Sarah Penniston-Dorland | Geology Reports

USGS2021

The systematics of chlorine, lithium, and boron and δ37Cl, δ7Li, and δ11B in the hydrothermal system of the Yellowstone Plateau Volcanic Field

Chlorine, lithium, and boron are trace elements in rhyolite but are enriched in groundwater flowing through rhyolite because they tend to partition into the fluid phase during high‐temperature fluid‐rock reactions. We present a large data set of major element and δ 37 Cl, δ 7 Li, and δ 11 B compositions of thermal water and rhyolite from Yellowstone Plateau Volcanic Field (YPVF). The Cl/B, Cl/Li, δ 37 Cl (−0.2‰ to +0.7‰), and δ 11 B (−6.2‰ to −5.9‰) values of alkaline‐chloride thermal waters reflect high‐temperature leaching of chlorine, lithium, and boron from rhyolite that has δ 37 Cl and δ 11 B values of +0.1‰ to +0.9‰ and −6.3‰ to −6.2‰, respectively. Chlorine and boron are not reactive, but lithium incorporation into hydrothermal alteration minerals results in a large range of Cl/Li, B/Li, and δ 7 Li (−1.2‰ to +3.8‰) values in thermal waters. The relatively large range in δ 7 Li values of thermal waters reflects a large range of values in rhyolite. Large volumes of rhyolite must be leached to account for the chloride, lithium and boron fluxes, implying deep groundwater flow through rhyolite flows and tuffs representing Yellowstone's three eruptive cycles (∼2.1 Ma). Lower Cl/B values in acid‐sulfate waters result from preferential partitioning of boron into the vapor phase and enrichment in the near‐surface water condensate. The Cl/B, Cl/Li, δ 7 Li (−0.3‰ to +2.1‰), and δ 11 B (−8.0‰ to −8.1‰) values of travertine depositing calcium‐carbonate thermal waters which discharge in the northern and southern YPVF suggest that chlorine, lithium, and boron are derived from Mesozoic siliciclastic sediments which contain detrital material from the underlying metamorphic basement.

Wyoming↗

USGS2019

Temperature-dependent variations in mineralogy, major element chemistry and the stable isotopes of boron, lithium and chlorine resulting from hydration of rhyolite glass: Constraints from hydrothermal experiments at 150 to 350°C and 25 MPa

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m ) to hydroxyl (OH − ) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes.

Geochimica et Cosmochimica Acta↗