% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Brandt:202213,
author = {Brandt, F. and Curti, E. and Klinkenberg, M. and Rozov, K.
and Bosbach, D.},
title = {{R}eplacement of barite by a ({B}a,{R}a){SO}4 solid
solution at close-to-equilibrium conditions: {A} combined
experimental and theoretical study},
journal = {Geochimica et cosmochimica acta},
volume = {155},
issn = {0016-7037},
address = {New York, NY [u.a.]},
publisher = {Elsevier},
reportid = {FZJ-2015-04502},
pages = {1 - 15},
year = {2015},
abstract = {Solid solution formation between RaSO4 and BaSO4 has long
been recognized as a process which potentially controls the
Raconcentration in the environment. Here, we have
systematically studied the replacement of pure barite by a
(Ba,Ra)SO4 solidsolution in 0.1 M NaCl through batch
experiments extending up to 883 days at close-to-equilibrium
(CTE) conditions, whichare relevant to disposal of nuclear
waste in a deep geological repository. Kinetic and
thermodynamic models were applied tosupport the
interpretation of the experiments, which were carried out at
room temperature and at two distinct solid/liquid ratio(0.5
or 5 g/L). Different stages of recrystallization were
observed, based on the rate of removal of Ra from aqueous
solution.After a first slow kinetic step, a change in the
slope of the aqueous Ra concentration vs. time is observed,
suggesting nucleationof a new (Ba,Ra)SO4 phase from
supersaturation. If this stage was considered to reflect
equilibrium between aqueous and solidsolution, one would
infer ideality or even negative interaction parameters (a0 6
0). After this fast nucleation step, in the 0.5
g/Lexperiments the Ra concentrations in the aqueous solution
slowly increase, approaching a concentration close to that
requiredfor equilibrium with a regular (Ba,Ra)SO4 solid
solution with an interaction parameter a0 = 1.0. Therefore,
these data suggest anon-equilibrium Ra entrapment during the
nucleation phase of the replacement, followed by slow
recrystallization toward truethermodynamic solid solution
equilibrium. Moreover, an interaction parameter value of a0
= 1.0 was inferred from our experiments,which is in good
agreement with theoretical predictions from atomistic
simulations.A key result from this study is that aqueous
solution and binary (Ba,Ra)SO4 approach full thermodynamic
equilibriumwithin laboratory time scales (2.5 years). This
justifies assuming complete thermodynamic equilibrium for
this system in geochemicalcalculations of processes
occurring on geological time scales. This finding is of
direct relevance for the safety assessmentof radioactive
waste disposal, since it may constrain the solubility and
thus the mobility of Ra in such environments.},
cin = {IEK-6},
ddc = {550},
cid = {I:(DE-Juel1)IEK-6-20101013},
pnm = {161 - Nuclear Waste Management (POF3-161) / 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)POF3-161 / G:(EU-Grant)269688},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000351732800001},
doi = {10.1016/j.gca.2015.01.016},
url = {https://juser.fz-juelich.de/record/202213},
}