The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

<p>Abstract</p> <p>Background</p> <p>A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., <inline-formula><m:math name="1467-4866-13-1-i1" xmlns:m="http://www.w3.org/1998/Math/MathML"><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:math></inline-formula>). To better understand the effect of ion activity ratios on CaCO₃precipitation kinetics and Sr²⁺co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω) for calcite was held constant at 9.4, but the ion activity ratio <inline-formula><m:math name="1467-4866-13-1-i2" xmlns:m="http://www.w3.org/1998/Math/MathML"><m:mrow><m:mo class="MathClass-open">(</m:mo><m:mrow><m:mi>r</m:mi><m:mo class="MathClass-rel">=</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:mrow><m:mo class="MathClass-close">)</m:mo></m:mrow></m:math></inline-formula> was varied between 0.0032 and 4.15.</p> <p>Results</p> <p>Calcite was the only phase observed, by XRD, at the end of the experiments. Precipitation rates increased from 41.3 ± 3.4 μmol m^-2min^-1at <it>r = </it>0.0315 to a maximum rate of 74.5 ± 4.8 μmol m^-2min^-1at <it>r = </it>0.306 followed by a decrease to 46.3 ± 9.6 μmol m^-2min^-1at <it>r </it>= 1.822. The trend was simulated using a simple mass transfer model for solute uptake at the calcite surface. However, precipitation rates at fixed saturation states also evolved with time. Precipitation rates accelerated for low <it>r </it>values but slowed for high <it>r </it>values. These trends may be related to changes in effective reactive surface area. The <inline-formula><m:math xmlns:m="http://www.w3.org/1998/Math/MathML" name="1467-4866-13-1-i1"><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:math></inline-formula> ratios did not affect the distribution coefficient for Sr in calcite (D^P_Sr²⁺), apart from the indirect effect associated with the established positive correlation between D^P_Sr²⁺and calcite precipitation rate.</p> <p>Conclusion</p> <p>At a constant supersaturation state (Ω = 9.4), varying the ion activity ratio affects the calcite precipitation rate. This behavior is not predicted by affinity-based rate models. Furthermore, at the highest ion ratio tested, no precipitation was observed, while at the lowest ion ratio precipitation occurred immediately and valid rate measurements could not be made. The maximum measured precipitation rate was 2-fold greater than the minima, and occurred at a carbonate to calcium ion activity ratio of 0.306. These findings have implications for predicting the progress and cost of remediation operations involving enhanced calcite precipitation where mineral precipitation rates, and the spatial/temporal distribution of those rates, can have significant impacts on the mobility of contaminants.</p

Feldspar dissolution kinetics and equilibrium: Implications for natural and engineered systems

The chemical composition of groundwater is controlled largely by subsurface mineral/fluid interactions. Experimental measurement of plagioclase dissolution rates provides a critical means of understanding the relationship between groundwater composition and reservoir characteristics. This thesis focuses on two areas in which understanding of crystal dissolution is poor, i.e., dissolution kinetics as a function of undersaturation under near-equilibrium conditions, and the relationship between dissolution rate, mechanism, crystallography and surface reactivity. We employ a powerful approach: quantification of crystal surface normal retreat rates using vertical scanning interferometry (VSI), which provides direct observation of changes in the mineral surface due to dissolution reactions. This thesis presents results from three experimental studies during which we measured the dissolution rates of albite and anorthite single-crystal, cleavage surfaces as a function of solution saturation state during flow-through experiments over a wide range of temperatures (25--200&deg;C). In addition, we identified specific dissolution mechanisms on reacted crystal surfaces using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The first study compared the dissolution rates of a fine-grained albite powder with those of two albite cleavage surfaces [(010) and (001)]. The dissolution rates of fine-grained albite powders are substantially enhanced compared to those prevailing on large single crystal cleavage surfaces. The second study compared the dissolution rates on previously dissolved albite surfaces exhibiting etch pits and pristine surfaces lacking dissolution features. Experimental results document an up to 2 orders of magnitude difference in dissolution rate between the differently pretreated surfaces, which are dominated by different dissolution mechanisms. The rate difference, which persists over a range of solution saturation state, indicates that the dissolution mechanisms obey different Gibbs free energy difference (DeltaG) dependencies. We propose that the rate gap is the direct consequence of a kinetic bifurcation in dissolution rate and mechanism as DeltaG varies. The existence of the kinetic bifurcation indicates that a single, continuous function describing the relationship between dissolution rate and DeltaG is insufficient. The third study focused on the dissolution kinetics of anorthite with respect to DeltaG and surface reactivity. Our results indicate that dissolution experiments conducted with mineral powders have limited relevance to natural systems

