Abstract
Two-line ferrihydrite (2LFh) was aged for 12 years under ambient conditions and sheltered from light in the presence of Lu(III) used as surrogate for trivalent actinides. 2LFh aging produced hematite rhombohedra with overgrown acicular goethite particles. Analysis of the homogeneous suspension by asymmetrical flow field-flow fractionation (AsFlFFF) coupled to ICP-MS indicated that particles have a mean hydrodynamic diameter of about 140 nm and the strong correlation of the Fe and Lu fractograms hinted at a structural association of the lanthanide with the solid phase(s). Unfortunately, recoveries were low and thus results cannot be considered representative of the whole sample. The suspension was centrifuged and X-ray absorption spectroscopy (XAS) at the Lu L3-edge on the settled particles indicated that Lu(III) is sixfold coordinated by oxygen atoms, pointing to a retention by structural incorporation within particles. This result is consistent with AsFlFFF results on the same suspension without centrifugation. The detection of next nearest Fe and O atoms were consistent with the structure of goethite, ruling out incorporation within hematite. After centrifugation of the suspension, only nanoparticulate needle-like particles, very likely goethite, could be detected in the supernatant by ESEM. AsFlFFF data of the supernatant were comparable to that obtained for the homogeneous suspension, whereas XAS indicated that Lu(III) is predominantly present as dissolved species in the supernatant. Results from both techniques can be interpreted as a major fraction of Lu present as aqueous ions and a minor fraction as structurally incorporated. Findings from this study are corroborated by STEM-HAADF data and results from DFT calculations in a companion paper.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ankudinov AL, Ravel B, Rehr JJ, Conradson SD (1998) Real-space multiple-scattering calculations and interpretation of x-ray-absorption near-edge structure. Phys Rev B 58(12):7565–7576. https://doi.org/10.1103/PhysRevB.58.7565
Bianconi A, Dell’Ariccia M, Gargano A, Natoli CR (1983) Bond length determination using XANES. In: Bianconi A, Incoccia L, Stipcich S (eds) EXAFS and near edge structure. Springer-Verlag, Berlin, pp 57–61. https://doi.org/10.1007/978-3-642-50098-5_8
Bots P, Shaw S, Law GTW, Marshall TA, Mosselmans JFW, Morris K (2016) Controls on the fate and speciation of Np(V) during iron (oxyhydr)oxide crystallization. Environ Sci Technol 50(7):3382–3390. https://doi.org/10.1021/acs.est.5b05571
Bouby M, Geckeis H, Manh TN, Yun JI, Dardenne K, Schafer T, Walther C, Kim JI (2004) Laser-induced breakdown detection combined with asymmetrical flow field-flow fractionation: application to iron oxi/hydroxide colloid characterization. J Chromatogr A 1040(1):97–104. https://doi.org/10.1016/j.chroma.2004.03.047
Bouby M, Geckeis H, Geyer FW (2008) Application of asymmetric flow field-flow fractionation (AsFlFFF) coupled to inductively coupled plasma mass spectrometry (ICPMS) to the quantitative characterization of natural colloids and synthetic nanoparticles. Anal Bioanal Chem 392(7-8):1447–1457. https://doi.org/10.1007/s00216-008-2422-0
Bouby M, Geckeis H, Lutzenkirchen J, Mihai S, Schäfer T (2011) Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: a flow field-flow fractionation study. Geochim Cosmochim Acta 75(13):3866–3880. https://doi.org/10.1016/j.gca.2011.04.015
Bouby M, Finck N, Geckeis H (2012) Flow field-flow fractionation (FlFFF) coupled to sensitive detection techniques: a way to examine radionuclide interactions with nanoparticles. Mineral Mag 76(7):2709–2721. https://doi.org/10.1180/minmag.2012.076.7.06
Bouby M, Finck N, Geckeis H (2015) Synthetic smectites colloids: characterization of nanoparticles after co-precipitation in the presence of lanthanides and tetravalent elements (Zr, Th). Chromatography 2(3):545–566. https://doi.org/10.3390/chromatography2030545
