Calcium carbonate precipitation rate as a function of ion ratio in the presence & absence of Sr2+

Tsigabu Gebrehiwet 1*, Mikala Beig 2, Yoshiko Fujita 3, George Redden 3 and Robert W. Smith 1 1University of Idaho, 1776 Science Center Dr, Idaho Falls,ID, 83402 (*tgebrehiwet@uidaho.edu; smithbob@uidaho.edu ) 27963 Grasmere Dr.Boulder, CO 80301(mbeig@alumni.rice.edu) 3Idaho National Laboratory, MS 2208, Idaho Falls, ID 83415 (Yoshiko.Fujita@inl.gov; George.Redden@inl.gov) Engineered in situ precipitation of calcium carbonate is a proposed strategy for remediating toxic or radioactive metals (e.g., Sr2+)in subsurface environments as well as for modifying the physical properties (e.g., stiffness, permeability) of geomedia. Inducing the precipitation reaction will likely involve manipulating the geochemical conditions by adding calcium, (bi)carbonate, or both, and relying on mixing of the two reactants. Under these conditions, the ratio of Ca2+ to CO32- will vary with distance from the mixing interface, and for most or all of the porous medium, a 1:1 stoichiometry between calcium and carbonate is unlikely to be achieved. Indeed, in engineered systems where rapid treatment is an important objective, very steep ion concentration gradients may be generated, which would result in local reactant ratios varying from very small to very large over short distances, depending on the mixing geometry and particular chemical composition of the mixing fluids. This in turn has an impact on the rate of mineral precipitation. Typically, the rate of calcium carbonate precipitation is expressed with an affinity-based rate law of the type: Rate = k(Ω-1)n, where k is a rate constant, Ω is the saturation state for the mineral (e.g., calcite), and n is an empirical reaction order. The saturation state Ω is defined as the ratio of the ion activity product to the mineral solubility product. In this expression, the rate is simply dependent on the value of Ω; the actual activities of the individual ions (Ca2+ and CO32-) do not appear in the expression. In support of the development of engineered calcite precipitation schemes for contaminant immobilization, we have conducted experiments on CaCO3 precipitation kinetics under constant composition conditions where the supersaturation state (Ω) with respect to calcite is held constant at 12.8, but the ion activity ratio (Ca2+:CO32-) is varied. The objective is to examine the effect of the ion ratio on the mineral precipitation rate and on the distribution coefficient for co-precipitated Sr (DexSr). Our results to date indicate that precipitation rates vary by up to a factor of two with the maximum rate occurring at r=0.23, where r is carbonate to calcium ions ratio. In addition, although the extent of variation in the DexSr values is similar to that for the calcite precipitation rate, we have observed low correlation between strontium distribution coefficients and precipitation rates.