Honey is a natural product well known for its beneficial properties. It contains phytochemicals, a wide class of nutraceuticals found in plants, including compounds with highly demonstrated antimicrobial and antioxidant capacities as phenolic compounds and flavonoids. The main goal of this work is the development of a miniaturized and environmentally friendly methodology to obtain the phenolic profile of Galician honeys (Northwest Spain) from different varieties such as honeydew, chestnut, eucalyptus, heather, blackberry and multi-floral. The total phenolic content (TPC) and antioxidant activity (AA) were also evaluated. As regards sample preparation, miniaturized vortex (VE) and ultrasound assisted extraction (UAE) employing aqueous-based solvents were performed. Individual quantification of 41 target phenolic compounds was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Results revealed the presence of 25 phenolic compounds in the 91 analyzed samples, reaching concentrations up to 252 µg g⁻¹. Statistical tools such as analysis of variance (ANOVA) and principal component analysis (PCA) were employed to obtain models that allowed classifying the different honeys according to their botanical origin. Obtained results, based on TPC, AA and ∑phenolic compounds showed that significant differences appeared depending on the honey variety, being several of the identified phenol compounds being responsible of the main differentiation.

A fast, efficient, and simple air sampling methodology was developed to study a high number of volatile and semivolatile organic compounds in air above tire rubber materials and surfaces made of recycled tire rubber. The proposed method, based on active sampling (solid-phase extraction, SPE) using a small quantity of sorbent material (25 mg) followed by solid-phase microextraction (SPME) and gas chromatography-tandem mass spectrometry analysis, was developed with the aim of determining 40 organics substances including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants, and vulcanization agents. An experimental design was carried out to study the influence of main factors such as type of SPME fibre, solvent addition, headspace volume, stirring, as well as the factor interactions. Method performance showed good linearity in a broad concentration range (0.05 to 200 ng m^-3, for most compounds), with coefficients of determination (R²) higher than 0.9900. Whole method precision (≤ 16 %) and accuracy were also satisfactory, obtaining quantitative recoveries (mean values between 80 and 110 % in most cases). Limits of detection and quantification have also been calculated, yielding values of sub ng m^-3 for most compounds. The validated method was applied to outdoor and indoor air environments including playgrounds, football pitches and warehouses showing the presence of most target compounds in the samples achieving high levels for some PAHs (concentrations up to 51 ng m^-3), benzothiazole (BTZ), diisobutyl- dibutyl- and di-(2-ethylhexyl)- phthalate, among others, reaching concentrations up to hundreds of ng m^-3 (BTZ). This is the first time that the combination of techniques SPE and SPME is applied for these families of chemicals, and it is also the first time that this approach is proposed for the simultaneous multiclass compound extraction of substances of different chemical families. The whole sampling and extraction procedure is performed in a short period of time (61 min) allowing high throughput. The elimination of the use of organic solvents and waste generation by using only 25 mg of sorbent and a SPME fibre than are both reused makes the method sustainable and in consonance with the principles of the green chemistry. The method can be implemented in any routine lab and easily automated using a SPME autosampler.

Tires, apart from being formed by rubber and filling materials, contain organic compounds added to make them resistant and durable. The widely use of recycled tire crumb rubber (RTCR), main product of the shredding process of end-of-life tires, can cause human exposure to these chemicals due to its use in synthetic football fields and kid's playgrounds. In 2023, the European Commission banned the use of recycled tire crumb rubber in synthetic fields, giving eight years to replace the used material. This study intends to assess the oral bioaccessibility of antiozonants, crosslinking and vulcanizer agents present in RTCR. With this purpose, the Unified Bioaccessibility Method (BARGE) was used to simulate the material ingestion. RTCR is put into contact with the four simulated biological fluids including saliva, gastric and duodenal juice and bile, attempting to simulate human digestion. Afterwards, the organic compounds present in the fluid need to be extracted and Solid-phase extraction (SPE) was the technique selected after being optimized to obtain the best extraction conditions. Ultrasound assisted extraction was performed to evaluate the total concentration of the target compounds in the crumb rubber matrixes. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was employed to identify and quantify the target compounds. The results showed the bioaccessibility of all the studied analytes, with values ranging from 0.1 % up to 70 %. Benzothiazole was the compound with the highest bioaccessibility with a mean value of 40 % and concentrations reaching 32000 ng g^-1 in the bioaccessible fraction. N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and its transformation product ((4-Methylpentan-2-yl)amino)-5-(phenylamino)cyclohexa-2,5-diene-1,4-dione) showed an average bioaccessibility of 0.1 % and 1.8 %, respectively, the latter being present in all the analysed samples.

Honey is a natural food product well known for its high nutritional value. Apart from sugars, it contains phytochemicals, including polyphenols and flavonoids, that are compounds with highly demonstrated antimicrobial and antioxidant capacities. The main goal of this work is the development of an analytical methodology to obtain the polyphenolic profile of honeys from different varieties and pollen sources. To isolate the target compounds from the samples, miniaturized vortex (VE) and ultrasound-assisted extraction (UAE) employing aqueous solvent followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) were employed. The results revealed that more than 20 different polyphenols were detected in the analyzed samples among the 40-targeted compounds, reaching total concentrations up to hundreds of µg g⁻¹. Other indexes such as the total polyphenolic content (TPC) and antioxidant activity (AA) were also evaluated by spectrophotometric techniques. ANOVA and PCA based on the results from TPC, AA and individual polyphenol concentrations showed that significant differences appeared depending on the honey variety, being several of the identified polyphenols, especially hydroxycinnamic acids, responsible for the main differentiation. The results also revealed that two components were enough to explain more than 90% of variance and honey classification in six different groups. Having regard to the occurence and concentrations of individual polyphenols, it is shown that the combination of chromatographic analysis, mass spectrometry detection and PCA are suitable tools to investigate the botanical authentication of honey.