Metal(loid)s, phthalate esters and polycyclic aromatic hydrocarbons in Croatian natural mineral waters: Regulatory compliance and associated health risk

A leading Croatian manufacturer of natural mineral waters and soft drinks utilizes two artesian wells located in the western part of the Pannonian region to produce over 600 million liters per year. In order to assess the chemical contamination levels in natural mineral waters sourced from these wells, this study examined the presence of metal(loid)s [by inductively coupled plasma mass spectrometry (ICP-MS)], phthalate esters (PAEs) [by gas chromatography-mass spectrometry (GC-MS)], and polycyclic aromatic hydrocarbons (PAHs) [by gas chromatography-tandem mass spectrometry (GC-MS/MS)] at various stages of bottled water production (artesian wells, tanks before filling, products after bottling). The results revealed considerable variability in metal(loid)s concentrations between wells due to differences in local lithology. Concentrations of individual PAEs (<LOD–1.435 µg/L) and PAHs (<LOD–6.528 ng/L) were generally low or below detection limits, with diethyl phthalate (DEP) and bis(2-ethylhexyl) phthalate (DEHP) being the most prevalent PAEs and fluoranthene (FLU) and pyrene (PYR) being the most prevalent PAHs. The storage medium had a significant effect on the inorganic chemical composition of the freshly filled products. Antimony (Sb) was the dominant element leached from plastic packaging, whereas chromium (Cr), copper (Cu), lead (Pb), tin (Sn), and strontium (Sr) leached from glass packaging. All compounds analyzed in water samples were significantly below the legal thresholds for drinking water. The probabilistic analysis indicated that cumulative non-carcinogenic and carcinogenic risks associated with ingestion of bottled waters containing metal(loid)s, PAEs, and PAHs were mostly below the safe thresholds (HI<1.0; CCR<10⁻⁴) for both children and adults.