Elena Butovskaya

Botanical food supplements are increasingly consumed worldwide. As finished products, they may be contaminated with pesticide residues, which can potentially become concentrated relative to the raw botanical materials during processing steps. In this study, analytical methods were developed for the quantification of 252 pesticide residues in botanical food supplements using LC-MS/MS and GC-MS/MS, with both techniques employing a common sample preparation procedure. Sample extraction and clean-up were performed using a QuEChERS-based approach combined with dispersive solid-phase clean-up step using graphitized carbon black (GCB) and primary–secondary amine (PSA) sorbents followed by Oasis^® WAX cartridge purification. Method validation was performed in accordance with the EU guidance document SANTE/11312/2021. The validated methods were subsequently applied to ten plant extract samples to assess their applicability to different botanical food supplement matrices. Multiple pesticide residues were detected in three samples, with concentrations ranging from 0.01 to 0.19 mg/kg. The application of the methods to real samples confirmed suitability for the analysis of diverse botanical matrices and underscored the need for robust analytical approaches to support the routine monitoring of pesticide residues in botanical food supplements and ensure consumer safety.

Hydroxyanthracene derivatives (HADs) are natural compounds that occur in several botanical species belonging to the genera Aloe L., Cassia L., Rheum L., Frangula Mill., and Rhamnus L. While they are widely used for their laxative effects, concerns persist about their potential genotoxicity and carcinogenicity. This study presents the development, validation, and application of a sensitive and rapid LC-MS/MS method to detect HAD (aloins, aloe-emodin, emodin, and danthron) levels in botanical food products and supplements. The method was validated according to criteria established by the European Union Reference Laboratory for Mycotoxins and Plant Toxins, and Regulation (EU) No 2783/2023 and was demonstrated to be fit-for-purpose. It was applied to 43 samples collected from the Italian market, including beverages, liquid and solid food supplements, herbal infusions, and jam based on aloe, senna, cassia, rhubarb, and frangula. The results revealed that 33% of the analyzed samples contained detectable HAD concentrations above the limit of quantification (LOQ = 0.5 mg/kg). The highest concentrations, up to 1352.9 mg/kg for the sum of aloin A and B, were found in solid food supplements derived from senna, cascara, rhubarb, and frangula. Aloe-emodin reached 213.4 mg/kg in a solid food supplement sample containing the same plant species, while the maximum detected concentration of emodin was 259.7 mg/kg in a senna-based supplement. No sample contained danthron. Conversely, in the majority of aloe beverage samples, HAD levels were found to be below the LOQ. In order to ensure the safety of consumers, it is essential that a more rigorous market surveillance of botanical food products is implemented, along with further toxicological studies.

Tetracyclines are a group of antibiotic substances largely administered through medicated feed to control diseases in food-producing animals. Fine dosing of antibiotics contained in medicated feed is crucial for the success of the treatment as well as minimising potential threats such as the spread of antimicrobial resistance and the transfer of antibiotic residues in food. A rapid analytical method based on HPLC with diode array detection (HPLC-DAD) was developed to quantify oxytetracycline, chlortetracycline and doxycycline in medicated feed. The reported method underwent in-house validation and was found to be suitable for the quantification of three target tetracyclines within the concentration range of 40-1000 mg kg-1 in official routine analysis. The method was applied to 103 official samples in the framework of the Italian National Plan on animal feed during the years 2021-2023 and nine non-compliant concentrations were identified in swine and fish feed samples.

In a balanced diet, regular fish consumption provides positive outcomes for human health. On the other hand, the seafood supply chain faces a significant food safety risk due to the presence of potentially toxic elements (PTEs). In the present study, to assess the risk for Italian consumers, the concentrations of five PTEs, namely lead, chromium, cadmium, mercury, nickel, and aluminum, were determined in the three most consumed preserved fish in Italy: tuna (Thunnus albacares, Katsuwonus pelamis), mackerel (Scomber scombrus) and anchovy (Engraulis encrasicolus). Samples were collected from the national market, and the instrumental analysis was performed by inductively coupled plasma mass spectrometry (ICP-MS). The analyzed PTEs were found in all the species that were investigated. However, after considering the target hazard quotient (THQ) and the hazard index (HI), it was observed that the three fish preserves did not pose any risk of chronic toxicity for the average consumer, even at the highest concentrations detected. However, for significant consumers, mercury detected in tuna samples represented almost 90% of the tolerable weekly intake (TWI) reported by the European Food Safety Authority (EFSA), representing a matter of concern for consumers, particularly regarding developmental neurotoxicity, whose HI exceeded 111%. The acute toxicity of nickel was also considered for significant consumers at the highest concentration detected, and the margin of exposure (MOE) calculated was above 7000, much higher than the value of 30 indicated by EFSA. Due to the lack of data on non-professional carcinogenicity or human intake through foods with low cancer risk, this toxicity was not considered in the analysis of PTEs.

Intensive agricultural practices, such as pesticides use, may negatively affect bee health and hive products. Glyphosate is one of the most widely used polar pesticides applied in crops for weed control. In this study, honey samples, collected from beekeeping farms located in the Lombardy and Emilia-Romagna regions in Italy in the framework of regional monitoring plans activated from 2020 to 2022, were analyzed for the presence of residues of polar pesticides. The analytical method based on ion chromatography coupled to high-resolution mass spectrometry was applied to quantify glyphosate, glufosinate, ethephon, fosetyl aluminum, and their related metabolites. Residues of glyphosate were detected in around 28% of analyzed honey samples. Observations on the distribution of the honey-production-site locations suggest that honey samples originating from the provinces within the Lombardy region, where the agricultural sector is highly developed, were more affected by glyphosate contamination than the samples collected from the areas with low agricultural activity, where no glyphosate residues were detected over the three years of the monitoring program.