Abstract
Polynuclear species of zirconium in acidic aqueous solution are investigated by combining X-ray absorption spectroscopy (XAFS) and nanoelectrospray mass spectrometry (ESI-MS). Species distributions are measured between pHC 0 and pHC 3 for [Zr] = 1.5–10 mM. While the monomer remains a minor species, with increasing pH the degree of polymerization increases and the formation of tetramers, pentamers, octamers, and larger polymers is observed. The high resolution of the mass spectrometer permits the unambiguous determination of polynuclear zirconium hydroxide complexes by means of their isotopic patterns. The relative abundances of mononuclear and polynuclear species present simultaneously in solution are measured, even if one of the species contributes only 0.1% of the Zr concentration. For the first time it has been directly observed that the hydrolysis of polynuclear Zr species is a continuous process which leads to charge compensation through the sequential substitution of water molecules by hydroxide ligands until doubly charged polymers dominate at conditions (H+ and Zr concentrations) close to the solubility of Zr(OH)4(am). The invasiveness of the electrospray process was minimized by using very mild declustering conditions, leaving the polynuclear species within a solvent shell of approximately 20 water molecules.
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Rose J, Bruin TJMD, Chauveteau G, Tabary R, Hazemann JL, Proux O, Omari A, Toulhoat H, Bottero JY (2003) J Phys Chem B 107:2910–2920
Chiavacci LA, Santilli CV, Pulcinelli SH, Bourgaux C, Briois V (2004) Chem Mater 16:3995–4004
Curti E, Degueldre C (2002) Radiochim Acta 90:801–804
Brown P, Curti E, Grambow B, Ekberg C, Mompean F, Perrone J, Illemassene M (2005) Chemical thermodynamics of zirconium (Chemical Thermodynamics Series vol. 8). OECD/Elsevier, Amsterdam
Blumenthal W (1958) The chemical behavior of zirconium. van Nostrand, Princeton, NJ
Clearfield A, Vaughan PA (1956) Acta Crystallogr 9:555–558
Peter D, Ertel T, Bertagnolli H (1994) J Sol-Gel Sci Tec 3:91–99
Helmerich A, Raether F, Peter D, Bertagnolli H (1994) J Mat Sci 29:1388–1393
Turrilas X, Barnes P, Gascoigne JD, Turner JZ, Jones SL, Norman CJ, Pygall CF, Dent AJ (1995) Radiat Phys Chem 45:491–508
Hu MZC, Zielke JT, Lin JS, Byers CH (1999) J Mat Res 14:103–113
Southon PD, Bartlett JR, Woolfrey JL, Ben-Nissan B (2002) Chem Mat 14:4313–4319
Hagfeldt C, Kessler V, Persson I (2004) Dalton Trans 14:2142–2151
Cho H, Walther C, Rothe J, Neck V, Denecke M, Dardenne K, Fanghänel T (2005) Anal Bioanal Chem 383:28–40
Singhal A, Toth LM, Lin JS, Affholter K (1996) J Am Chem Soc 118:11529–11534
Connick RE, Reas WH (1951) J Am Chem Soc 73:1171–1176
Zielen A, Connick R (1956) J Am Chem Soc 78:5785–5792
Pokras L (1956) J Chem Edu 33:152–161
Tribalat S, Schriver L (1975) Bull Soc Chim Fr 9:2012–2014
Tulock JJ, Blanchard GJ (2002) J Phys Chem B 106:3568–3575
Johnson JS, Kraus KA (1956) J Am Chem Soc 78:3937–3943
Angstadt R, Tyree S (1962) J Inorg Nucl Chem 24:913–917
