title: Investigating the stability of gadolinium based contrast agents towards UV radiation.
abstract: Since the 1980s, the broad application of gadolinium(Gd)-based contrast agents for magnetic resonance imaging (MRI) has led to significantly increased concentrations of Gd in the aqueous environment. Little is known about the stability of these highly polar xenobiotics under environmental conditions, in wastewater and in drinking water treatment. Therefore, the stability of frequently applied Gd-based MRI contrast agents towards UV radiation was investigated. The hyphenation of hydrophilic interaction liquid chromatography (HILIC) with inductively coupled plasma mass spectrometry (ICP-MS) and of HILIC with electrospray ionization mass spectrometry (ESI-MS) provided quantitative elemental information as well as structural information. The contrast agents Gd-DTPA, Gd-DOTA and Gd-BT-DO3A showed a high stability in irradiation experiments applying a wavelength range from 220 nm to 500 nm. Nevertheless, the degradation of Gd-BOPTA as well as the formation of Gd-containing transformation products was observed by means of HILIC-ICP-MS. Matrix-dependent irradiation experiments showed a degradation of Gd-BOPTA down to 3% of the initial amount in purified water after 300 min, whereas the degradation was slowed down in drinking water and surface water. Furthermore, it was observed that the sum of species continuously decreased with proceeding irradiation in all matrices. After irradiation in purified water for 300 min only 16% of the sum of species was left. This indicates a release of Gd(III) ions from the complex in course of irradiation. HILIC-ESI-MS measurements revealed that the transformation products mostly resulted from O-dealkylation and N-dealkylation reactions. In good correlation with retention times, the majority of transformation products were found to be more polar than Gd-BOPTA itself. Based on accurate masses, sum formulas were obtained and structures could be proposed.
authors.affiliation: University of Münster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 28/30, 48149 Münster, Germany.
authors.forename: Marvin
authors.initials: M
authors.lastname: Birka
authors.affiliation: University of Münster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 28/30, 48149 Münster, Germany.
authors.forename: Jörg
authors.initials: J
authors.lastname: Roscher
authors.affiliation: University of Münster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 28/30, 48149 Münster, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Holtkamp
authors.affiliation: University of Münster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 28/30, 48149 Münster, Germany; European Virtual Institute for Speciation Analysis (EVISA), Mendelstraße 11, 48149 Münster, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Sperling
authors.affiliation: University of Münster, Institute of Inorganic and Analytical Chemistry, Corrensstraße 28/30, 48149 Münster, Germany. Electronic address: uk@uni-muenster.de.
authors.forename: Uwe
authors.initials: U
authors.lastname: Karst
mesh_terms: D002853:Chromatography, Liquid; D003287:Contrast Media / Q000528:radiation effects*; D005682:Gadolinium / Q000528:radiation effects*; D013058:Mass Spectrometry; D021241:Spectrometry, Mass, Electrospray Ionization; D014466:Ultraviolet Rays; D014865:Waste Disposal, Fluid; D062065:Wastewater / Q000032:analysis*; D014874:Water Pollutants, Chemical / Q000528:radiation effects*
chemical_list: D003287:Contrast Media; D005682:Gadolinium; D062065:Wastewater; D014874:Water Pollutants, Chemical
keywords: Contrast agents; Gadolinium; Speciation analysis; UV radiation; Xenobiotics