Understanding barite and gypsum precipitation in upland acid-sulfate soils: An example from a Lufkin Series toposequence, south-central Texas, USA

Abstract

Although low-temperature barite precipitation has been previously documented in soils and paleosols, pedogenic barite precipitation remains poorly understood. This study characterizes the micromorphology, elemental trends, and stable isotope geochemistry of sulfates in a barite-bearing soil (Lufkin Series) toposequence using optical microscopy, XRD, ICP-MS, and stable S and O isotope data. Synthesized data indicate that fluctuating redox processes and microbial activity resulting from epiaquatic and evaporative conditions lead to the precipitation of sulfates in the Lufkin soils. Stable sulfur and oxygen isotopes indicate that the primary source of sulfur is the partial dissolution of jarosite during microbial sulfate reduction. Barium-rich parent material provides adequate barium for barite precipitation. Barium is mobilized and concentrated in Btg horizons ~100–160cm below the surface. The presence of humic acids in profiles lower on the landscape prevents barite precipitation and drives the precipitation of gypsum between saturated, anoxic conditions (November to May) and drier, more oxic conditions (May to November). Barite precipitation is a slow, punctuated process. Micromorphological data reveal that barite precipitates first along evacuated macropores and then in the adjacent matrix. In general, optimal conditions for pedogenic barite precipitation in upland wetland acid-sulfate soils are: 1) warm soil temperature that supports active sulfur-reducing and sulfur oxidizing microbes; 2) distinct wet/dry seasons that allow alternating redox conditions; 3) low-gradient landscape; 4) parent material that contains barium- and sulfur-rich constituents; and 5) a long-lived, stable landscape.