Abstract
Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) were optimised for the direct determination of gadolinium-based contrast agents in tap water. In comparison to our previous work, a new developed zwitterionic HILIC column (ZIC-cHILIC) was used for speciation of Gd-containing contrast agents. The limit of quantification (LOQ) for the five contrast agents Gd-BOPTA, Gd-DPTA-BMA, Gd-BT-DO3A, Gd-DOTA and Gd-DTPA are in the range of 5–12 ng Gd per litre. Additionally, a new internal standard, Pr-DOTA, was investigated to correct intensity drifts, minor and major changes in the sample volumes and possible matrix effects. With the speciation method described, tap water samples from the area of Berlin were analysed and for the first time, three Gd species, Gd-BT-DO3A, Gd-DOTA and Gd-BOPTA, were found in tap water samples at concentrations of about 10–20 ng Gd per litre. These are the same Gd species which have been previously detected predominantly in surface waters of the Berlin area.
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Grobe TG, Dörning H, Schwartz FW (2011) BARMER GEK Arztreport 2011, Schwerpunkt: Bildgebende Diagnostik. Schriftrenreihe zur Gesundheitsanalyse, vol Band 6. ISEG, Institut für Sozialmedizin, Epidemiologie und Gesundheitssystemforschung, Hannover
Idée J-M, Port M, Raynal I, Schaefer M, Le Greneur S, Corot C (2006) Clinical and biological consequences of transmetallation induced by contrast agents for magnetic resonance imaging: a review. Fundam Clin Pharmacol 20(6):563–576. doi:10.1111/j.1472-8206.2006.00447.x
Hermann P, Kotek J, Kubicek V, Lukes I (2008) Gadolinium(III) complexes as MRI contrast agents: ligand design and properties of the complexes. Dalton Trans 23:3027–3047. doi:10.1039/B719704g
Ersoy H, Rybicki FJ (2007) Biochemical safety profiles of gadolinium-based extracellular contrast agents and nephrogenic systemic fibrosis. J Magn Reson Imaging 26(5):1190–1197. doi:10.1002/Jmri.21135
Telgmann L, Wehe CA, Birka M, Künnemeyer J, Nowak S, Sperling M, Karst U (2012) Speciation and isotope dilution analysis of gadolinium-based contrast agents in wastewater. Environ Sci Technol 46(21):11929–11936. doi:10.1021/es301981z
Möller P, Morteani G, Dulski P (2003) 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):225–239. doi:10.1002/aheh.200300492
Bau M, Dulski P (1996) Anthropogenic origin of positive gadolinium anomalies in river waters. Earth Planet Sci Lett 143(1–4):245–255
Elbaz-Poulichet F, Seidel JL, Othoniel C (2002) Occurrence of an anthropogenic gadolinium anomaly in river and coastal waters of southern France. Water Res 36(4):1102–1105
Morteani G, Moller P, Fuganti A, Paces T (2006) Input and fate of anthropogenic estrogens and gadolinium in surface water and sewage plants in the hydrological basin of Prague (Czech Republic). Environ Geochem Health 28(3):257–264. doi:10.1007/s10653-006-9040-6
Knappe A, Möller P, Dulski P, Pekdeger A (2005) Positive gadolinium anomaly in surface water and ground water of the urban area Berlin, Germany. Chem Erde 65:167–189
Rabiet M, Togola A, Brissaud F, Seidel JL, Budzinski H, Elbaz-Poulichet F (2006) Consequences of treated water recycling as regards pharmaceuticals and drugs in surface and ground waters of a medium-sized Mediterranean catchment. Environ Sci Technol 40(17):5282–5288. doi:10.1021/Es060528p
Nozaki Y, Lerche D, Alibo DS, Tsutsumi M (2000) Dissolved indium and rare earth elements in three Japanese rivers and Tokyo Bay: evidence for anthropogenic Gd and In. Geochim Cosmochim Acta 64(23):3975–3982
Zhu Y, Hoshino M, Yamada H, Itoh A, Haraguchi H (2004) Gadolinium anomaly in the distributions of rare earth elements observed for coastal seawater and river waters around Nagoya City. Bull Chem Soc Jpn 77(10):1835–1842. doi:10.1246/Bcsj.77.1835
Verplanck PL, Taylor HE, Nordstrom DK, Barber LB (2005) Aqueous stability of gadolinium in surface waters receiving sewage treatment plant effluent, Boulder Creek, Colorado. Environ Sci Technol 39(18):6923–6929. doi:10.1021/es048456u
Kulaksiz S, Bau M (2007) 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):361–371. doi:10.1016/j.epsl.2007.06.016
Lawrence MG, Jupiter SD, Kamber BS (2006) Aquatic geochemistry of the rare earth elements and yttrium in the Pioneer River catchment, Australia. Mar Freshw Res 57(7):725–736. doi:10.1071/Mf05229
Hennebrüder K, Wennrich R, Mattusch J, Stärk H-J, Engewald W (2004) Determination of gadolinium in river water by SPE preconcentration and ICP-MS. Talanta 63(2):309–316
Hemstrom P, Irgum K (2006) Hydrophilic interaction chromatography. J Sep Sci 29(12):1784–1821. doi:10.1002/jssc.200600199
Künnemeyer J, Terborg L, Nowak S, Scheffer A, Telgmann L, Tokmak F, Günsel A, Wiesmüller G, Reichelt S, Karst U (2008) Speciation analysis of gadolinium-based MRI contrast agents in blood plasma by hydrophilic interaction chromatography/electrospray mass spectrometry. Anal Chem 80(21):8163–8170. doi:10.1021/ac801264j
