『Abstract
Coupled CaCO3 dissolution-otavite (CdCO3) precipitation experiments have been performed
to 1) quantify the effect of mineral coatings on dissolution rates,
and 2) to explore the possible application of this coupled process
to the remediation of polluted waters. All experiments were performed
at 25℃ in mixed-flow reactors. Various CaCO3
solids were used in the experiments including calcite, aragonite,
and ground clam, mussel, and cockle shells. Precipitation was
induced by the presence of Cd(NO3)2
in the inlet solution, which combined with aqueous carbonate liberated
by CaCO3 dissolution to supersaturate otavite.
The precipitation of an otavite layer of less than 0.01μm in thickness
on calcite surfaces decreases its dissolution rate by close to
two orders of magnitude. This decrease in calcite dissolution
rates lowers aqueous carbonate concentrations in the reactor such
that the mixed-flow reactor experiments attain a steady-state
where the reactive fluid is approximately in equilibrium with
otavite, arresting its precipitation. In contrast, otavite coatings
are far less efficient in lowering aragonite, and ground clam,
mussel, and cockle shell dissolution rates, which are comprised
primarily of aragonite. A steady-state is only attained after
the precipitation of an otavite layer of 3-10μm thick; the steady
state CaCO3 dissolution rate is 1-2 orders
of magnitude lower than that in the absence of otavite coatings.
The difference in behavior is interpreted to stem from the relative
crystallographic structures of the dissolving and precipitating
minerals. As otavite is isostructural with respect to calcite,
it precipitates by epitaxial growth directly on the calcite, efficiently
slowing dissolution. In contrast, otavite's structure is appreciably
different from that of aragonite. Thus, it will precipitate by
random three dimensional heterogeneous nucleation, leaving some
pore space at the otavite-aragonite interface. This pore space
allows aragonite dissolution to continue relatively unaffected
by thin layers of precipitated otavite. Due to the inefficiency
of otavite coatings to slow aragonite and ground aragonite shell
dissolution, aragonite appears to be a far better Cd scavenging
material for cleaning polluted waste waters.』
1. Introduction
2. Methods
3. Theoretical background
3.1. Standard states
3.2. The thermodynamic behavior of the mixed-flow reactor coupled
dissolution/precipitation experiments
3.3. Kinetics of calcium carbonate dissolution
3.4. Inhibition of calcium carbonate dissolution by Cd
3.5. Otavite precipitation kinetics
3.6. Calculation of pH
4. Results
4.1. Summary of results
4.2. Coupled calcite dissolution/otavite precipitation experiments
4.3. Coupled agaronite and shell dissolution/otavite precipitation
experiments
5. Discussion
5.1. How do surface precipitates affect dissolution rates?
5.2. Otavite precipitation mechanisms
5.3. Application to remediating polluted waste water
6. Conclusions
Acknowledgments
References