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The concentration in urine of N-acetyl-hydroxy-propyl-cisteine (3HPMA), an acrolein metabolite, has been employed as a marker of the risk of illness of smokers and the relative concentration of creatinine has been evaluated to verify the effect of moving from the practice of burning tobacco to nicotine vaping. From the results concerning the urine samples of 38 subjects, collected from 2021 to 2023 and analyzed by LC-MS/MS, corresponding to 5 active smokers, 13 previously heavy smokers who replaced traditional tobacco by vaping, and 20 non-smokers, a dramatic reduction was found in 3HPMA/creatinine in urine. 3HPMA varied from values of 2150–3100 µg gcreatinine-1 to levels of 225–625 µg gcreatinine-1 found for non-smokers, with the time decay described by the equation y = 0.3661x2 - 94.359x + 6246.4 (R2: 0.757), providing a time of approximately 10 years for tobacco memory after the cessation of the consumption of burned tobacco., The present study has been co-funded by “Contrato de investigación ESPANA SALUD-UNIVERSITAT DE VALENCIA para el desarrollo del Proyecto: Evaluación de marcadores en orina de riesgo para la salud de fumadores que hayan reemplazado el Tabaco tradicional por HNB o vapeo” (CPI-21-147) and the European Union through the European Regional Development Fund Operational Programme (ERDF) of the Valencian Region (2014–2020). The European Commission financed the analytical instruments used here through the European Regional Development Funds (ERDF) Operation Program of the Valencian Region (2014–2020), Peer Reviewed, Postprint (published version)

A periodic study of the engine oil can allow to anticipate possible breakdowns that the vehicle could have. Due to the complexity of the matrix of this type of samples, a sample treatment prior to analysis is necessary. Analytical chemistry is constantly searching for simpler, more sensitive and environmentally friendly methods. The reverse phase dispersive liquid-liquid microextraction fulfills all the characteristics for the analysis in this type of sample by microwave plasma atomic emission spectrometry (MIP OES). In this work, the extractant solvent used for the microextraction procedure is a diluted acid solution (i.e., 3 M HCl), which is a less-hazardous solvent, in comparison with other solvent used in microextraction procedures. Besides, it is perfectly compatible with MIP OES. The main experimental factors affecting the extraction of Cr, Cu, Mn, Mo, and Ni (i.e., amount of sample, extractant type, acid concentration, extractant volume, extractant time, and centrifugation time and speed) are optimized using a multivariate analysis consisting in two steps: a Plackett-Burman design followed by a circumscribed central composite design. Under optimum conditions (i.e., amount of sample: 5.9 g; extractant volume: 60 µL; extractant type: HCl; acid concentration: 3 M; extraction time: 3 min; centrifugation time: 3 min; centrifugation speed: 2000 rpm), the proposed analytical method is validated and employed to analyze different samples (i.e., used and unused engine oils). Two calibration methods have been evaluated since matrix effects have been observed in the used engine oil sample. These effects have been eliminated using standard addition calibration obtaining RSD and recovery values in the range of 4-12 % and 94-106 % respectively, for samples spiked with 1 µg g-1 of Cr, Cu, Mn, Mo and Ni. Finally, the greenness of this method has been assessed by the Eco-Scale metrics.

The exposure to smoking related products has been evaluated through urine illness risk marker determination through the analysis of urine samples of smokers and vapers. Biomarkers and their metabolites such as N-acetyl-S-(2-cyanoethyl)-L cysteine (CEMA), N-acetyl-S-(3,4-dihydroxybutyl)-L-cysteine (DHBMA), N-acetyl-S-[1-(hydroxymethyl)-2-propen-1-yl)-L cysteine (MHBMA), N-acetyl-S-(3-hydroxypropyl)-L-cysteine (3HPMA), 2R-N-acetyl-S-(4-hydroxybutan-2-yl)-L-cysteine (HMPMA), and N-acetyl-S-(3-carboxy-2-propyl)-L-cysteine (CMEMA) together with nicotine and cotinine were identifed and quantifed by LC-HRMS and LC-MS/MS, and data found normalized to the creatinine level. One hundred two urine samples were collected from smokers, non-smokers, and vapers, spanning an age range from 16 to 79 years. Results obtained showed that CEMA was only detected in urine samples from smokers and MHBMA was in the same order of magnitude in all the urine samples analyzed. HMPMA was found in the urine of vapers at the same order of concentration as in non smokers. 3HPMA in vapers was lower than in the urine of smokers, presenting an intermediate situation between smokers and non-smokers. On the other hand, DHBMA in vapers can reach similar values to those found for smokers, while CMEMA shows concentrations in the urine of vapers higher than in the case of non-smokers and traditional smokers, requiring new research to link this metabolite to the use of electronic cigarettes and possible alternative metabolomic routes. In general, this study seems to verify that traditional smoking practice constitutes a major source of carcinogenic chemicals compared with substitutive practices, although those practices are not free of potential harm., Peer Reviewed, Postprint (published version)