A rapid and simple HS-SPME–GC–MS method was developed and applied to investigate the effect of the storage time on the release of not intentionally added substances (NIAS) in PET bottled mineral water. The method, validated in terms of linearity, precision, detection, and quantification limits, resulted highly reproducible with limits of detection ranging between 0.05 and 0.17 µg/L. Saturated and 2-unsaturated aliphatic aldehydes, ketones, aliphatic and aromatic hydrocarbon, terpenes, and phthalates were identified and quantified, most of them for the first time in PET bottled mineral water. The levels of the identified NIAS showed statistically significant increases during the shelf-life. Decanal and nonanal were the most abundant compounds identified with levels increasing from 1.42 to 5.07 µg/L and from 0.61 to 1.25 µg/L, respectively. Considering the identified substances, a migration not only from packaging materials but also from the closure caps and adhesive used for sticking the bottle labels may be plausible. Due to the growing popularity of bottled water consumption, the determination of NIAS in mineral water is becoming a top priority. In this context, the method, here developed, could be of great importance not only to assure the safety of bottled mineral water but also to guarantee the sensory quality during the shelf-life.
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