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Determination of gadolinium-based MRI contrast agents in fresh and oceanic waters of Australia

(14.02.2021)


Background:
Structures of the frequently applied gadolinium-based contrast agents for MRI examinations with respective trademarksA variety of gadolinium complexes are used as contrast agents to improve diagnostic capabilities of magnetic resonance imaging (MRI). The most often administered chelates are depicted in Fig. 1.


Figure 1: Structures of the frequently applied gadolinium-based contrast agents for MRI examinations with respective trademarks

On a global scale, more than 30 million examinations per year are performed with the aid of such gadolinium-based contrast agents (GBCAs). After their intravenous injection, the contrast agents are rapidly and mostly unmetabolized excreted via the urine and enter unaltered the aquatic environment via effluents of local waste-water treatment plants. The relatively high amount of approx. 1 g of gadolinium per administration and the frequent use of GBCAs results in a substantial discharge of gadolinium into the environment around medical centers, causing anthropogenic Gd anomalies in the natural distribution of rare earth elements. Such anomalies have been reported for surface waters around the globe and GBCAs could be traced even in the drinking water originating from such aquatic resources (EVISA has frequently reported about such studies, see the related news below). While methodology has been improved over recent years, allowing the determination of GBCAs at trace levels found in drinking water, methods for speciation analysis in complex matrices like seawater have not been reported so far.

The new study:
Now a group of researchers from Australia and Germany aimed at the development of a method for the gadolinium speciation analysis of seawater. Such method not only calls for very low detection limits but also for the elimination of the complex seawater matrix. The researchers achieved these goals by combination of preconcentration via micro-solid phase extraction (µSPE) and separation of Gd-species by hydrophilic interaction liquid chromatography (HILIC). The detection by quadrupole-based inductively coupled plasma mass spectrometry (ICP-MS) was specially tuned for improved ion transmission by modifying ion extraction, transport and increasing the mass bandwidth of the quadrupole.

For the preconcentration of GBCAS from seawater, an automated µSPE method was developed making use of µCARB extraction cartridges. Sample volumes between 250 and 1000 µL were loaded onto the sorbent material and eluted with 250 µL of 73% acetonitrile.  
Chromatographic separations of the GBCAs were performed using an Accucore HILIC silica column with isocratic elution using ammonium acetate buffer  at a pH of 5.3 and 80% acetonitrile. Under optimized conditions with column temperature set to 40°C, and a relatively high flow rate of 1.1. ml/min, separation was achieved in less than three minutes.

Detection of the Gd-species was performed by using a 7700 series ICP-MS system (Agilent Technologies). To improve the detection of Gd at 156 amu, the system was used with an increased mass bandpass mode. The parameters of the bandpass mode consisting of a DC voltage and a RF voltage applied to the four rods of the quadrupole were optimized for best signal to noise ratios of Gd (see figure 2).



The bandpass mode is decreasing mass resolution allowing for transmission of several isotopes simultaneously (see figure 3). The increased ion transmission of the bandpass mode increases sensitivity for Gd by a factor of 44 compared against the standard mode for monitoring the most abundant Gd isotope (158Gd, 24.84%). To prevent potential polyatomic interferences and to reduce background noise, He and H2 were used as cell gases.


 
A standard mix containing four GBCAs at a level of 100 ng/L were analysed by HILIC-ICP-MS employing a standard mode and the bandpass mode, respectively. Figure 4 shows the appropriate separation of all four species in less than three minutes. The detection limits for all four species were between 18 and 24 ng/L in the bandpass mode, about a factor of 5 better than the standard mode. Using this method, Gd-DOTA and Gd-BT-DO3A were detected in coastal seawater within the proximity of a wastewater effluent.



The Original study

Maximilian Horstmann, Raquel Gonzalez de Vega, David. P. Bishop, Uwe Karst, Philip A. Doble, David Clases, Determination of gadolinium MRI contrast agents in fresh and oceanic waters of Australia employing micro-solid phase extraction, HILIC-ICP-MS and bandpass mass filtering, J. Anal. At. Spectrom., 2021. DOI: 10.1039/d0ja00493f

Used techniques and instrumentation:

Agilent Technologies Inc. - 7700X ICP-MS
Agilent 1200 Infinity HPLC


Related studies

Satoki Okabayashi, Leona Kawane, Nanda Yusentri Mrabawani, Takahiro Iwai, Tomohiro Narukawa, Motohiro Tsuboi, Koichi Chiba, Speciation analysis of Gadolinium-based contrast agents using aqueous eluent-hydrophilic interaction liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry, Talanta, 222 (2021) 121531. DOI: 10.1016/j.talanta.2020.121531

Robert Brünjes, Thilo Hofmann, Anthropogenic gadolinium in freshwater and drinking water systems, Water Res., 182 (2020) 115966. DOI: 10.1016/j.watres.2020.115966

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

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

Jens Künnemeyer, Lydia Terborg, Björn Meermann, Christine Brauckmann, Ines Möller, Andy Scheffer, Uwe Karst, Speciation Analysis of Gadolinium Chelates in Hospital Effluents and Wastewater Treatment Plant Sewage by a Novel HILIC/ICP-MS Method, Environ. Sci. Technol., 43/8 (2009) 2884-2890. DOI: 10.1021/es803278n

Serkan Kulaksiz, Michael Bau, Contrasting behaviour of anthropogenic gadolinium and natural rare earth elements in estuaries and the gadolinium input into the North Sea, Earth Planet. Sci. Lett., 260/1-2 (2007) 361-371. DOI: 10.1016/j.epsl.2007.06.016

Andrea Knappe, Peter Möller, Peter Dulski, Asaf Pekdeger, Positive gadolinium anomaly in surface water and ground water of the urban area Berlin, Germany, Chem. Erde Geochem., 65/2 (2005) 167-189. DOI: 10.1016/j.chemer.2004.08.004

Peter Möller, Giulio Morteani, Peter Dulski, Anomalous Gadolinium, Cerium, and Yttrium Contents in the Adige and Isarco River Waters and in the Water of Their Tributaries (Provinces Trento and Bolzano/Bozen, NE Italy), Acta Hydrochim. Hydrobiol., 31/3 (2003) 225-239. DOI: 10.1002/aheh.200300492

Françoise Elbaz-Poulichet, Jean-Luc Seidel, Clara Othoniel, Occurrence of an anthropogenic gadolinium anomaly in river and coastal waters of Southern France, Water Research, 36/4 (2002) 1102-1105. DOI: 10.1016/S0043-1354(01)00370-0

Klaus Kümmerer, Eckard Helmers, Hospital Effluents as a Source of Gadolinium in the Aquatic Environment, Environ. Sci. Technol., 34/2 (2000) 573-577. DOI: 10.1021/es990633h

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