Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. II: insights from STEM-EDXS and DFT calculations
- 473 Downloads
Transformation products of two-line ferrihydrite associated with Lu(III) were studied after 12 years of aging using aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), high-efficiency energy-dispersive X-ray spectroscopy (EDXS), and density functional theory (DFT). The transformation products consisted of hematite nanoparticles with overgrown goethite needles. High-efficiency STEM-EDXS revealed that Lu is only associated with goethite needles, and atomic-resolution HAADF-STEM reveals structural incorporation of Lu within goethite, partially replacing structural Fe sites. This finding corroborates those recently obtained by AsFlFFF and EXAFS spectroscopy on the same sample (Finck et al. 2018). DFT calculations indicate that Lu incorporation within goethite or hematite are almost equally likely, suggesting that experimental parameters such as temperature and reaction time which affect reaction kinetics, play important roles in determining the Lu uptake. It seems likely that these results may be transferable to predict the behavior of chemically homologous trivalent actinides.
KeywordsTwo-line ferrihydrite Lutetium Transformation products Hematite Goethite Incorporation STEM-EDXS DFT
The authors would like to thank D. Wang at Karlsruhe Institute of Technology for useful discussions. S.J.H. acknowledges support from EPSRC (EP/M010619/1 and EP/K016946/1) and NNUMAN.
- Bouby M, Geckeis H, Manh TN, Yun JI, Dardenne K, Schäfer T, Walter C, Kim JI (2004) Laser-induced breakdown detection combined with asymmetrical flow field-flow fractionation: application to iron oxi/hydrooxide colliod characterization. J Chromatogr A 1040:97–104. https://doi.org/10.1016/j.chroma.2004.03.047 CrossRefGoogle Scholar
- Finck N, Bouby M, Dardenne K (2018) 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. https://doi.org/10.1007/s11356-018-1314-x
- Hazemann JL, Bérar J, Manceau A (1991) Rietveld studies of the aluminium-iron substitution in synthetic goethite. Mater Sci Forum 79-82:821–826. https://doi.org/10.4028/www.scientific.net/MSF.79-82.821 CrossRefGoogle Scholar
- Kresse G, Marsman M, Furthmüller J (2016) VASP the GUIDE Available at: https://cms.mpi.univie.ac.at/vasp/vasp/vasp.html
- Schlossmacher P, Klenov DO, Freitag B, von Harrach S, Steinbach A (2010) Nanoscale chemical compositional analysis with an innovative S/TEM-EDX system. Microsc Anal Nanotechnol Suppl S5–S8Google Scholar
- Schwertmann U, Cornell RM (1991) Iron oxides in the laboratory. Preparation and characterization. VCH Verlagsgesellschaft mbH: Weinheim, Germany; VCH Publishers, Inc.: New York, USA. https://doi.org/10.1002/9783527613229
- 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 CrossRefGoogle Scholar
- Tertre E, Berger G, Simoni E, Castet S, Giffaut E, Loubet M, Catalette H (2006) Europium retention onto clay minerals from 25 to 150°C. Experimental measurements, spectroscopic features and sorption modelling. Geochim Cosmochim Acta 70:4563–4578. https://doi.org/10.1016/j.gca.2006.06.1568 CrossRefGoogle Scholar
- TURBOMOLE, TURBOMOLE V7.0 (2015) A development of University of Karlsruhe and Forschungszentrum Karlsruhe GmbH, 1989-2007, TURBOMOLE GmbH, since 2007; available from http://www.turbomole.com
- Utsunomiya S, Ewing RC (2003) Application of high-angle annular dark field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive X-ray spectrometry, and energy-filtered transmission electron microscopy to the characterization of nanoparticles in the environment. Environ Sci Technol 37:786–791. https://doi.org/10.1021/es026053t CrossRefGoogle Scholar
- Varela M, Lupini AR, van Benthem K, Borisevich AY, Chisholm MF, Shibata N, Abe E, Pennycook SJ (2005) Materials characterization in the aberration-corrected scanning transmission electron microscope. Annu Rev Mater Res 35:539–569. https://doi.org/10.1146/annurev.matsci.35.102103.090513 CrossRefGoogle Scholar