title: Application of metabolite profiling tools and time-of-flight mass spectrometry in the identification of transformation products of iopromide and iopamidol during advanced oxidation.
abstract: The efficiency of wastewater treatment systems in removing pharmaceuticals is often assessed on the basis of the decrease in the concentration of the parent compound. However, what is perceived as "removal" during treatment may not necessarily mean mineralization of the pharmaceutical compound but simply conversion into different transformation products (TPs). Using liquid chromatography coupled to a quadrupole time-of-flight mass spectrometer (LC-QToF-MS), we demonstrated conversion of iopromide in wastewater to at least 14 TPs after an advanced oxidation process (AOP) using UV (fluence = 1500 mJ/cm(2)) and H2O2 (10 mg/L). Due to the complexity of the wastewater matrix, the initial experiments were performed using a high concentration (10 mg/L) of iopromide in order to facilitate the identification of TPs. Despite the high concentration of iopromide used, cursory inspection of UV and mass spectra only revealed four TPs in the chromatograms of the post-AOP samples. However, the use of METLIN database and statistics-based profiling tools commonly used in metabolomics proved effective in discriminating between background signals and TPs derived from iopromide. High-resolution mass data allowed one to predict molecular formulas of putative TPs with errors below 5 ppm relative to the observed m/z. Tandem mass spectrometry (MS/MS) data and isotope pattern comparisons provided necessary information that allowed one to elucidate the structure of iopromide TPs. The presence of the proposed iopromide TPs was determined in unspiked wastewater from a municipal wastewater treatment plant, but no iopromide and TPs were detected. Using analogous structural modifications and oxidation that results from the AOP treatment of iopromide, the potential TPs of iopamidol (a structurally similar compound to iopromide) were predicted. The same mass fragmentation pattern observed in iopromide TPs was applied to the predicted iopamidol TPs. LC-QToF-MS revealed the presence of two iopamidol TPs in unspiked AOP-treated wastewater.
authors: Department of Chemistry, The State University of New York at Buffalo , Buffalo, New York 14260, United States.
authors: Randolph R
authors: RR
authors: Singh
authors: Yaal
authors: Y
authors: Lester
authors: Karl G
authors: KG
authors: Linden
authors: Nancy G
authors: NG
authors: Love
authors: G Ekin
authors: GE
authors: Atilla-Gokcumen
authors: Diana S
authors: DS
authors: Aga
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D006861:Hydrogen Peroxide / Q000737:chemistry; D007472:Iohexol / Q000031:analogs & derivatives* / Q000032:analysis; D007479:Iopamidol / Q000032:analysis*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D062065:Wastewater / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D006861:Hydrogen Peroxide; D007472:Iohexol; D007479:Iopamidol; D062065:Wastewater; D014874:Water Pollutants, Chemical; C038192:iopromide