Künnemeyer J, Terborg L, Nowak S, Telgmann L, Tokmak F, Kramer BK, Günsel A, Wiesmüller GA, Waldeck J, Bremer C, Karst U (2009) Analysis of the contrast agent magnevist and its transmetalation products in blood plasma by capillary electrophoresis/electrospray ionization time-of-flight mass spectrometry. Anal Chem 81(9):3600–3607. doi:10.1021/Ac8027118
Kunnemeyer J, Terborg L, Nowak S, Brauckmann C, Telgmann L, Albert A, Tokmak F, Kramer BK, Gunsel A, Wiesmuller GA, Karst U (2009) Quantification and excretion kinetics of a magnetic resonance imaging contrast agent by capillary electrophoresis-mass spectrometry. Electrophoresis 30(10):1766–1773. doi:10.1002/elps. 2008-00831
Künnemeyer J, Terborg L, Meermann B, Brauckmann C, Möller I, Scheffer A, Karst U (2009) 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):2884–2890
Raju CSK, Cossmer A, Scharf H, Panne U, Lück D (2010) 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(1):55–61
Lindner U, Lingott J, Richter S, Jakubowski N, Panne U (2013) Speciation of gadolinium in surface water samples and plants by hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry. Anal Bioanal Chem 405:1865–1873. doi:10.1007/s00216-012-6643-x
Birka M, Wehe CA, Telgmann L, Sperling M, Karst U (2013) Sensitive quantification of gadolinium-based magnetic resonance imaging contrast agents in surface waters using hydrophilic interaction liquid chromatography and inductively coupled plasma sector field mass spectrometry. J Chromatogr A 1308:125–131. doi:10.1016/j.chroma.2013.08.017
Kulaksız S, Bau M (2011) Anthropogenic gadolinium as a microcontaminant in tap water used as drinking water in urban areas and megacities. Appl Geochem 26(11):1877–1885. doi:10.1016/j.apgeochem.2011.06.011
Idee JM, Port M, Medina C, Lancelot E, Fayoux E, Ballet S, Corot C (2008) Possible involvement of gadolinium chelates in the pathophysiology of nephrogenic systemic fibrosis: a critical review. Toxicology 248(2–3):77–88. doi:10.1016/j.tox.2008.03.012
Bayer (2014) Product Monograph Magnevist. http://www.bayer.ca/files/magnevist-pm-en-07feb2014-170935.pdf
Port M, Idee JM, Medina C, Robic C, Sabatou M, Corot C (2008) Efficiency, thermodynamic and kinetic stability of marketed gadolinium chelates and their possible clinical consequences: a critical review. Biometals 21(4):469–490. doi:10.1007/s10534-008-9135-x
Baranyai Z, Palinkas Z, Uggeri F, Maiocchi A, Aime S, Brucher E (2012) Dissociation kinetics of open-chain and macrocyclic gadolinium(III)-aminopolycarboxylate complexes related to magnetic resonance imaging: catalytic effect of endogenous ligands. Chem Eur J 18(51):16426–16435. doi:10.1002/chem.201202930
Kim YH, Kim KH (2012) Ultimate detectability of volatile organic compounds: how much further can we reduce their ambient air sample volumes for analysis? Anal Chem 84(19):8284–8293. doi:10.1021/Ac301792x
Benetollo F, Bombieri G, Calabi L, Aime S, Botta M (2003) Structural variations across the lanthanide series of macrocyclic DOTA complexes: insights into the design of contrast agents for magnetic resonance imaging. Inorg Chem 42(1):148–157. doi:10.1021/Ic025790n
Tweedle MF, Hagan JJ, Kumar K, Mantha S, Chang CA (1991) Reaction of gadolinium chelates with endogenously available ions. Magn Reson Imaging 9(3):409–415. doi:10.1016/0730-725x(91)90429-P
Sarka L, Burai L, Brucher E (2000) The rates of the exchange reactions between [Gd(DTPA)](2-) and the endogenous ions Cu2+, and Zn2+: a kinetic model for the prediction of the in vivo stability of [Gd(DTPA)](2-) used as a contrast agent in magnetic resonance imaging. Chem Eur J 6(4):719–724. doi:10.1002/(Sici)1521-3765(20000218)6:4<719::Aid-Chem719>3.0.Co;2-2
Johannesson KH, Stetzenbach KJ, Hodge VF, Lyons WB (1996) Rare earth element complexation behavior in circumneutral pH groundwaters: assessing the role of carbonate and phosphate ions. Earth Planet Sci Lett 139(1–2):305–319. doi:10.1016/0012-821x(96)00016-7
Kautenburger R, Beck HP (2007) Complexation studies with lanthanides and humic acid analyzed by ultrafiltration and capillary electrophoresis-inductively coupled plasma mass spectrometry. J Chromatogr A 1159(1–2):75–80. doi:10.1016/j.chroma.2007.03.092
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Published in the topical collection Spectrochemical Plasmas for Clinical and Biochemical Analysis with guest editors Alfredo Sanz-Medel and María Montes Bayón.
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Lindner, U., Lingott, J., Richter, S. et al. 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, 2415–2422 (2015). https://doi.org/10.1007/s00216-014-8368-5
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DOI: https://doi.org/10.1007/s00216-014-8368-5