Boudeulle M, Muller JP (1988) Structural characteristics of hematite and goethite and their relationships with kaolinite in a laterite from Cameroon—a TEM study. Bull Mineral 111:149–166
Carlson L, Schwertmann U (1981) Natural ferrihydrites in surface deposits from Finland and their association with silica. Geochim Cosmochim Acta 45(3):421–429. https://doi.org/10.1016/0016-7037(81)90250-7
Chivot J (2004) Thermodynamique des produits de corrosion : Fonctions thermodynamiques, diagrammes de solubilité, diagrammes E-pH des systèmes Fe-H2O, Fe-CO2-H2O, Fe-S-H2O, Cr-H2O et Ni-H2O en fonction de la température. ANDRA, Châtenay-Malabry
Cornell RM (1985) Effect of simple sugars on the alkaline transformation of ferrihydrite into goethite and hematite. Clays Clay Min 33(3):219–227. https://doi.org/10.1346/CCMN.1985.0330308
Cornell RM, Schwertmann U (1996) The iron oxides: structure, properties, reactions, occurrences and uses. VCH, Weinheim
Cornell RM, Giovanoli R, Schindler PW (1987) Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkalin media. Clays Clay Min 35(1):21–28. https://doi.org/10.1346/CCMN.1987.0350103
Cornell RM, Giovanoli R, Schneider W (1989) Review of the hydrolysis of iron(III) and the crystallization of amorphous iron(III) hydroxide hydrate. J Chem Technol Biotechnol 46:115–134
Cornell RM, Schneider W, Giovanoli R (1992) The effect of nickel on the conversion of amorphous iron(III) hydroxide into more crystalline iron-oxides in alkaline media. J Chem Technol Biotechnol 53:73–79
Cudennec Y, Lecerf A (2006) The transformation of ferrihydrite into goethite end hematite, revised J. Solid State Chem 179(3):716–722. https://doi.org/10.1016/j.jssc.2005.11.030
Dardenne K, Schafer T, Denecke MA, Rothe J, Kim JI (2001) Identification and characterization of sorbed lutetium on 2-line ferrihydrite by sorption data modeling. TRLFS EXAFS Radiochim Acta 89(7):469–479. https://doi.org/10.1524/ract.2001.89.7.469
Dardenne K, Schafer T, Lindqvist-Reis P, Denecke MA, Plaschke M, Rothe J, Kim JI (2002) Low temperature XAFS investgations on the lutetium binding changes during the 2-line ferrihydrite alteration process. Environ Sci Technol 36(23):5092–5099. https://doi.org/10.1021/es025513f
Finck N, Schlegel ML, Bosbach D (2009) Sites of Lu(III) sorbed to and coprecipitated with hectorite. Environ Sci Technol 43(23):8807–8812. https://doi.org/10.1021/es901940v
Finck N, Bouby M, Dardenne K, Geckeis H (2012) Characterization of Eu(III) co-precipitated with and adsorbed on hectorite: from macroscopic crystallites to nanoparticles. Mineral Mag 76(7):2723–2740. https://doi.org/10.1180/minmag.2012.076.7.07
Finck N, Nedel S, Dideriksen K, Schlegel ML (2016) Trivalent actinide uptake by iron (hydr)oxides. Environ Sci Technol 50(19):10428–10436. https://doi.org/10.1021/acs.est.6b02599
Ford RG, Bertsch PM, Farley KJ (1997) Changes in transition and heavy metal partitioning during hydrous iron oxide aging. Environ Sci Technol 31(7):2028–2033. https://doi.org/10.1021/es960824+
Freyria FS, Barrera G, Tiberto P, Belluso E, Levy D, Saracco G, Allia P, Garrone E, Bonelli B (2013) Eu-doped alpha-Fe2O3 nanoparticles with modified magnetic properties. J Solid State Chem 201:302–311. https://doi.org/10.1016/j.jssc.2013.03.018
Giddings JC (1993) Field-flow fractionation: analysis of macromolecular, colloidal, and particulate materials. Science 260(5113):1456–1465. https://doi.org/10.1126/science.8502990
Giddings JC, Yang FJ, Myers MN (1976) Theoretical and experimental characterization of flow field-flow fractionation. Anal Chem 48(8):1126–1132. https://doi.org/10.1021/ac50002a016
Hazemann JL, Berar JF, Manceau A (1991) Rietveld studies of the aluminium-iron substitution in synthetic goethite. Mater Sci Forum 79:821–826. https://doi.org/10.4028/www.scientific.net/MSF.79-82.821
