu, Cr, Mn, Ni, and Pb, respectively, while Cd and Co levels were below the detection limit. Consumers of these spices/herbs would not be exposed to any risk associated with the daily intake of 10 g of spices per day as far as metals Fe, Zn, Cu, Cr, Mn, Ni, and Pb are concerned.

Quality assessment of the saffron samples using second-order spectrophotometric data assisted by three-way chemometric methods via quantitative analysis of synthetic colorants in adulterated saffron.

Saffron is a valuable culinary spice that can be used not only for dyes and cooking, but also for many medical purposes. Due to its high price and restriction of its production, various fraud manners in its production have been growing. Addition of synthetic colorants to saffron is the most common way for adulteration. In this work, chemometric methods are proposed to resolve the three-dimensional absorbance spectra-pH data for simultaneous determination of the two colorants Tartrazin and Sunset yellow, in adulterated saffron. The rank deficiency in the concentration mode impaired the system. Therefore, to extirpate the ambiguity, which results from rank deficiency, three-way variation array V was generated by subtracting the first pH spectrum from each spectrum at each pH. This allows the extraction of extent reaction profile and mixture reaction spectral profiles, as well as the relative concentrations of the analytes.

Synthetic food colours in saffron solutions, saffron rice and saffron chicken from restaurants in Tehran, Iran.

Saffron solutions, saffron rice and saffron chicken samples were considered for synthetic colours as additives, which are forbidden according to Iranian national standards. Samples were taken from restaurants of three locations and analysed by high-performance liquid chromatography. Of the total 573 samples, 52% were positive for at least one colour. The most prevalent colours were Tartrazine, Quinoline Yellow and Sunset Yellow, with 44%, 9.1% and 8.4% of the samples testing positive for these colours, respectively. Carmoisine and Ponceau were both detected only in 0.5% of the positive samples and found only in saffron solution. In conclusion, synthetic food colours, especially Tartrazine should be regarded as a potential risk in saffron and its related food. Therefore, new attempts for food safety and quality should be undertaken to eliminate the use of these colours in restaurants.

Moisture content and its impact on aflatoxin levels in ready-to-use red chillies.

Moisture content (MC) and aflatoxin contamination were analysed to determine Red Chilli quality. A wide range (9.1-19.8%) of MC with a mean value of 11.4 ± 2.4% was found. Of 116 chilli samples, about 37% had low MC (<10%), 29.4% had medium-low MC (10-12%), 18.9% had medium-high MC (12 < MC < 14%) and 14.7% were above 14%. These four chilli groups had average aflatoxin levels of 2.1 ± 1.1, 5.3 ± 4.2, 8.9 ± 5.9 and 37 ± 20 µg/Kg, respectively. A direct relationship between moisture and aflatoxin content was found. The data best fitted a polynomial trend (R² = 0.89). The obtained equation could be utilised to assess aflatoxin levels based on MC. This study highlights the importance of using properly dried chillies with low MC, that is, ≤10%, to minimise health hazards associated with aflatoxin contamination.

Occurrence of toxigenic fungi and determination of mycotoxins by HPLC-FLD in functional foods and spices in China markets.

Twenty-four samples including 14 functional foods and 10 spices obtained from Chinese markets were examined for their mould profile. The mycotoxin contamination levels were also determined by an optimized HPLC-FLD method. 124 fungal isolates belonging to four different genera were recovered with Aspergillus and Penicillium as predominant fungi, with an incidence of 66.1% and 15.3%, respectively. In functional foods Aspergillus niger section (57.1%) was isolated more frequently, followed by Aspergillus flavi section (50.0%) and Aspergillus ochraceus section (21.4%), with the most contaminated samples being Coix seeds. Similar fungal presence and frequency were encountered in spice with A. niger section group (60.0%) and A. flavi section (40.0%) as main fungi. Cumin and Pricklyash peel samples showed the highest fungal contamination. Four functional foods and three spices were found to be positive at low levels for mycotoxins including aflatoxin B1 (up to 0.26µg/kg) and ochratoxin A (OTA) (5.0µg/kg). The more frequently detected mycotoxin was AFB1 (16.7%).