Evaluation of parabens and their metabolites in fish and fish products : a comprehensive analytical approach using LC-HRMS

Parabens (PBs) are preservatives frequently used in cosmetics and personal care products as well as in the pharmaceutical and food industries due to their extensive defence mechanisms against multiple categories of microorganisms. Although they are considered safe when used within defined concentration limits, concern about their potential toxicity is still particularly active. Revealed as emerging pollutants, their incidence and behaviour in the aquatic environment have been studied, but there is only sporadic information when it comes to their extent and distribution in seafood. This study explores the presence of methyl- (MeP), ethyl-, propyl-, butyl-, and benzylparaben and their main degradation product 4-hydroxybenzoic acid (pHBA) in several fish species and bivalve samples with the aim to evaluate these food matrices as potentially important contamination sources of PB. Additionally, infant food containing fish was also enrolled in this survey: firstly, due to the absence of any information regarding this exceptionally important food item, and secondly, because of the necessity to estimate the PB content in the processed food. For this purpose, a fast, reliable and robust method was developed based on a simple liquid-liquid extraction followed by high-performance LC, coupled with a benchtop Q-Exactive Orbitrap high-resolution MS. The Q-Exactive parameters were carefully scheduled to achieve a balance between the optimal scan speed and selectivity, considering the limitations that are associated with generic sample preparation methodology. The method was validated through specificity, linearity, recovery, intra- and inter-day repeatability, LOD and LOQ. LOD and LOQ reached the ranges 0.65-3.5 and 2.15-11.7 ng g-1, respectively, while overall recovery ranged from 77% to 118%. The PBs were more frequently present in bivalves than in fish samples with MeP as the main PB detected. No PBs were found in infant food, but pHBA was observed in all samples.