Geochemical constraints for coexisting CO 2 gas hydrate and calcite: implications for sheet cracks, stromatactis, zebra and tepee-like structures

Abstract

The Ordovician Meiklejohn Peak mud-mound in western Nevada contains sedimentary structures (e.g., stromatactis and “zebra-rock”) that resemble features found in modern methane hydrate deposits. However, the δ 13C of the mud-mound carbonates (−1 to 1‰ PDB) does not suggest interaction with δ 13C-depleted methane. Consequently, Krause (Sedimentary Geology 145 (2001) 189) proposed that the Meiklejohn structures might have been produced by the formation and dissociation of CO 2 gas hydrate rather than methane gas hydrate. Structures in Neoproterozoic cap carbonates, sheet cracks and tepee-like structures have also been suggested to represent gas hydrate interaction with carbonate sediments (Geology 29 (2001) 443), but, similarly, δ 13C values do not suggest direct interaction with methane. The objective of this contribution is to see if the presence of CO 2 gas hydrate is plausible for either setting. To test the feasibility of CO 2 gas hydrate involvement in the formation of these structures, necessary concentrations of TCO 2 were calculated based on required phase equilibria using the quadruple points Q1 (−1.73 °C, 10.2 atm) and Q2 (10.2 °C, 44.5 atm) from the phase diagram for CO 2 gas hydrate (Miller, S.L., 1974. The Nature and Occurrence of Clathrate Hydrates. In: Kaplan, I.R. (Ed.), Natural Gases in Marine Sediments. Plenum, New York, NY, pp. 151–178). A limit for Ca +2 was established based on the lack of evidence for gypsum formation in this environment and the assumption that sulfate was up to 100% of its present oceanic value; the calculated TCO 2 concentration, however, is relatively insensitive to the concentration of SO 4 −2 used. The lowest permissible value of pCO 2 and TCO 2 were found at Q1, where TCO 2 must be at least 300 times the present value. These conditions are implausible for the formation of the Meiklejohn Peak mud-mound. Although some models for Neoproterozoic “Snowball Earth” require highly elevated atmospheric CO 2, these models predict pCO 2 that is still too low to permit the formation of CO 2 gas hydrates in carbonate sediments. In addition, if the required conditions could be achieved during “Snowball Earth”, one would expect to find the associated structures only at the base of the section, while they are commonly observed meters to tens of meters above the base. Therefore, we conclude that it is unlikely these structures were produced by the formation and dissociation of CO 2 gas hydrate.