Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: I. Major, minor, and trace elements

Abstract

The Eocene Green River Formation contains the largest oil shale deposits in the world and is a welldocumented example of a lacustrine depositional system. In addition, mineral resources associated with oil shale in the Piceance Basin nahcolite [NaHCO3] and dawsonite [NaAl(CO3)(OH)2)] are of current and potential economic value, respectively. Detailed geochemical analysis across the basin can aid in the understanding of the depositional environment, sedimentary processes, and water-chemistry evolution in this system. Quantitative geochemical data for Green River oil shale from the Piceance Basin of Colorado were collected by inductively coupled plasma optical emission spectroscopy and mass spectrometry as part of this study. The basin margin is represented by samples from exposures at Douglas Pass (Garfield County) and the basin center area is characterized by core samples from two drilled wells: the Shell 23X-2 and John Savage 24-1 (Rio Blanco County). Major elements and groups of elements are used as proxies for clastic influx (Si, Al, K, Ti), carbonate deposition (Ca, Mg), salinity (Na), paleo-productivity (P), and redox state (Fe, S), respectively. Minor and trace elements reinforce observations based on major elements, including Rb, Zr, Nb for clastic influx and Mn, Sr for carbonate. Trace elements are used to characterize redox conditions (As, Mo, U, V, Co, Ni, Cu, Zn) and salinity (Rb/K, B/Ga). Chemical distinctions between the basin margin and the basin center, in terms of these components and total organic carbon concentrations, support the model of a permanently stratified lake through most of the depositional interval. A primary purpose of the study was to conduct more extensive sampling to confirm conclusions of a previous reconnaissance study. Geochemical data from this study indicates elevated Na around the basin margin occurring earlier than in the deeper basin. Early in the history of Lake Uinta, the salinity may have been elevated first in the shallower marginal waters, due to increased evaporation, which then led to elevated salinity in the basin center through transport of saline density currents. Other indicators of salinity (Rb/K, B/Ga) do not track Na content in intervals where clay minerals are absent due to diagenetic alteration under hypersaline conditions but may be used to indicate the salinities at which authigenic Na-bearing minerals begin to form. Most Na-rich samples show high proportions of clastic constituents (Si, Al, K, Ti) compared to conventional carbonate constituents (Ca, Mg). Redox-sensitive period IV transition metal elements (V, Co, Ni, Cu, Zn) show only local occurrence of significant enrichment relative to average shale abundances. Analysis of Fe/Al ratios for this dataset suggests that the depletion of these elements may be related to source rocks depleted in mafic constituents, with apparent redox-related enrichments subdued by this effect. The basin margin samples reflect generally oxic bottom waters, with some intervals deposited under more reducing, possibly dysoxic to anoxic conditions. The basin center results indicate more reducing conditions, with Mo and U enrichment factors suggesting operation of a particulate shuttle mechanism that scavenged Mo on Fe/Mn-oxyhydroxides that redissolved at depth, with Mo precipitating along with sulfides and/or organic matter at or near the sediment/water interface.