Ge isotopic equilibrium fractionation between Ge-containing ferrihydrite and the aqueous solution

Ge isotopic equilibrium fractionation between Ge-containing ferrihydrite and the aqueous solution

Peng-dong Wang

School of Earth Science and Engineering, Hebei University of Engineering, Handan 056038, China

Since Ge has a strong affinity for Fe, iron oxyhydroxide is assumed to be one of the potential “missing sinks” of Ge. Ferrihydrite is commonly found in soil and sediments and has a strong affinity for heavy metals. In this study, the first principle method based on density functional theory was used to optimize the geometry of Ge-containing ferrihydrites and H4GeO4 aqueous solution molecular clusters at B3LYP/6-311G(d) level. Solvation effects are treated by “water-droplet” method. Finally, at 298.15 K we obtained the Ge isotopic equilibrium fractionation between Ge-containing ferrihydrites and H4GeO4 aqueous solution, Δ74/70Geferrihydrite-aq= -1.97‰. It enriches the document of Ge isotopic fractionation and helps to assist the study of Ge global cycle.

Keywords: Ge isotopes; isotopic equilibrium fractionation; first-principles calculation; ferrihydrite

Free Full-text PDF

How to cite this article:

Peng-dong Wang. Ge isotopic equilibrium fractionation between Ge-containing ferrihydrite and the aqueous solution. American Journal of Basic and Applied Sciences, 2022; 5:25. DOI:10.28933/ajbas-2022-10-2505

References:

1. Bigeleisen J, Mayer M G. 1947. Calculation of Equilibrium Constants for Isotopic Exchange Reactions[J]. The Journal of chemical physics, 15(5): 261-267.
2. Blaudeau J, Mcgrath M P, Curtiss L A, Radom L. 1997. Extension of Gaussian-2 (G2) theory to molecules containing third-row atoms K and Ca[J]. The Journal of chemical physics, 107(13): 5016-5021.
3. Das B. 2018. Theoretical Study of Small Iron–Oxyhydroxide Clusters and Formation of Ferri-hydrite[J]. The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 122(2): 652-661.
4. Escoube R, Rouxel O J, Luais B, Ponzevera E, Donard O F X. 2012. An intercomparison study of the germanium isotope composition of ge-ological reference materials[J]. Geostandards and geoanalytical research, 36(2): 149-159.
5. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE Jr, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Comperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dan-nenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. 2010. Gaussian 09, Revision C.01[J].
6. Guillermic M, Lalonde S V, Hendry K R, Rouxel O J. 2017. The isotope composition of inorganic germanium in seawater and deep sea sponges [J]. Geochimica et cosmochimica acta, 212: 99-118.
7. He H, Zhang S, Zhu C, Liu Y. 2016. Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth’s surface environments[J]. Acta geo-chimica, 35(1): 15-24.
8. Ji X, Wang Y, Xing L, Liu J, Wang P, Zhang T, Zhao H. 2022. First-principle study of Ba iso-topic fractionation during ion exchange pro-cesses[J]. Acta geochimica, 41(1): 121-131.
9. Jotautas Baronas J, Hammond D E, Mcmanus J, Wheat C G, Siebert C. 2017. A global Ge isotope budget[J]. Geochimica et cosmochimica acta, 203: 265-283.
10. Li X F, Liu Y. 2010. First principles study of Ge isotope fractionation during adsorption onto Fe(III)-oxyhydroxide surfaces[J]. Chemical ge-ology, 278(1-2): 15-22.
11. Li X, Zhao H, Tang M, Liu Y. 2009. Theoretical prediction for several important equilibrium Ge isotope fractionation factors and geological implications[J]. Earth and planetary science letters, 287(1-2): 1-11.
12. Liu Q, John A T, Liu Y. 2010. On the proper use of the Bigeleisen-Mayer equation and correc-tions to it in the calculation of isotopic frac-tionation equilibrium constants[J]. Geochimica et cosmochimica acta, 74(24): 6965-6983.
13. Liu Y, Tossell J A. 2005. Ab initio molecular or-bital calculations for boron isotope fractiona-tions on boric acids and borates[J]. Geochimica et cosmochimica acta, 69(16): 3995-4006.
14. Mclean A D, Chandler G S. 1980. Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z =11–18[J]. The Journal of chemical physics, 72(10): 5639-5648.
15. Meng Y, Qi H, Hu R, Wang R, Zhou M. 2015. Determination of germanium isotopic composi-tions of sulfides by hydride generation MC-ICP-MS and its application to the Pb-Zn deposits in SW China[J]. Ore geology reviews, 65: 1095-1109.
16. Paktunc D, Manceau A, Dutrizac J, Argonne National Lab. Anl A I U S. 2013. Incorporation of Ge in ferrihydrite; implications for the structure of ferrihydrite[J]. The American mineralogist, 98(5-6): 848-858.
17. Pokrovsky O S, Galy A, Schott J, Pokrovski G S, Mantoura S. 2014. Germanium isotope frac-tionation during Ge adsorption on goethite and its coprecipitation with Fe oxy(hydr)oxides[J]. Geochimica et cosmochimica acta, 131: 138-149.
18. Qi H, O R, Hu R, Bi X, Wen H. 2011. Germanium isotopic systematics in Ge-rich coal from the Lincang Ge deposit, Yunnan, southwestern China[J]. Chemical geology, 286(3-4): 252-265.
19. Richet P, Bottinga Y, Javoy M. 1977. A review of hydrogen, carbon, nitrogen, oxygen, sulphur, and chlorine stable isotope fractionation among gaseous molecules[J]. Annual review of earth and planetary sciences, 5(1): 65-110.
20. Rosman K J R, Taylor P D P. 1998. Isotopic Compositions of the Elements 1997[J]. Journal of physical and chemical reference data, 27(6): 1275-1287.
21. Rouxel O, Galy A, Elderfield H. 2006. Germa-nium isotopic variations in igneous rocks and marine sediments[J]. Geochimica et cosmo-chimica acta, 70(13): 3387-3400.
22. Urey H C. 1947. The thermodynamic properties of isotopic substances[J]. Journal of the Chemical Society: 562-581.