Bilinski H, Branica M, Sillen L (1966) Acta Chem Scand 20:853–861
Bertin F, Bouix J, Hannane S, Paris J (1987) R Acad Sci Ser II 304:405–410
Aberg M, Glaser J (1993) Inorg Chim Acta 206:53–61
Veyland A (1999) Propriétés thermodynamiques, cinétiques et structurales de complexes simples et mixtes du zirconium(IV) avec les ions hydroxyle et carbonate. Ph.D. thesis, Univ. Reims Champagne-Ardenne
Dole M, Mack L, Hines R, Mobley R, Ferguson L, Alice M (1968) J Chem Phys 49:2240–2249
Yamashita M, Fenn J (1984) J Phys Chem 88:4451–4459
Fenn J (2002) J Biomol Tech 13:101–118
Cole R (1997) Electrospry ionization mass spectrometry. Wiley, New York
Pramanik B, Ganguly A, Gross M (2002) Applied electrospray mass spectrometry. Marcel Dekker, New York
Agnes GR, Horlick G (1995) Appl Spectr 49:324–334
Rosen AL, Hieftje GM (2004) Spectrochim Acta B 59:135–146
Gross J (2004) Mass spectrometry: a textbook. Springer, Berlin
Stewart I (1999) Spectrochim Acta B 54:1649–1695
Stewart I, Horlick G (1996) J Anal Atom Spectrosc 11:1203–1214
Rodriguez-Cruz S, Jockusch R, Williams E (1999) J Am Chem Soc 121:8898–8906
Sarpola A, Hietapelto V, Jalonen J, Jokela J, Laitinen RS, Ramo J (2004) J Mass Spectr 39:1209–1218
Sarpola A, Hietapelto V, Jalonen J, Jokela J, Laitinen RS (2004) J Mass Spectr 39:423–430
Hellmann H, Laitinen RS, Kaila L, Jalonen J, Hietapelto V, Jokela J, Sarpola A, Rämö J (2006) J Mass Spect 41:1421–1429
Peschke M, Blades AT, Kebarle P (1999) Int J Mass Spectr 187:685–699
Blades AT, Peschke M, Verkerk UH, Kebarle P (2004) J Am Chem Soc 126:11995–12003
Hartke B, Charvat A, Reich M, Abel B (2002) J Chem Phys 116:3588–3600
Moulin C (2003) Radiochim Acta 91:651–657
Plancque G, Maurice Y, Moulin V, Toulhoat P, Moulin C (2005) Appl Spectr 59:432–441
Vercouter T, Amekraz B, Moulin C, Giffaut E, Vitorge P (2005) Inorg Chem 44:7570–7581
Moulin C, Charron N, Plancque G, Virelizier H (2000) Appl Spectr 54:843–848
Moulin C, Amekraz B, Hubert S, Moulin V (2001) Anal Chim Acta 441:269–279
Moulin C, Amekraz B, Colette S, Doizi D, Jacopin C, Lamouroux C, Plancque G (2006) J Alloys Comp 408:1242–1245
Lamouroux C, Moulin C, Tabet JC, Jankowski CK (2000) Rapid Comm Mass Spectr 14:1869–1877
Veyland A, Dupont L, Pierrard JC, Rimbault J, Aplincourt M, Devoldere L (2000) Inorg Chem Comm 3:600–607
Lover T, Henderson W, Bowmaker GA, Seakins JM, Cooney RP (1997) J Mat Chem 7:1553–1558
Bergmann T, Martin TP, Schaber H (1989) Rev Sci Instrum 60:347–349
Bergmann T, Martin TP, Schaber H (1990) Rev Sci Instrum 61:2592–2600
Bergmann T, Goehlich H, Martin TP, Schaber H, Malegiannakis G (1990) Rev Sci Instrum 61:2585–2591
Denecke MA, Dardenne K, Marquardt CM (2005) Talanta 65:1008–1014
Sayers D, Bunker B (1988) In: Koningsberger DC, Prins R (eds) X-ray absorption: techniques of EXAFS, SEXAFS and XANES. Wiley, New York, pp 211–253
Ravel B, Newville M (2006) EXAFS analysis software: ATHENA. Accessed 13 March 2007. http://cars9.uchicago.edu/~ravel/software/aboutathena.html
Stern EA, Newville M, Ravel B, Yacoby Y, Haskel D (1995) Physica B 209:117–120
Mak C (1967) Can J Chem 46:3491–3497
