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@INPROCEEDINGS{Brandt:138578,
author = {Brandt, Felix and Klinkenberg, Martina and Vinograd, Victor
and Rozov, Konstantin and Bosbach, Dirk},
title = {{S}olid solution formation and uptake of {R}adium in the
presence of barite},
reportid = {FZJ-2013-04677},
year = {2013},
abstract = {The phase relations in the BaSO4-RaSO4-H2O system may
determine the solubility of radium in natural waters due to
the formation of a solid solution. In the near-field of
nuclear waste repositories for spent fuel, radium may enter
a system in which barite is in equilibrium with the aqueous
solution. Thermodynamically, a RaxBa1-xSO4 solid solution is
expected to form as solubility controlling phase rather than
RaSO4. However, due to a lack of reliable data, the solid
solution system RaSO4-BaSO4-H2O is currently not considered
in long term safety assessments for nuclear waste
repositories. The solubility product of the pure RaSO4
endmember is poorly constrained between pKRaSO4 = 10.26 to
10.41 by only very few experimental data [1,2]. Published
interaction parameters WBaRa of the RaSO4-BaSO4-H2O system
varies varies in different studies [3, 4] between 0.9 and
3.9 - 6.5 kJ/mol. In this study we have combined
experimental data, atomistic calculations and thermodynamic
modeling to study in detail how a radium containing solution
will equilibrate with solid BaSO4 under repository relevant
conditions. Batch sorption experiments at close to
equilibrium conditions indicate the formation of a
RaxBa1-xSO4 solid. Our first principles calculations based
on the single defect method [5] indicate a value of WBaRa =
2.5 ± 1.0 kJ/mol, implying a non-ideal solid solution.
Thermodynamic assessment calculations indicate that the
final experimental Ra(aq) concentration at room temperature
and 90 °C can be matched with WBaRa ≈ 1.5 kJ/mol and
pKRaSO4 ≈ 10.41. [1] Lind, S. C., et al (1918). J Am Chem
Soc 40, 465-472. [2] Paige, C. R. et al.(1998). Geochim.
Cosmochim. Acta 62, 15-23. [3] Zhu, C., 2004. Geochim.
Cosmochim. Acta 68, 3327-3337. [4] Curti, E., et al. (2010).
Geochim. Cosmochim. Acta 74, 3553-3570. [5] Sluiter $\&$
Kawazoe (2002) Europhys Lett. 57, 526-532.},
month = {Aug},
date = {2013-08-25},
organization = {Goldschmidt Conference 2013, Firenze
(Italy), 25 Aug 2013 - 30 Aug 2013},
subtyp = {Other},
cin = {IEK-6},
cid = {I:(DE-Juel1)IEK-6-20101013},
pnm = {142 - Safety Research for Nuclear Waste Disposal (POF2-142)
/ SKIN - Slow processes in close-to-equilibrium conditions
for radionuclides in water/solid systems of relevance to
nuclear waste management (269688)},
pid = {G:(DE-HGF)POF2-142 / G:(EU-Grant)269688},
typ = {PUB:(DE-HGF)6},
url = {https://juser.fz-juelich.de/record/138578},
}