『Abstract
Dissolution rates of calcite, dolomite and magnesite were measured
at 25℃ and pH from 3 to 4 as a function of salinity (0.001 M≦[NaCl]≦1
M) and partial pressure of CO2 (10-3.5≦p
CO2≦55 atm) Experiments on calcite and
dolomite crystal planes dissolution were performed i a batch reactor
under controlled hydrodynamic conditions using the rotating disk
technique. Dissolution experiments using mixed-flow reactors were
also conducted on calcite and dolomite powders of 100-200μm. Magnesite
dissolution rates were measured using a batch titanium high-pressure
reactor on 100-200μm powders. The pH was measured in-situ using
a solid-contact electrode in a cell without liquid junction. At
pH〜4.0 and constant hydrodynamic conditions pH-independent calcite
dissolution rate increases by a factor of 3 from 1 to 〜20 atm
p CO2 and stays constant at 25 to
50 atm. These rates do not depend on NaCl concentration from 0.01
to 1.0 M and pH of 4 to 8. Calcite dissolution rates depend strongly
on stirring between 200 and 2000 rpm at 2, 10, and 50 atm p
CO2 suggesting mass transport control at
these conditions. Both for polycrystalline samples and cleavage
planes, dolomite dissolution rate increases with increasing p
CO2 at 1≦p CO2≦10
atm and stays constant when p CO2 is
further increased to 50 atm. These rates depend on stirring velocity
and increases by a factor of 2-3 from 200 to 2500 rpm reflecting
moderate transport contribution to dissolution at these conditions.
Within the experimental uncertainty, dolomite dissolution rates
are independent of ionic strength between 0.1 and 1 M NaCl and
5 to 50 atm p CO2. This is also confirmed
by powder dissolution experiments performed in mixed-flow reactors.
Magnesite dissolution rate increases by a factor of 3 at 0 to
5 atm p CO2 but remains constant from
5 to 55 atm p CO2.
The results obtained in this study demonstrate that carbonate
mineral dissolution rates are not proportional to H2CO3*(aq) and depend only weakly on p
CO2. For dolomite (cleavage planes) and magnesite,
the surface complexation model (SCM) of Pokrovsky et al. [Pokrovsky,O.S.,
Schott,J., Thomas,F., 1999a. Processes at the magnesium-bearing
carbonates/solution interface. I. A surface speciation model of
magnesite. Geochim.Cosmochim.Acta, 63, 863-880; Pokrovsky,O.S.,
Schott,J., Thomas,F., 1999b. Dolomite surface speciation and reactivity
in aquatic systems. Geochim.Cosmochim.Acta, 63, 3133-3143.] predicts
dissolution rates up to 50 atm p CO2
with a good accuracy. Because the dissolution of calcite at 3<pH<4
is controlled by transport processes, experimental and theoretical
difficulties do not permit this mineral dissolution rate to be
accurately modeled within the framework of SCM.
Keywords: Calcite; Dolomite; Magnesite; Dissolution; Kinetics;
p CO2; Salinity』
1. Introduction
2. Experimental methods
2.1. Carbonate samples
2.2. Experimental procedure
2.2.1. Mixed-flow reactors
2.2.2. Batch reactors
2.3. In-situ pH measurements in high-pressure batch reactors
2.4. Analyses
2.5 Calculations
3. Results and discussion
3.1. Kinetics of calcite dissolution
3.2. Kinetics of dolomite dissolution
3.3. Kinetics of magnesite dissolution
4. Conclusions and geological applications
Acknowledgments
Appendix A
Appendix B
References