『Abstract
We present here a field geochemical study of controls on carbonate
weathering within rapidly circulating, shallow groundwater-surface
water systems in the glaciated mid-continent region. Groundwaters
and surface waters in three watersheds spanning the Upper to Lower
Peninsulas of Michigan consist of Ca2+-Mg2+-HO3- solutions derived from the open-system
dissolution of calcite and dolomite in soils developed on mixed
mineralogy glacial drift. The thermodynamic stabilities of calcite
and dolomite both decrease with decreasing temperature, with dolomite
more strongly affected. Thus, the low mean annual temperature
of these temperate weathering environments maximizes the absolute
solubility of dolomite as well as its solubility relative to calcite.
Many groundwaters in the study area approach equilibrium with
respect to the more soluble dolomite and are moderately supersaturated
with respect to calcite. Groundwaters in each watershed have distinct
and relatively narrow ranges of carbon dioxide partial pressure
(PCO2) values, which
increase significantly from north to south (log PCO2 of -3.0 to -2.2 atm), suggesting that there
are landscape-level differences in carbon transformation rates
in soil weathering zones. Increases in weathering-zone PCO2 values produce HCO3- concentrations that vary by a factor
of five, but the Mg2+/Ca2+ and Mg2+/HCO3- ratios of all groundwaters are similar,
suggesting relatively constant weathering input ratios of calcite
and dolomite. Although surface waters commonly are between 2 and
10 times supersaturated with respect to calcite, the Mg2+/HCO3- ratios of surface waters are very
close to initial groundwater values, suggesting that back precipitation
of calcite is not a significant process in these systems. The
enhanced solubility of dolomite at low temperatures coupled with
the landscape-level differences in carbon cycling suggest that
temperate-zone weathering reactions in glaciated terrains are
significant contributors to continent-scale fluxes of both Mg2+
and HCO3-.
keywords: carbon; groundwaters; Michigan; carbonate saturation;
dolomite dissolution; carbon dioxide.』
Introduction
Hydrogeologic framework of field study sites
Methods
Field sampling
Laboratory analyses
Thermodynamic modeling and aqueous speciation
Results and interpretations
Elemental stoichiometries and mineral-water reactions
Carbonate speciation and carbonate mineral equilibria
Mass balancing dissolution and precipitation: Mg2+/HCO3- as conservative tracer
Comparisons with North American drainage: Divalent cation and
inorganic carbon budgets
Summary and conclusions
Acknowledgments
References cited