A team of researchers from Germany and the US have developed a method based on ion-chromatography for the sensitive and selective determination of gadolinium-based contrast agents in surface waters. The method is implemented on an automated workstation coupled to an inductively coupled plasma mass spectrometer, providing fully automated analysis with high sample throughput, high selectivity and excellent detection power.
Background:Magnetic resonance imaging (MRI) is an indispensable method for clinical diagnostic, used for imaging inner organs. Gadolinium-based contrast agents (GBCAs) are used in 1 out of 3 MRI scans to improve the clarity and quality of images of the body's internal structures. Normally, a person of 75 kg body weight will receive a dose of about 1.2 g of Gadolinium.
The MRI agents are excreted nearly quantitatively from the patient’s body, unmetabolized and fast via the urine. Depending on the number and activity of clinical centres performing MRI examinations within the catchment area of a sewage treatment plant, the input of Gadolinium (Gd) into the public sewer is therefore relatively high. Hence, it can be estimated that in Europe alone, up to 19 tons of Gd are discharged into the environment every year, making GBCAs an emerging contaminant in aquatic systems.
As has been demonstrated in earlier research, the highly stable GBCAs are neither significantly retained nor degraded in standard waste water treatment plants, and are released into the aquatic environment. Since gadolinium is a "rare earth element", such pollution can enhance the natural background concentration of gadolinium in water markedly, which has been recognized by many scientists via the observation of an unnatural distribution pattern of the rare earth elements with an enhanced fraction of gadolinium called "gadolinium anomaly". However, such anomaly can also have biogeochemical causes resulting from the geological situation or the chemistry within the water body. In order to monitor the distribution of the GBCAs and their fate in the aquatic environment, therefore, a highly sensitive and selective speciation analysis is required. Since long-term ecotoxicological effects of GBCAs are mainly unknown, such speciation analysis is mandatory as a first step for gaining information about their environmental behaviour.
The new method:Working on this topic since 2006, the researchers from the University of Münster cooperated with the instrument manufacturer
Elemental Scientific (ESI) to fully automate the speciation analysis of GBCAs based on ion-chromatography coupled to inductively coupled plasma-mass spectrometry (ICP-MS). The developed method is able to determine the five complexes Gd-HP-DO3A, Gd-BT-DO3A, Gd-DOTA, Gd-DTPA, and Gd-BOPTA that are commonly administered in the European Union within a chromatographic run of less than 2 minutes.
The method is implemented on an automated workstation (
prepFast IC) for total metal analysis and syringe-driven chromatography. Furthermore, the use of an automated inline-dilution function allowed a fast-external calibration from single stock standards. Using an anion-exchange chromatography (IC) method for separation and a quadrupole ICP-MS for detection, species-specific detection limits between 11 and 19 pmol L-1 proved to be very competitive to previously published methods, that had to use special sample introduction systems (ultrasonic nebulizers, desolvation systems) in combination with high sensitivity sector-field ICP-MS.
The automated IC-ICP-MS method was applied to monitor GBCAs in a couple of surface waters collected from five different river and creek systems in the German state of North Rhine-Westphalia. All sampled surface waters are affected by the discharge of municipal WWTPs and are also relevant for the local drinking water supply. 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.
The original publication
Marcel Macke,
C. Derrick Quarles Jr, Michael Sperling,
Uwe Karst,
Fast and Automated Monitoring of Gadolinium-based Contrast Agents in Surface Waters, Water Res., 207 (2021) 117836. DOI: 10.1016/j.watres.2021.117836.
Instrumentation used:
Thermo Scientific - iCAP-TQ ICP-MS
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