Lai, W.W.-P.W.W.-P.LaiHsu, M.-H.M.-H.HsuANGELA YU-CHEN LIN2020-02-252020-02-252017https://scholars.lib.ntu.edu.tw/handle/123456789/462697Bicarbonate anion (HCO3 −) is a major constituent in wastewater and natural water matrices, and the aim of this study was to investigate its roles in the degradation of the antineoplastic agent methotrexate via UV/TiO2. A comprehensive investigation of reaction mechanisms was performed by conducting scavenger experiments and substructure reactivity and Microtox®toxicity tests. In the presence of HCO3 −, the methotrexate degradation rate substantially increased, indicating the involvement of [rad]CO3 −. The estimated second-order rate constants of methotrexate with [rad]CO3 −and [rad]OH were 1.4 × 107 M−1 s−1and 8.7 × 109 M−1 s−1, respectively. Both the valence hole (hvb +) and [rad]OH resulted in the generation of [rad]CO3 −. Initial transformation pathways of methotrexate were proposed, including the addition of atomic oxygen, hydroxylation, deamination, C[sbnd]C cleavage and C[sbnd]N cleavage. C[sbnd]N cleavage at the aniline moiety (the N(13) position) is the primary decomposition pathway, leading to an aminopterin yield of 43%. [rad]CO3 −preferentially reacted with the 4-aminobenzamide (ABZ) moiety and generated toxic byproducts during the later stages of decomposition, which was not observed in the UV/TiO2system. The reactivity of the three methotrexate substructures decreased in the following order in the presence of HCO3 −: ABZ ≫ DHP ≫ LG∼0; however, without HCO3 −, the following order was observed: ABZ ∼ DHP > LG. The results of this work suggest that the increase in toxicity induced by the presence of HCO3 −likely occurs in many other [rad]OH-based advanced oxidation processes in wastewater containing pharmaceutical cocktails with ABZ moieties. © 2017 Elsevier LtdCarbonate radical; Methotrexate; Photocatalysis; Titanium dioxide; Toxicity[SDGs]SDG6Byproducts; Degradation; Negative ions; Photocatalysis; Rate constants; Titanium dioxide; Advanced Oxidation Processes; Antineoplastic agents; Carbonate radical; Methotrexate; Natural-water matrices; Primary decomposition; Second-order rate constants; Transformation pathways; Toxicity; 4 aminobenzamide; aminopterin; aniline; anion; bicarbonate; carbon; methotrexate; nitrogen; oxygen; sulfanilamide; titanium dioxide; bicarbonate; titanium; waste water; water pollutant; bicarbonate; carbonate; catalysis; chemical compound; decomposition; degradation; photolysis; radical; toxicity; toxicity test; transformation; ultraviolet radiation; wastewater treatment; Article; controlled study; deamination; decomposition; drug degradation; hydroxylation; oxidation; priority journal; reaction analysis; toxicity testing; ultraviolet radiation; chemistry; oxidation reduction reaction; waste water; water pollutant; Bicarbonates; Methotrexate; Oxidation-Reduction; Titanium; Waste Water; Water Pollutants, Chemicaljournal article10.1016/j.watres.2017.01.0402-s2.0-85010943883https://www.scopus.com/inward/record.uri?eid=2-s2.0-85010943883&doi=10.1016%2fj.watres.2017.01.040&partnerID=40&md5=5394c65fe19638059ab18eb57cfd7507