Ankudinov AL, Ravel B, Rehr JJ, Conradson SD (1998) Phys Rev B 58:7565–7576
Ankudinov AL, Rehr JJ (1997) Phys Rev B 56:1712–1728
Lee P, Citrin P, Eisenberger P, Kincaid B (1981) Rev Mod Phys 53:769–806
Kovalenko P, Bagdasarov K (1961) Russ J Inorg Chem 6:272–275
Adair J, Denkewicz R, Arriagada F (1987) Ceramic Trans 1:135–145
Ekberg C, Kallvenius G, Albinsson Y, Brown PL (2004) J Sol Chem 33:47–79
Muha GM, Vaughan PA (1960) J Chem Phys 33:194–199
Li P, Chen IW, Pennerhahn JE (1993) Phys Rev B 48:10063–10073
Rothe J, Walther C, Denecke MA, Fanghänel T (2004) Inorg Chem 43:4708–4718
Conradson SD, Begg BD, Clark DL, den Auwer C, Ding M, Dorhout PK, Espinosa-Faller FJ, Gordon PL, Haire RG, Hess NJ, Hess RF, Keogh DW, Lander GH, Manara D, Morales LA, Neu MP, Paviet-Hartmann P, Rebizant J, Rondinella VV, Runde W, Tait CD, Veirs DK, Villella PM, Wastin F (2005) J Solid State Chem 178:521–535
Iribarne J, Thomson B (1976) J Chem Phys 64:2287–2294
Zhou SL, Cook KD (2000) Anal Chem 72:963–969
Wilm M, Mann M (1996) Anal Chem 68:1–8
Wortmann A, Kister-Momotova A, Wilhelm O, Zenobi R (2005) In: ANAKON 05, 15–18 March 2005, Regensburg, Germany
Neck V, Kim JI (2001) Radiochim Acta 89:1–16
Zhou SL, Edwards AG, Cook KD, Van Berkel GJ (1999) Anal Chem 71:769–776
Zhou SL, Prebyl BS, Cook KD (2002) Anal Chem 74:4885–4888
Van Berkel GJ, Asano KG, Schnier PD (2001) J Am Soc Mass Spectr 12:853–862
Grenthe I, Wanner H, Östhols E (2000) Guidelines for the extrapolation to zero ionic strength (Chemical Thermodynamics Series vol. 2). Elsevier, Amsterdam
Metivier H, Guillaumont R (1972) Radiochem Radioanal Lett 10:27–35
Baes CF, Mesmer RE (1976) The hydrolysis of cations. Wiley, New York
Moriyama H, Sasaki T, Kobayashi T, Takagi I (2005) J Nucl Sci Tech 42:626–635
Moriyama H, Sasaki T, Kobayashi T, Takagi I (2006) J Alloys Comp 408:1302–1306
Nabivanets B (1962) Russ J Inorg Chem 7:609–611
Lister B, McDonald L (1952) J Chem Soc 4315–4330
Sasaki T, Kobyashi T, Takagi I, Moriyama H (2006) Radiochim Acta 94:489–494
Schindler P, Althau H, Hofer F, Minder W (1965) Helvet Chim Acta 48:1204–1215
Schindler P (1967) Adv Chem Ser 67:196–221
Sasaki T, Kobayashi T, Takagi I, Moriyama H (2005) In: Actinides 2005—Recent Advances in Actinide Science, 4–8 July 2005, Manchester, UK
Ciavatta L (1980) Ann Chim (Rome) 70:551–562
Grenthe I, Fuger J, Konings R, Lemire R, Muller A, Nguyen-Trung C, Wanner H (1992) Chemical thermodynamics of uranium (Chemical Thermodynamics Series, vol. 1). OECD/Elsevier, Amsterdam
Neck V, Kim J, Seidel B, Marquardt C, Dardenne K, Jensen M, Hauser W (2001) Radiochim Acta 89:439–446
Neck V, Kim JI (2000) Radiochim Acta 88:815–822
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Walther, C., Rothe, J., Fuss, M. et al. Investigation of polynuclear Zr(IV) hydroxide complexes by nanoelectrospray mass-spectrometry combined with XAFS. Anal Bioanal Chem 388, 409–431 (2007). https://doi.org/10.1007/s00216-007-1223-1
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DOI: https://doi.org/10.1007/s00216-007-1223-1