Final report for grant number DE-FG02-06ER64244 to the University of Idaho (RW Smith)-coupling between flow and precipitation in heterogeneous subsurface environments and effects on contaminant fate and transport

Engineered remediation strategies for inducing mineral precipitation in the subsurface typically involve the introduction of at least one reactant either by direct injection or by in situ generation. The localization of reactant sources means a wide range of saturation states and ion ratios will be created as reactants are mixed: These conditions together can result in a wide range of precipitation rates, as well as impact which mineral phase precipitates. This is potentially important for the capacity of the precipitates to take up of trace metal contaminants, for their long term stability. Aragonite, for example, is able to sequester a larger amount of Sr than calcite. However, aragonite is less stable under typical groundwater conditions, and so may release sequestered Sr over time as the aragonite transforms to a more stable phase. In addition, previous experimental studies have indicated that other system constituents may influence calcium carbonate precipitation and consequently the Sr uptake potential of a system. For example, dissolved organic carbon (at levels typical of groundwaters) can suppress crystal growth. As a result, the continuous nucleation of small crystals, rather than growth of existing crystals, may be the dominant mode of precipitation. This has the potential for greater uptake of Sr because the smaller crystal sizes associated with nucleated calcite may more readily accommodate the distortion resulting from substitution of the larger Sr ion for Ca ions than can larger crystals. However, these smaller crystals may also be less stable and over the long term release Sr as a result of Ostwald ripening. To better understand the formation and composition of relevant calcium carbonate mineral phases two related series of mineral precipitation experiments were conducted. The first series of experiments, conducted using a Continuously Stirred Tank Reactor (CSTR) operated at steady state rates of precipitation was focused on understanding the influence of pH and ammonium carbonate (the hydrolysis product of urea: ureolytically driven calcium carbonate precipitation has been demonstrated to be a promising method of inducing mineral precipitation in the field) on calcium carbonate polymorph and Sr co-precipitation. The second series of experiments, conducted at constant pH and saturation state, was focused on understanding the influence of aqueous carbonate to calcium ratios on the precipitation rate of calcite. In 12 CSTR experiments (three pH levels, two ammonium carbonate levels, and two strontium levels) we found that lower pH values and ammonium carbonate concentration promoted the precipitation of calcite and the higher pH values and ammonium carbonate concentration promoted the precipitation of aragonite (as determined by X-ray diffraction). Overall, the rate of calcium carbonate precipitation increased with increasing pH and ammonium carbonate concentration, consistent with increasing values of Q/K. Intermediate conditions resulted in the precipitation of a mixture of calcite and aragonite. There was no discernible effect of strontium on the rate of precipitation or the phase precipitated. In our experiments we precipitated rhombohedral calcite, lath-shaped aragonite and inter-grown calcite-aragonite mixtures. Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometer we characterized the composition of solids from an experiment in which both calcite and aragonite precipitates were identified by X-ray diffraction. We found a range in composition from a high Sr and low Mg phase (inferred to be aragonite) to a coexisting lower Sr and higher but variable Mg phase (inferred to be calcite). Values of the distribution coefficient for strontium of 1.1 and 0.2 for aragonite and calcite, respectively were estimated from the data. These values compare to values of 1.1 and 0.1 for aragonite and calcite, respectively, determined from bulk analysis of precipitates from experiments in which only calcite or only aragonite were detected. In our experiments to assess the influence of solution composition on precipitation rate (at a constant value of Q/K), we found that the precipitation rate varied by approximately a factor of 2 over the range of conditions considered, with a maximum rate observed at a carbonate to calcium ion molar ratio of approximately 0.2. Precipitation kinetics at the extremes tested in this study exhibited interesting behavior. At the lowest ion ratio (carbonate to calcium ion molar ratio of 0.004), a metastable solution was not achievable. At the highest ion ratio (carbonate to calcium ion molar ratio of 4), the solution was indefinitely metastable: no amount of seed material added initiated a drop in pH that would indicate the onset of precipitation. Under conditions considered to date, we cannot definitively quantify the influence (if any) of Sr at 0.1 mM on the measured precipitation rates (work continues in this area through the INL SFA)