Why Small Differences Matter: Elucidation of the Mechanisms Underlying the Transformation of 2OH- and 3OH-Carbamazepine in Contact with Sand Filter Material.

Carbamazepine (CBZ) is a worldwide used antiepileptic drug, which is metabolized to a large extent in the human body to several metabolites, including 10,11-dihydroxy-10,11-dihydrocarbamazepine (DiOHCBZ), 2-hydroxycarbamazepine (2OHCBZ), and 3-hydroxycarbamazepine (3OHCBZ). 2OHCBZ and 3OHCBZ were previously detected in raw and treated wastewater revealing their widespread emission into the aquatic environment, eventually leading to the contamination of drinking water resources. Sand filtration is frequently applied in drinking water treatment for the removal of inorganic species and suspended particles but has been shown to be capable of removing trace organic contaminants. This study focuses on the elucidation of the (bio)transformation mechanisms of 2OHCBZ and 3OHCBZ in contact with material taken from a rapid sand filter of a German waterworks. Despite their similar structure, which differs only in the position of the phenolic OH moiety, both compounds underwent distinct transformation reactions leading to the formation of a variety of transformation products (TPs). The main biochemical reactions thereby included enzymatic transformation of 2OHCBZ resulting in the formation of a reactive iminoquinone intermediate (2OHCBZ) and nitration via peroxynitrite (2OHCBZ and 3OHCBZ) as well as formation of radicals leading to dimerization (3OHCBZ). Further transformation reactions included hydroxylation, ring cleavage, loss of carbamoyl group, and decarboxylation, as well as O-methylation.