German researchers from the University of Münster investigated the fate of Gadolinium-based contrast agents emitted to the environment via wastewater discharge and were able to follow it into the processed drinking water of several water plants in Germany.
Background:
Gadolinium is a so called "rare-earth element" occuring naturally in the earth crust at relatively low concentration of about 6.2 ppm. In recent decades, a significant amount of anthropogenic gadolinium has been released into the environment as a result of the broad application of contrast agents for magnetic resonance imaging (MRI). While the gadolinium(III) ion occurring in water-soluble salts is quite toxic to mammals, the chelated gadolinium(III) compounds used as contrast agents are far less toxic because they carry gadolinium(III) through the kidneys and out of the body before the free ion can be released into tissue. However the kinetic and thermodynamic stability of the gadolinium chelates makes these complexes also quite resistant against wasterwater treatment and environmental degradation.
The new studies:
In order to follow the gadolinium-based contrast agents from the wastewater discharge through the aquatic environment, the researchers developed sensitive and selective methods for the species determination of Gd-based contrast agents that allows the differentiation of complexed gadolinium from other (natural) Gd species occuring at background levels in the aquatic environment. In earlier studies it was shown that Gd-based contrast agents are neither significantly retained nor degraded during wastewater processing. Using the developed methods for speaciation analysis, the researchers investigated the stability of frequently applied Gd-based MRI contrast agents towards UV radiation. 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.
Figure 1: Structures of the frequently applied gadolinium-based
contrast agents for MRI examinations with respective trademarks
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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.
In a second study the group than followed the gadolinium species through different steps of drinking water purification from surface water in a series of waterworks. Water samples from six waterworks in Germany were analyzed during this study, covering different techniques of drinking water purification. Applied purification techniques involve ground filtration, filtration through activated carbon as well as ozonation. Disinfection of the drinking water is carried out in those water-works by addition of chlorine dioxide or UV irradiation. Using sector-field ICP-MS in combination with ultrasonic nebulization for sample introduction and a HILIC method for on-line separtion of the Gd-based contrast agents, very low detection limits between 8 and 14 pmol/L were obtained for the different contrast agents. This high detection power enabled to follow the frequently applied contrast agents Gd-DTPA, Gd-DOTA and Gd-BT-DO3A throughout the purification steps of the different water works. There was no evidence for additional Gd species or transformation products being present in the analyzed samples. Since sampling schemes were not sufficient for a mass balance throughout the water processing, an interpretation of the data regarding a possible removal of contrast agents was not possible. However measured concentration levels of Gd-based contrast agents did not significantly diminish through the process.
The cited studies:
Marvin Birka, Jörg Roscher, Michael Holtkamp,
Michael Sperling,
Uwe Karst,
Investigating the stability of gadolinium based contrast agents towards UV radiation, Water Research, 91 (2016) 244-250.
DOI: 10.1016/j.watres.2016.01.012 Marvin Birka,
Christoph A. Wehe, Oliver Hachmölle,
Michael Sperling,
Uwe Karst,
Tracing gadolinium-based contrast agents from surface water to drinking water by means of speciation analysis, J. Chromatogr. A, 1440 (2016) 105–111.
DOI: 10.1016/j.chroma.2016.02.050
Related studies (newest first): U. Lindner, J. Lingott, S. Richter, W. Jiang,
N. Jakubowski, U. Panne,
Analysis of Gadolinium-based contrast agents in tap water with a new hydrophilic interaction chromatography (ZIC-cHILIC) hyphenated with inductively coupled plasma mass spectrometry, Anal. Bioanal. Chem., 407 (2014) 2415–2422.
DOI: 10.1007/s00216-014-8368-5 N. Tepe, M. Romero, M. Bau,
High-technology metals as emerging contaminants: strong increase of anthropogenic gadolinium levels in tap water of Berlin, Germany, from 2009 to 2012, Appl. Geochem., 45 (2014) 191-197.
DOI: 10.1016/j.apgeochem.2014.04.006 G. Klaver, M. Verheul, I. Bakker, E. Petelet-Giraud, P. Negrel,
Anthropogenic rare earth element in rivers: gadolinium and lanthanum. Partitioning between the dissolved and particulate phases in the Rhine River and spatial propagation through the Rhine-Meuse Delta (the Netherlands), Appl. Geochem., 47 (2014) 186-197.
DOI: 10.1016/j.apgeochem.2014.05.020 M. Birka,
C.A. Wehe,
L. Telgmann,
M. Sperling,
U. Karst,
Sensitive quantification of gadolinium-based magnetic resonance imaging contrast agents in surface waters using hydrophilic interaction liquid chromatography inductively coupled plasma sector field mass spectrometry, J. Chromatogr. A, 1308 (2013) 125–131.
DOI: 10.1016/j.chroma.2013.08.017 U. Lindner, J. Lingott, S. Richter,
N. Jakubowski, U. Panne,
Speciation ofgadolinium in surface water samples and plants by hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry, Anal. Bioanal. Chem., 405 (2013) 1865–1873.
DOI: 10.1007/s00216-012-6643-x J. Rozemeijer, C. Siderius, M. Verheul, H. Pomarius,
Tracing the spatial propagation of river inlet water into an agricultural polder area using anthropogenic gadolinium, Hydrol. Earth Syst. Sci., 16 (2012) 2405–2415.
