Impurity ion and isotope partitioning into carbonate minerals provide a window into the molecular processes occurring at the fluid-mineral interface during crystal growth. Here, we employ calcium isotope fractionation together with process-based modeling to elucidate the mechanisms by which two divalent cations with starkly contrasting compatibility, magnesium and manganese, inhibit calcite growth and incorporate into the mineral lattice. Calcite growth inhibition by Mg2+ is log-linear and KMg is on the order of 0.02–0.03 throughout the range of {Mg2+}/{Ca2+} studied here (0.01–2.6). Mn2+ exhibits much stronger log-linear growth rate inhibition at low Mn2+ concentrations (fluid {Mn2+}/{Ca2+} = 0.001–0.02). Mn2+ is readily incorporated into the calcite lattice to form a calcite-rhodochrosite solid solution, with large partition coefficients (KMn 4.6–15.6) inversely correlated to growth rate. For both Mn2+ and Mg2+, calcium isotope fractionation is found to be invariant with {Me2+}/{Ca2+} despite more than an order of magnitude decline in growth rate. This invariant Δ44/40Ca suggests that the presence of Mn2+ or Mg2+ does not significantly change the relative rates of Ca2+ attachment and detachment at kink sites during growth, indicative of a dominantly kink blocking inhibition mechanism. Because the partitioning behavior dictates that Mn2+ must attach to the surface significantly faster than Ca2+, attachment of Mn2+ is likely to be as a non-monomer species such as an ion pair or possibly a larger polynuclear cluster. We propose that calcite growth rate inhibition by Mn is determined by the kinetics of carbonate attachment at Mn-occupied kink sites, potentially due to slow re-orientation kinetics of carbonate ions that have formed an inner-sphere complex with Mn2+ at the surface but must reorient to incorporate into the lattice. We demonstrate that patterns in Mg2+ partitioning and inhibition behavior are broadly consistent with growth inhibition driven by slow Mg2+-aquo complex dehydration relative to Ca2+ but argue that this mechanism likely represents one endmember scenario, seen in Mg-calcite growth at low supersaturations and net precipitation rates. During growth at faster net precipitation rates, some portion of Mg2+ is likely incorporated as a partially hydrated or otherwise complexed species, but calcite growth remains significantly inhibited by the kinetics of CO32− attachment at Mg2+ kink sites. These findings suggest a hybrid classical/nonclassical growth mechanism whereby Ca2+ incorporates largely as a free ion at kink sites while Mn2+ and some portion of Mg2+ are incorporated via non-monomer attachment. This pattern may be generalizable; trace constituent cations with aquo-complex desolvation rates significantly slower than the mineral growth rate preferentially incorporate as a non-monomer species during otherwise classical crystal growth.

Deserts comprise a large portion of the Earth's land area, yet their role in the fluxes and cycles of greenhouse gases is poorly known and their likely response to climate change largely unexplored. We report a reconnaissance investigation of the concentrations and fluxes of CO2, CH4, and N2O along two elevation (climate) gradients in the southwestern United States. In-soil concentrations of CO2 increased with elevation (up to 5,000 ppm). Concentrations of CH4 declined with depth in all soils (to less than 1 ppm), but the rates of decrease with depth increased with elevation. In contrast, concentrations and depth trends of N2O varied erratically. Soils were net CO2 sources (0 to >1,500 kg CO2·ha−1·year−1), and net CH4 sinks (0.2 to >3 kg CH4·ha−1·year−1). The small and variable N2O fluxes were inconsistent with the trends in soil N δ15N values, which decreased by 5‰ to 6‰ over about 1,000 m of elevation. The high soil N δ15N values (up to nearly 17‰ at the lowest elevation) indicate that there is a soil N loss mechanism that is highly depleted in 15N, and gaseous losses—either NH3 or N2O/N2—are suspected of driving these values. In summary, there appears to be a strong climate control on both soil CO2 and CH4 concentrations and to a lesser degree on calculated fluxes. The soil N trace gas concentrations indicate that deserts can be either small sources or sinks of N2O and that there may be significant consumption of arid soil N2O.