Pesticide residues in herbs and their transfer for infusions.

In this work, a cost-effective gas chromatography-mass spectrometry method was validated for the analysis of twenty-five pesticide residues in herbs and infusions using a quick, easy, cheap, effective, rugged, and safe procedure or a dispersive liquid-liquid microextraction method, respectively. Figures of merit of the method showed good accordance with current guidelines. From the 58 herb samples studied (pertaining to 20 different species), 80% presented at least one detectable pesticide, with 62% of them above the maximum residual level. Results showed that pesticide residues from naturally contaminated herbs were not transferred at a significant rate to the herbal infusions. When a control assay was conducted by spiking a blank herb sample with a large amount of each pesticide (7 mg/L) 15 analytes were detected below the limit of quantification in the infusion.

Herbs and herbal infusions: Determination of natural contaminants (mycotoxins and trace elements) and evaluation of their exposure.

Herbal infusions are amongst the world's most popular and widely enjoyed beverages, due to both large variety and convenience. However, natural contaminants, such as mycotoxins and trace elements can accumulate in aromatic herbs, which may have serious food safety and public health implications. In this study, the presence of mycotoxins, as well as the content of trace elements was evaluated in herbs and herbal infusions commercialized in Brazil. For the determination of fourteen mycotoxins, including the emerging mycotoxins enniatins (EN), beauvericin (BEA), and sterigmatocystin (STE), a liquid-chromatography tandem mass spectrometry (LC-MS/MS) method was validated. Overall, 42 out of 58 herb samples (72%) were contaminated, being BEA the most usual mycotoxin, present in 43% of the samples, followed by STE and HT-2 toxin, present in 37% and 24% of the samples, respectively. In herbal infusions, the occurrence of mycotoxins was 88% lesser than those verified in raw products. Despite these low levels, the hazard quotient (HQ) calculated revealed a potential health concern for HT-2 in infusions. The margin of exposure values for aflatoxins (AF), and ochratoxin A (OTA) from six herbal infusions were below 10,000, indicating also potential health risks. The twenty-one trace elements comprising toxic elements such as arsenic (As), cadmium (Cd), and lead (Pb) were determined in herb raw materials by inductively coupled plasma-mass spectrometry (ICP-MS). The levels of trace elements in herbs were very varied, with aluminum (Al) presenting the highest amount. The levels of legislated elements (As, Cd, Pb) analyzed in herbs were lower than 3.03 µg g-1 (Pb), thus not exceeding the legal limits defined for herbal medicinal by both European and Brazilian pharmacopeia.

Phthalic acid esters and adipates in herbal-based soft drinks: an eco-friendly method.

Phthalic acid esters (PAEs) and adipates are plasticizers with high applicability in several products and building materials (e.g. cosmetics, packing) very persistent in the environment, features which render them ubiquitous pollutants. These substances can contaminate food through the environment (water, air, and soil) and/or migration from packaging materials, which creates a health concern due to their toxicity. This paper describes an eco-friendly dispersive liquid-liquid microextraction (DLLME) procedure to extract five phthalates and bis(2-ethylhexyl) adipate (DEHA) from bottled herbal-based beverages followed by GC-MS/MS quantification. The method showed low limits of detection (5.0-13 µg L-1) and quantification (20-35 µg L-1), good inter- and intraday precision (RSD < 19%), and recoveries ranging from 82 to 111%. It was applied to 16 real samples, of which 13 showed the presence of at least one of the analytes under study. Additionally, an exposure assessment was performed, and resulted in a hazard quotient less than 1 (HQ < 1) for all analytes. Therefore, PAEs and DEHA found in samples do not pose a health issue.

A novel dispersive liquid-liquid microextraction using a low density deep eutectic solvent-gas chromatography tandem mass spectrometry for the determination of polycyclic aromatic hydrocarbons in soft drinks.

Ready-to-drink teas can provide, if properly packaged, the taste and wellness character of traditional teas. Nevertheless, in tea processing, there may be several contaminations, among which polycyclic aromatic hydrocarbons (PAHs), anthropogenic contaminants that can present carcinogenic and mutagenic properties. In this work, a novel low-density deep eutectic solvent-based dispersive liquid-liquid microextraction (LDDES-DLLME) procedure followed by gas chromatography tandem mass spectrometry (GC-MS/MS) was optimized for analysis of 15 polycyclic aromatic hydrocarbons (PAHs) in ready-to-drink herbal-based beverages. The new deep eutectic solvent (DES) was synthesized with natural compounds (camphor and hexanoic acid). Several parameters of the extraction procedure such as type and volume of extraction solvent, type, volume of dispersive solvent, and time of extraction were evaluated to achieve the highest yield and to attain the lowest detection limits. The validated method showed very low limits of detection (0.01 µg L-1) and quantification (0.2 µg L-1), good inter- and intra-day precisions (RSD<16.87%), and recoveries higher than 69%. The method was applied to 16 type of samples and it was found total PAHs levels ranging from 0.20 to 1.82 µg L-1. The developed LDDES-DLLME showed a reliable and innovative alternative for the extraction of PAHs from beverages, cost-effective and environmentally friendly, and providing a satisfactory throughput.

Chlorogenic and caffeic acids in 64 fruits consumed in Brazil.

This study presents unpublished data on the chlorogenic acid and caffeic acid content in fruits. Sixty-four fruits consumed in Brazil, most of which were produced domestically, were evaluated based on their levels of 3-caffeoylquinic acid, 4-caffeoylquinic acid, 5-caffeoylquinic acid, 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid and caffeic acid. The study investigated 15 fruits that have not been reported in the literature in relation to these compounds, including several native species. The highest concentration of mono-caffeoylquinic acid was observed in strawberry, cherry, bilberry, quince and mulberry, while the dicaffeoylquinic acid was present with highest concentration in kumquat, passion fruit and sweet granadilla. Regarding caffeic acid, the highest content was found in bilberry and yellow pitaya. Considering the sum of the concentrations of these compounds, quince, cherry, bilberry, mulberry and sweet granadilla were exceptional, with concentrations between 200.0 and 569.7 mg kg-1.

Chlorogenic acid isomer contents in 100 plants commercialized in Brazil.

This study analysed 100 plants employed in Brazil as ingredients to infusions for their caffeic acid, 3-caffeoylquinic acid (3-CQA), 4-caffeoylquinic acid (4-CQA), 5-caffeoylquinic acid (5-CQA), 3,4-dicaffeoylquinic acid (3,4-DQA), 3,5-dicaffeoylquinic acid (3,5-DQA), and 4,5-dicaffeoylquinic acid (4,5-DQA) contents. The samples were collected from public markets and analysed using ultra-high performance liquid chromatography (UPLC). The highest concentrations of chlorogenic acids were found in yerba mate (Ilex paraguariensis), 9,2g·100g-1, white tea (Camellia sinensis), winter's bark (Drimys winteri), green tea (Camellia sinensis), elderflower (Sambucus nigra), and Boehmeria caudata (known as assa-peixe in Brazil), 1,1g·100g-1. The present work showcased the investigation of chlorogenic acids in a wide range of plants not yet studied in this regard and also resulted in a comparative table which explores the content of six isomers in the samples.