Speciation Analysis of Gadolinium Chelates in Hospital Effluents and Wastewater Treatment Plant Sewage by a Novel HILIC/ICP-MS Method

The behavior of Gd chelates used in magnetic resonance imaging (MRI) within the process of sewage treatment is widely unknown. Due to the varying toxicity of the particular Gd species [J. M. Idee et al. Fundam. Clin. Pharmacol. 2006, 20, 563−576], it is important to not only investigate total Gd concentrations, but the Gd species as well. This work describes a novel method for speciation analysis of the most important gadolinium chelates in wastewaters. This novel approach consists of coupling hydrophilic interaction chromatography (HILIC) with inductively coupled plasma mass spectrometry (ICP-MS). HILIC/ICP-MS exhibits high separation efficiency for the simultaneous separation of the five predominantly applied MRI contrast agents and the required selectivity and sensitivity for trace determination in wastewater samples. For the first time, the distribution of particular Gd chelate complexes was determined in hospital effluent, municipal sewage, and wastewater treatment plant (WWTP) samples. The data were compared with the total concentration of Gd as determined by ICP-MS. The active compounds of Multihance, Dotarem, and Gadovist were identified in local WWTP samples. Interestingly, the macrocyclic, nonionic compound Gd-BT-DO3A (Gadovist) was found to be the most abundant Gd complex in all investigated samples. This is in contrast to prevalent assumptions that linear ionic Gd chelates such as Gd-DTPA (Magnevist) would be the predominant species [G. Morteani et al. Environ. Geochem. Health 2006, 28, 257−264 and M. Bau and P. Dulski, Earth Planet. Sci. Lett. 1996, 143, 245−255]. Although contrast agent concentrations tend to be reduced during wastewater treatment, Gd-BT-DO3A was still found in WWTP effluents.