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@INPROCEEDINGS{Bosbach:138581,
author = {Bosbach, Dirk and Brandt, Felix and Klinkenberg, Martina
and Rozov, Konstantin and Vinograd, Victor},
title = {{R}adium solubility control in the ${B}a{SO}_4$ –
${R}a{SO}_4$ solid-solution aqueous solution system},
reportid = {FZJ-2013-04680},
year = {2013},
abstract = {Radium is a decay product of 238U and 232Th and plays an
important role regarding the dose rate in long term safety
assessments for the direct disposal of nuclear fuel
elements. The solubility control of Ra by the formation of a
RaxBa1-xSO4 solid solution has been demonstrated in many
cases [1]. Coprecipitation leads to the formation of
structurally incorporated Radium within the barite
structure. Such solid solutions are ubiquitous in natural
systems – most minerals in nature are atomistic mixtures
of elements rather than pure compounds. In many cases the
formation of solid solutions leads to a thermodynamically
more stable situation compared to the formation of pure
compounds, due to a negative excess Gibbs energy of mixing.
However, radionuclide solubility controlled by solid
solutions is currently not considered in long term safety
assessments for a nuclear waste repository system. One
reason is related to the fact that only a limited number of
rather simple solid solution systems have been studied to a
sufficient level. Nevertheless, the thermodynamic concepts
for solid solution formation under repository relevant
conditions are very well developed. Here we have combined
microscopic and spectroscopic experimental approaches to
study in detail how a Ra containing solution will
equilibrate with solid BaSO4 under repository relevant
conditions. In combination with atomistic modeling a
molecular level mixing model has been derived. In general,
Radium solubility is significantly reduced if it is
controlled by a binary (Ra,Ba)SO4 solid solution. Atomistic
modeling indicates that a regular solid solution model may
be applied. The thermodynamic parameters for the solid
solution have been derived and can now be applied in the
safety assessment of the direct disposal of nuclear fuel
elements. Literature: [1] H. A. Doerner, $\&$ W. M. Hoskins,
(1925) Journal of the American Chemical Society, 47,
662-675},
month = {Sep},
date = {2013-09-01},
organization = {GDCh-Wissenschaftsforum Chemie 2013,
Darmstadt (Germany), 1 Sep 2013 - 4 Sep
2013},
subtyp = {Invited},
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/138581},
}