Fast and automated monitoring of gadolinium-based contrast agents in surface waters

Marcel Macke; C Derrick Quarles Jr; Michael Sperling; Uwe Karst

doi:10.1016/j.watres.2021.117836

Fast and automated monitoring of gadolinium-based contrast agents in surface waters

Water Res. 2021 Dec 1:207:117836. doi: 10.1016/j.watres.2021.117836. Epub 2021 Nov 5.

Authors

Marcel Macke¹, C Derrick Quarles Jr², Michael Sperling³, Uwe Karst⁴

Affiliations

¹ Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstr. 28/30, 48149 Münster, Germany.
² Elemental Scientific, Inc., 7277 World Communications Dr., Omaha, NE 68022, United States.
³ Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstr. 28/30, 48149 Münster, Germany; European Virtual Institute for Speciation Analysis (EVISA), Germany.
⁴ Institute of Inorganic and Analytical Chemistry, University of Münster, Corrensstr. 28/30, 48149 Münster, Germany. Electronic address: uk@uni-muenster.de.

PMID: 34798450
DOI: 10.1016/j.watres.2021.117836

Abstract

Gadolinium-based contrast agents (GBCAs) are frequently used for magnetic resonance imaging to improve image contrast. These inert complexes are excreted unmetabolized from the human body and pass through wastewater treatment plants almost unaffected, leading to a significant release of anthropogenic Gd into the environment. However, long-term ecotoxicological effects of GBCAs are mainly unknown and thus powerful methods of speciation analysis are required to monitor their distribution and fate in aquatic systems. In this work, a rapid and efficient monitoring method was developed utilizing a fully automated single platform system for total metal analysis and syringe-driven chromatography in combination with inductively coupled plasma-mass spectrometry (ICP-MS). An anion-exchange chromatography (IC) method was developed and applied to achieve a rapid separation and sensitive detection of the five complexes Gd-HP-DO3A, Gd-BT-DO3A, Gd-DOTA, Gd-DTPA, and Gd-BOPTA that are commonly administered in the European Union. Furthermore, the use of an automated inline-dilution function allowed a fast-external calibration from single stock standards. A chromatographic run time of less than 2 min and species-specific detection limits between 11 and 19 pmol L^-1 on a quadrupole ICP-MS proved to be competitive compared to previously published methods, but without the use of aerosol desolvation and/or sector field ICP-MS to enhance sensitivity. The automated IC-ICP-MS method was applied for quantitative GBCA monitoring in a multitude of surface water samples that were obtained in the German state of North Rhine-Westphalia. The complexes Gd-HP-DO3A, Gd-BT-DO3A, and Gd-DOTA, were detected and quantified. In addition, the occurrence of an unidentified Gd species was observed for one of the sampled river systems.

Keywords: Automation; Gadolinium-based contrast agents; Inductively coupled plasma-mass spectrometry; Ion exchange chromatography; Speciation analysis; Water monitoring.

MeSH terms

Contrast Media*
Gadolinium
Gadolinium DTPA
Humans
Magnetic Resonance Imaging
Organometallic Compounds*
Rivers

Substances

Contrast Media
Organometallic Compounds
Gadolinium
Gadolinium DTPA