Heberling F, Vinograd VL, Polly R, Gale JD, Heck S, Rothe J, Bosbach D, Geckeis H, Winkler B (2014) A thermodynamic adsorption/entrapment model for selenium(IV) coprecipitation with calcite. Geochim Cosmochim Acta 134:16–38. https://doi.org/10.1016/j.gca.2014.02.044
Hiemstra T, Van Riemsdijk WH (2009) A surface structural model for ferrihydrite I: sites related to primary charge, molar mass, and mass density. Geochim Cosmochim Acta 73(15):4423–4436. https://doi.org/10.1016/j.gca.2009.04.032
Huber F, Enzmann F, Wenka A, Bouby M, Dentz M, Schafer T (2012) Natural micro-scale heterogeneity induced solute and nanoparticle retardation in fractured crystalline rock. J Contam Hydrol 133:40–52. https://doi.org/10.1016/j.jconhyd.2012.03.004
Jambor JL, Dutrizac JE (1998) Occurrence and constitution of natural and synthetic ferrihydrite, a widespread iron oxyhydroxide. Chem Rev 98(7):2549–2586. https://doi.org/10.1021/cr970105t
Lion LW, Altmann RS, Leckie JO (1982) Trace-metal adsorption characteristics of estuarine particulate matter: evaluation of contributions of iron/manganese oxide and organic surface coatings. Environ Sci Technol 16(10):660–666. https://doi.org/10.1021/es00104a007
Lu N, Kung KS, Mason CFV, Triay IR, Cotter CR, Pappas AJ, Pappas MEG (1998) Removal of plutonium-239 and americium-241 from Rocky Flats soils by leaching. Environ Sci Technol 32(3):370–374. https://doi.org/10.1021/es970329t
Marshall TA, Morris K, Law GTW, Livens FR, Mosselmans JFW, Bots P, Shaw S (2014) Incorporation of uranium into hematite during crystallization from ferrihydrite. Environ Sci Technol 48(7):3724–3731. https://doi.org/10.1021/es500212a
Maslen EN, Streltsov VA, Streltsova NR, Ishizawa N (1994) Synchrotron X-ray study of the electron density in α-Fe2O3. Acta Crystallogr B 50(4):435–441. https://doi.org/10.1107/S0108768194002284
Nagano T, Mitamura H, Nakayama S, Nakashima S (1999) Formation of goethite and hematite from neodymium-containing ferrihydrite suspensions. Clays Clay Min 47(6):748–754. https://doi.org/10.1346/CCMN.1999.0470609
Ngo Manh T, Geckeis H, Kim JI, Beck HP (2001) Application of the flow field flow fractionation (FFFF) to the characterization of aquatic humic colloids: evaluation and optimization of the method. Colloids Surf A Physicochem Eng Asp 181(1-3):289–301. https://doi.org/10.1016/S0927-7757(00)00803-7
Novikov AP, Kalmykov SN, Utsunomiya S, Ewing RC, Horreard F, Merkulov A, Clark SB, Tkachev YY, Myasoedov BF (2006) Colloid transport of plutonium in the far-field of the Mayak production association, Russia. Science 314(5799):638–641. https://doi.org/10.1126/science.1131307
Ohta A, Kagi H, Nomura M, Tsuno H, Kawabe I (2009) Coordination study of rare earth elements on Fe oxyhydroxide and Mn dioxides: part II. Correspondence of structural change to irregular variations of partitioning coefficients and tetrad effect variations appearing in interatomic distances. Am Mineral 94(4):476–486. https://doi.org/10.2138/am.2009.2987
Persson I, D'Angelo P, De Panfilis S, Sandstrom M, Eriksson L (2008) Hydration of lanthanoid(III) ions in aqueous solution and crystalline hydrates studied by EXAFS spectroscopy and crystallography : the myth of the « gadolinium break ». Chem Eur J 14(10):3056–3066. https://doi.org/10.1002/chem.200701281
Phelan FR Jr, Bauer BJ (2007) Simulation of nanotube separation in field-flow fractionation (FFF). Chem Eng Sci 62(17):4620–4635. https://doi.org/10.1016/j.ces.2007.04.019
Phelan FR Jr, Bauer BJ (2009) Comparison of steric effects in the modeling of sphere and rodlike particles in field-flow fractionation. Chem Eng Sci 64(8):1747–1758. https://doi.org/10.1016/j.ces.2008.10.006
Qi Z, Liu M, Chen Y, Zhang G, Xu M, Shi C, Zhang W, Yin M, Xie Y (2007) Local structure of nanocrystalline Lu2O3:Eu studied by X-ray absorption spectroscopy. J Phys Chem C 111(5):1945–1950. https://doi.org/10.1021/jp066937p
Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Radiat 12(4):537–541. https://doi.org/10.1107/S0909049505012719
Rothe J, Butorin S, Dardenne K, Denecke MA, Kienzler B, Loble M, Metz V, Seibert A, Steppert M, Vitova T, Walther C, Geckeis H (2012) The INE-beamline for actinide science at ANKA. Rev Sci Instrum 83(4):043105. https://doi.org/10.1063/1.3700813
Schäfer T, Artinger R, Dardenne K, Bauer A, Schuessler W, Kim JI (2003) Colloid-borne americium migration in Gorleben groundwater: significance of iron secondary phase transformation. Environ Sci Technol 37(8):1528–1534. https://doi.org/10.1021/es015832r
Schimpf ME, Caldwell K, Giddings JC (2000) Field-flow fractionation handbook. Wiley-Interscience, John Wiley & Sons, New York ISBN: 978-0471184300
Schmidt M, Stumpf T, Marques Fernandes M, Walther C, Fanghänel T (2008) Charge compensation in solid solutions. Angew Chem Int Ed 47(31):5846–5850. https://doi.org/10.1002/anie.200705827
Schwertmann U, Cornell RM (1991) Iron oxides in the laboratory. Preparation and characterization. VCH, Weinheim
Schwertmann U, Murad E (1983) Effect of pH on the formation of goethite and hematite from ferrihydrite. Clays Clay Min 31(4):277–284. https://doi.org/10.1346/CCMN.1983.0310405
Shannon RD (1976) Revised effective ionic radii and systemaic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 32(5):751–767. https://doi.org/10.1107/S0567739476001551
Sharma V, Park K, Srinivasarao M (2009) Shape separation of gold nanorods using centrifugation. Proc Natl Acad Sci 106(13):4981–4985. https://doi.org/10.1073/pnas.0800599106
Stegemeier JP, Reinsch BC, Lentini CJ, Dale JG, Kim CS (2015) Aggregation of nanoscale iron oxyhydroxides and corresponding effect on metal uptake, retention, and speciation: II. Temperature and time. Geochim Cosmochim Acta 148:113–129. https://doi.org/10.1016/j.gca.2014.08.031
Stumpf S, Stumpf S, Dardenne K, Hennig C, Foerstendorf H, Klenze R, Fanghänel T (2006) Sorption of Am(III) onto 6-line ferrihydrite and its alteration products: investigations by EXAFS. Environ Sci Technol 40(11):3522–3528. https://doi.org/10.1021/es052518e
Sun T, Paige CR, Snodgrass WJ (1996) The effect of cadmium on the transformation of ferrihydrite into crystalline products at pH 8. Water Air Soil Pollut 91(3-4):307–325. https://doi.org/10.1007/BF00666266
Wahlund KG, Giddings JC (1987) Properties of an asymmetrical flow field-flow fractionation channel having one permeable wall. Anal Chem 59(9):1332–1339. https://doi.org/10.1021/ac00136a016
Wijnhoven JEGJ, Koorn JP, Poppe H, Kok WT (1996) Influence of injected mass and ionic strength on retention of water-soluble polymers and proteins in hollow-fibre flow field-flow fractionation. J Chromatogr A 732(2):307–315. https://doi.org/10.1016/0021-9673(95)01263-X
Yokosawa T, Prestat E, Polly R, Bouby M, Dardenne K, Finck N, Haigh SJ, Denecke MA, Geckeis H (2018) Fate of Lu(III) sorbed on 2-lin ferrihydrite at pH 5.7 and aged for 12 years at room temperature. II: insights from STEM-EDXS and DFT calculations. Environ Sci Pollut Res (In this issue)
Acknowledgements
We thank S. Heck (KIT-INE) for ICP-OES, F. Geyer (KIT-INE) for ICP-MS analyses, and E. Soballa (KIT-INE) for SEM measurements. We acknowledge the synchrotron light source ANKA (Karlsruhe, Germany) for the provision of synchrotron radiation beamtime.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Responsible editor: Georg Steinhauser
Rights and permissions
About this article
Cite this article
Finck, N., Bouby, M. & Dardenne, K. Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES, XRD, ESEM, AsFlFFF/ICP-MS, and EXAFS spectroscopy. Environ Sci Pollut Res 26, 5238–5250 (2019). https://doi.org/10.1007/s11356-018-1314-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-018-1314-x