Comprehensive assessment of clean-up strategies for optimizing an analytical multi-method to determine pesticides and mycotoxins in Brazilian medicinal herbs using QuEChERS-LC-TQ-MS/MS.

The use of medicinal herbs has increased significantly. However, the presence of pesticide residues and mycotoxins in medicinal herbs has generated constant discussion and concern among regulatory agencies. Developing and validating an analytical method for determining pesticides and mycotoxins in medicinal plants is challenging due to the naturally occurring substances in these plants. The purpose of this work was to develop and to optimize a sensitive, accurate, precise, effective QuEChERS method for simultaneous determination of over 160 pesticide and mycotoxin residues in complex medicinal plant matrices using LC-TQ-MS/MS. A comprehensive comparison of clean-up procedures and other parameters was conducted to achieve this goal. The validation procedure was performed according to SANTE 11312/2021. More polar analytes, such as acephate, methamidophos and omethoate, presented a higher negative matrix effect in both Melissa officinalis L. and Malva sylvestris L. However, other molecules, such as spirodiclofen, showed a 24% signal enhancement in M. officinalis and a 46% signal suppression in M. sylvestris, indicating that a representative matrix-matched calibration would lead to inaccurate quantification of the analyte. Accuracy and precision were satisfactory according to SANTE 11312/2021 for 157 pesticide residues and mycotoxins in M. officinalis and for 152 molecules in M. sylvestris. LOQs at 10 µg kg-1 were achieved for 117 pesticides in M. officinalis and 99 pesticides in M. sylvestris. Among the mycotoxins, all four aflatoxins (B1, B2, G1 and G2) presented LOQs of 5 µg kg-1, and ochratoxin A had an LOQ of 10 µg kg-1 in M. officinalis. The same LOQ values were shown for these mycotoxins in M. sylvestris, except for aflatoxin B2 and ochratoxin A, which had LOQs of 20 µg kg-1. Moreover, in Southern Brazil, there has been no previous study on mycotoxin and pesticide contamination in medicinal herbs. Therefore, the application of this method was assessed through the analysis of forty-two real samples. Imidacloprid was found in M. officinalis, and methyl pirimiphos was found in M. sylvestris. The proposed method not only serves as a helpful tool for routine monitoring but also offers a basis for further research on risk assessment and control in food safety.

Spontaneously growing fungi on the surface and processing areas of matured sheep ham and volatile compounds produced.

Raw ham is a dried and matured product traditionally made from pork leg, but other animals, such as sheep, can be used. The natural presence of bacteria and fungi in this product influences its characteristics throughout the process. This study analysed the fungal populations present during raw sheep hams' processing. Two types of products were developed: without and with the addition of seasonings. Mycological analyses were carried out from the ingredients, seasonings, facilities air, as well as on the surfaces of the hams and the air in the chamber throughout the maturation period (0, 45, 90, and 180 days) using 18 % dichloran glycerol agar and the data were submitted to Principal Component Analysis. Volatile compounds were evaluated at the end of the sheep ham manufacturing process through a gas chromatograph coupled to a mass spectrometer. At 45 days of aging, a more remarkable similarity was observed between the fungi present on the non-seasoned hams and those in the ripening chamber's air, while the seasoned hams showed a more evident relation with those fungi present in the spices. With time, the fungi in the air of the ripening chamber started to be influenced by Aspergillus ser. Aspergillus and Aspergillus ser. Rubri already installed in the seasoned hams at 45 days, and then it probably dispersed the non-seasoned ones due to the airborne spores, becoming the most prevalent in both treatments at 90 days. At the end of ripening, the mycobiota of both raw hams was composed mainly by xerophilic species of Aspergillus section Aspergillus. The total fungal count was 5.78 log CFU/cm2 for the non-seasoned and 7.19 log CFU/cm2 for the seasoned ones. A potentially ochratoxigenic Aspergillus ser. Circumdati was detected at the end of aging in raw, unseasoned hams. In conclusion, seasoning directly influences the species developing on the surface of seasoned hams throughout the ripening process, and indirectly affects the mycobiota of the non-seasoned hams when sharing the same ripening chamber. The presence of fungi in the matured sheep ham seems to contribute to the formation of volatile compounds, which are related to the sensory quality of these products.

Multimycotoxin Determination in Grains: A Comprehensive Study on Method Validation and Assessment of Effectiveness of Controlled Atmosphere Storage in Preventing Mycotoxin Contamination.

Two simple and low-cost QuEChERS approaches were optimized and validated for multimycotoxin determination in grains by UPLC-MS/MS and applied to assess effectiveness of controlled atmosphere (CA) storage in preventing mycotoxin contamination. Common bean, soybean, and maize samples were stored for 6 months. CA treatments were conducted varying O2 and CO2 partial pressures, temperatures, and moisture contents of the chambers. In the validation study for common bean and maize, 8 out of 11 mycotoxins were successfully validated. For soybean, 10 out of 11 mycotoxins were validated. Aflatoxin B1 was detected in all commodities. Statistical tests suggest that storage temperature played a key role in aflatoxin B1 concentrations in common bean and soybean, but had no influence on maize. Maize was also positive for fumonisins B1 and B2. Differences in fumonisin concentrations were not significant among different treatments. Concentrations of aflatoxin B1 in some samples exceeded legislation's maximum levels. Thus, some of the CA treatments applied were effective in preventing mycotoxin contamination in common bean and soybean but were not effective for maize.

Chemical composition and oxidative stability of eleven pecan cultivars produced in southern Brazil.

Nuts are considered highly nutritious foods and a source of health-promoting compounds. Therefore, the aim of this study was to evaluate the chemical composition (proximate composition, fatty acids, volatile compounds, total phenolics, squalene, and ß-sitosterol) of eleven pecan cultivars harvested in Rio Grande do Sul State (Brazil) and investigate their oxidative stability by the Rancimat method. 'Barton' is the main cultivar produced in Brazil and presented the highest protein, linoleic acid, and linolenic acid values and the lowest saturated fatty acid values, which provide health benefits. 'Mahan' showed the highest oxidation induction time, both in extracted oil and ground samples, low abundance of lipid oxidation compounds, low polyunsaturated fatty acids, high levels of oleic acid and ß-sitosterol, which suggests potential for storage. 'Stuart' and 'Success' had the highest total dietary fiber values. Moreover, analysis showed that 'Chickasaw' and 'Success' had large quantities of compounds correlated to lipid oxidation, suggesting low stability for long-term storage. These results imply that the physicochemical characteristics and proximate composition of pecan nut cultivars from southern Brazil have variable parameters that may depend on their genetic variability.