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The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California
In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws
Unsaturated Zone CO2, CH4, and δ13C-CO2 at an Arid Region Low-Level Radioactive Waste Disposal Site
Elevated tritium, radiocarbon, Hg, and volatile organic compounds associated with low-level radioactive waste (LLRW) at the USGS Amargosa Desert Research Site (ADRS) have stimulated research on factors and processes that affect contaminant gas distribution and transport. Consequently, we examined the sources, mixing, and biogeochemistry of CO and CH, two additional important species in the unsaturated zone at ADRS. In spring 2015 and 2016, shallow unsaturated zone gas samples were collected from the 1.5-m depth both inside and outside the LLRW disposal area. Samples also were collected from two 110-m-deep multilevel gas-sampling boreholes and a distant background site. These samples were analyzed for CO mole fraction (CO) and C isotopic composition (δC-CO) and CH mole fraction (CH). Graphical analysis of the results indicates mixing of CO characteristic of the root zone (δC −18 to −19‰), deep soil gas of the capillary fringe (−13 to −15‰), and CO produced by microbial respiration of organic matter disposed in the LLRW trenches (−22 to −25‰). Distribution of CH overall reflects atmospheric sources and production in anaerobic microzones in the LLRW area and methanotrophy in the undisturbed shallow subsurface outside the LLRW area. Although CH reflecting lateral transport from the LLRW area is decreasing with time in the deep profiles, deep unsaturated zone CO has changed little in recent decades. The results imply that CH and δC-CO may serve as good tracers of anthropogenic effects in the unsaturated zone even when CO primarily reflects natural processes