DOI:10.5194/hess-16-2405-2012 L. Telgmann,
C.A. Wehe, M. Birka, J. Künnemeyer, S. Nowak,
M. Sperling,
U. Karst,
Speciation and isotope dilution analysis of gadolinium-based contrastagents in wastewater, Environ. Sci. Technol., 46 (2012) 11929–11936.
DOI: 10.1021/es301981z S. Kulaksiz, M. Bau,
Anthropogenic gadolinium as a microcontaminant in tapwater used as drinking water in urban areas and megacities, Appl. Geochem., 26 (2011) 1877–1885.
DOI: 10.1016/j.apgeochem.2011.06.011
C.S.K. Raju, A. Cossmer, H. Scharf, U. Panne, D. Lück,
Speciation of gadolinium based MRI contrast agents in environmental water samples using hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom. 25 (2010) 55–61.
DOI: 10.1039/b919959d P.L. Verplanck, E.T. Furlong, J.L. Gray, P.J. Phillips, R.E. Wolf, K. Esposito,
Evaluating the behavior of gadolinium and other rare earth elements through large metropolitan sewage treatment plants, Environ. Sci. Technol. 44 (2010) 3876–3882.
DOI: 10.1021/es903888t J. Künnemeyer, L. Terborg,
B. Meermann, C. Brauckmann, I. Möller, A. Scheffer,
U. Karst,
Speciation analysis of gadolinium chelates in hospital effluents and wastewater treatment plant sewage by a novel HILIC/ICP-MS method, Environ. Sci. Technol., 43 (2009) 2884–2890.
DOI: 10.1021/es803278n
M. Rabiet, F. Brissaud, J.L. Seidel, S. Pistre, F. Elbaz-Poulichet,
Positive gadolinium anomalies in wastewater treatment plant effluents and aquatic environment in the Hérault watershed (South France), Chemosphere, 75 (2009) 1057–1064.
DOI: 10.1016/j.chemosphere.2009.01.036 M.G. Lawrence, C. Ort, J. Keller,
Detection of anthropogenic gadolinium in treated wastewater in South East Queensland, Australia, Water Res., 43/14 (2009) 3534-3540.
DOI: 10.1016/j.watres.2009.04.033 S. Kulaksiz, M. Bau,
Contrasting behaviour of anthropogenic gadolinium andnatural rare earth elements in estuaries and the gadolinium input into the North Sea, Earth Planet. Sci. Lett., 260 (2007) 361–371.
DOI: 10.1016/j.epsl.2007.06.016 M. Bau, A. Knappe, P. Dulski,
Anthropogenic gadolinium as a micropollutant inriver waters in Pennsylvania, and in Lake Erie, northeastern United States, Chem. Erde—Geochem., 66 (2006) 143–152.
DOI: 10.1016/j.chemer.2006.01.002 A. Knappe, P. Möller, P. Dulski, A. Pekdeger,
Positive gadolinium anomaly insurface water and ground water of the urban area Berlin, Germany, Chem. Erde—Geochem., 65 (2005) 167–189.
DOI: 10.1016/j.chemer.2004.08.004 P.L. Verplanck, H.E. Taylor, D.K. Nordstrom, L.B. Barber,
Aqueous stability of gadolinium in surface waters receiving sewage treatment plant effluent, Boulder Creek, Colorado, Environ. Sci. Technol., 39 (2005) 6923–6929.
DOI: 10.1021/es048456u F. Elbaz-Poulichet, J.L. Seidel, C. Othoniel,
Occurrence of an anthropogenic gadolinium anomaly in river and coastal waters of Southern France, Water Res., 36 (2002) 1102–1105.
DOI: 10.1016/S0043-1354(01)00370-0
Y. Nozaki, D. Lerche, D.S. Alibo, M. Tsutsumi,
Dissolved indium and rare earth elements in three Japanese rivers and Tokyo Bay: evidence for anthropogenic Gd and In, Geochim, Cosmochim. Acta, 64 (2000) 3975–3982.
DOI: 10.1016/S0016-7037(00)00472-5
M. Bau, P. Dulski,
Anthropogenic origin of positive gadolinium anomalies in river waters, Earth Planet. Sci. Lett., 143 (1996) 245–255.
DOI: 10.1016/0012-821X(96)00127-6 
Related EVISA Resources
Brief summary: Speciation analysis for the study of metallodrugs and their biomolecular interactions Brief summary: ICP-MS - A versatile detection system for speciation analysis Brief summary: LC-ICP-MS - The most often used hyphenated system for speciation analysis
Brief summary: ESI-MS: The tool for the identification of chemical species Link Database: Toxicity of Gadolinium compounds
Link database: Use of Gadolinium in pharmaceuticals
Materials Database: Gadolinium Materials
Link page: All about Mass Spectrometry: Resources related to Mass Spectrometry
Link page: All about environmental sciences 
Related EVISA News
October 29, 2012: Identification and quantification of potential metabolites of Gd-based contrast agents October 18, 2012: The behavior of Gd-based contrast agents during wastewater treatment September 15, 2010: US FDA Announces Gadolinium-Based MRI Contrast Agent Warning March 25, 2010: Publication on the separation of Gd-based contrast agents awarded April 17, 2009: Gadolinium-based MRI contrast agents found intact in the outlet of a waste water treatment plant
last time modified: September 24, 2024
