Gas and Liquid Chromatography Mass Spectrometry as a Tool for Elucidating Volatile Organic Compounds (VOCs) and Metabolites in Maternal Milk: A Perspective on Infants’ Health Risk Assessment

Maternal milk is pivotal for infants’ nutrition. It also portrays the chemical burden to which the mother has been exposed. One of the chemical families that is prevalent and related to potential toxic effects are volatile organic compounds (VOCs). In the present study, motivated by the scarcity of works dealing with concomitant VOC and metabolite determination in maternal milk, two new gas/liquid chromatography tandem mass spectrometry (GC-MS/MS, LC-MS/MS) methods for the simultaneous measurement of 25 VOCs and 9 of their metabolites, respectively, in maternal milk were developed and applied to 20 maternal milk samples collected from mothers in Greece. In parallel, a headspace solid-phase microextraction (HS-SPME)–GC-MS method was employed for the untargeted screening of chemicals. Low detection rates for benzene, toluene, styrene and p,m-xylenes, and three of their metabolites, namely N-acetyl-S-(benzyl)-L-cysteine (BMA, metabolite of toluene), 3-methylhippuric (3-MHA, metabolite of xylenes) and mandelic acid (MA as DL and R isomers, metabolites of styrene and ethylbenzene), were evidenced in concentrations varying from <lower limit of quantification (LLOQ) to 0.79 ng mL−1. HS-SPME–GC-MS disclosed the presence of common maternal milk constituents such as fatty acids. Nevertheless, bisphenol-A, bisphenol derivatives and phthalates were also detected. The infants’ health risk assessment demonstrated a low risk and negligible carcinogenic risk, yet the detection of these compounds should not be underestimated.