Transformation of X-ray contrast media by conventional and advanced oxidation processes during water treatment: Efficiency, oxidation intermediates, and formation of iodinated byproducts

Abstract

X-ray contrast media (ICM), as the most widely used intravascular pharmaceuticals, have been frequently detected in various environmental compartments. ICM have attracted increasingly scientific interest owing to their role as an iodine contributor, resulting in the high risk of forming toxic iodinated byproducts (I-BPs) during water treatment. In this review, we present the state-of-the-art findings relating to the removal efficiency as well as oxidation intermediates of ICM by conventional and advanced oxidation processes. Moreover, formation of specific small-molecular I-BPs (e.g., iodoacetic acid and iodoform) during these processes is also summarized. Conventional oxidants and disinfectants including chlorine (HOCl) and chloramine (NH₂Cl) have low reactivities towards ICM with HOCl being more reactive. Iodinated/deiodinated intermediates are generated from reactions of HOCl/NH₂Cl with ICM, and they can be further transformed into small-molecular I-BPs. Types of disinfectants and ICM as well as solution conditions (e.g., presence of bromide (Br^-) and natural organic matters (NOM)) display significant impact on formation of I-BPs during chlor(am)ination of ICM. Uncatalyzed advanced oxidation process (AOPs) involving ozone (O₃) and ferrate (Fe(VI)) exhibit slow to mild reactivities towards ICM, usually leading to their incomplete removal under typical water treatment conditions. In contrast, UV photolysis and catalyzed AOPs including hydroxyl radical (HO^•) and/or sulfate radical (SO₄^.-) based AOPs (e.g., UV/hydrogen peroxide, UV/persulfate, UV/peroxymonosulfate (PMS), and CuO/PMS) and reactive chlorine species (RCS) involved AOPs (e.g., UV/HOCl and UV/NH₂Cl) can effectively eliminate ICM under various conditions. Components of water matrix (e.g., chloride (Cl^-), Br^-, bicarbonate (HCO₃^-), and NOM) have great impact on oxidation efficiency of ICM by catalyzed AOPs. Generally, similar intermediates are formed from ICM oxidation by UV photolysis and AOPs, mainly resulting from a series reactions of the side chain and/or C-I groups (e.g. cleavage, dealkylation, oxidation, and rearrange). Further oxidation or disinfection of these intermediates leads to formation of small-molecular I-BPs. Pre-oxidation of ICM-containing waters by AOPs tends to increase formation of I-BPs during post-disinfection process, while this trend also depends on the oxidation processes applied and solution conditions. This review summarizes the latest research findings relating to ICM transformation and (by)products formation during disinfection and AOPs in water treatment, which has great implications for the practical applications of these technologies.

Keywords: Advanced oxidation process (AOPs); Disinfection; Iodinated byproducts (I-BPs); X-ray contrast media (ICM).