Contents lists available at ScienceDirect Talanta journal homepage: www.elsevier.com/locate/talanta Quantitative and qualitative analysis of polycyclic aromatic hydrocarbons in urine samples using a non-separative method based on mass spectrometry Patricia Martín Santos, Miguel del Nogal Sánchez ⁎ , José Luis Pérez Pavón, Bernardo Moreno Cordero Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Ciencias Químicas, Universidad de Salamanca, 37008 Salamanca, Spain ARTICLE INFO Keywords: Fingerprint type signal Non-separative method Polycyclic aromatic hydrocarbons Chemometrics ABSTRACT In this work, a method for the quantitative and qualitative analysis of 11 polycyclic aromatic hydrocarbons (PAHs) in urine samples is reported. The method is based on the coupling of a programmed temperature va- porizer (PTV) with a quadrupole mass spectrometer (qMS), via a deactivated fused silica tubing. Before the PTV- qMS analysis, the samples were subjected to a liquid-liquid extraction (LLE). The method was rapid since no chromatographic separation was performed. The samples were introduced directly into the PTV, and the analytes were trapped in the Tenax-TA ® packed liner while the solvent was purged. After that, all the compounds reached the mass spectrometer, obtaining the fingerprint of the analysed samples. Urine samples free of PAHs and the same samples spiked with the compounds were analysed. The resulting profile signals were used to quantify the analytes using multivariate calibration, and to classify the samples according to the presence or absence of the PAHs. In the latter task, non-supervised and supervised pattern recognition techniques were employed. The calibration models worked satisfactorily and errors lower or equal to 15% were obtained, in most cases, when an external validation set was analysed. Regarding the classification of the samples, most of the supervised pattern recognition techniques provided excellent results (100% success), where all of the samples were classified correctly. 1. Introduction Polycyclic aromatic hydrocarbons (PAHs) are organic compounds that consist of, at least, two fused aromatic rings. These ubiquitous contaminants are released into the atmosphere by incomplete com- bustion from both natural (forest fires, volcanic eruptions) and an- thropogenic (vehicle emissions, cigarette smoke, cooking) sources. Since these processes are present in many industries, PAHs have been considered as exposure markers where higher levels of these com- pounds can be detected, for example, in different types of workers such as coke oven workers [1–5], firefighters [6,7], aluminium workers [8], and those workers exposed to diesel exhaust [9]. These compounds have also been detected depending on diet [10,11] and smoking habits [12]. Several PAHs have been classified by the International Agency for Research on Cancer (IARC) as possible or probable human carcinogens [13], raising great health concerns all over the world. For this reason, many studies are aimed at associating the risk of cancer [14,15] and the presence of other adverse health effects [16–18] with the concentration of PAHs found in people exposed to these compounds. In addition, the European Commission has established maximum levels for PAHs in several matrixes, for instance in food [19] and primary smoke products [20]. The maximum levels permitted are in the range of μg kg −1 . Once PAHs have entered the human body by the inhalation of contaminated air, ingestion or dermal absorption, they can be subjected to successive metabolic biotransformations, including oxidation, hy- droxylation and hydration, and generate derivatives of the corre- sponding PAHs. This is why most studies report the simultaneous quantification of hydroxylated metabolites [2,4–7,10,12]. However, the determination of unmetabolized PAHs is less explored. Very few ap- plications have been found in the literature for determining un- metabolized parent compounds in urine [1,3,4,8,9,11]. The con- centrations of PAHs for people exposed to these analytes found in literature have been reported to be mostly in the range of μg L −1 [1,3,4,21–24]. In addition, the analysis of PAHs has been performed in other matrices during the last few years, including hair [25], blood and plasma [26], edible vegetable oil [27], water [28], smoked fish [29], milk [30] and gasoline [31]. Because these compounds are present at trace concentrations, they must be extracted from the matrix and preconcentrated before analysis. https://doi.org/10.1016/j.talanta.2018.01.032 Received 22 November 2017; Received in revised form 11 January 2018; Accepted 12 January 2018 ⁎ Corresponding author. E-mail address: mns@usal.es (M. del Nogal Sánchez). Talanta 181 (2018) 373–379 0039-9140/ © 2018 Elsevier B.V. All rights reserved. T