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  1. The Paradox Basin in the Colorado Plateau (USA) has some of the most iconic records of paleofluid flow, including sandstone bleaching and ore mineralization, and hydrocarbon, CO2, and He reservoirs, yet the sources of fluids responsible for these extensive fluid-rock reactions are highly debated. This study, for the first time, characterizes fluids within the basin to constrain the sources and emergent behavior of paleofluid flow resulting in the iconic rock records. Major ion and isotopic (δ18Owater; δDwater; δ18OSO4; δ34SSO4; δ34SH2S; 87Sr/86Sr) signatures of formation waters were used to evaluate the distribution and sources of fluids and water-rock interactions by comparison with the rock record. There are two sources of salinity in basinal fluids: (1) diagenetically altered highly evaporated paleo-seawater-derived brines associated with the Pennsylvanian Paradox Formation evaporites; and (2) dissolution of evaporites by topographically driven meteoric circulation. Fresh to brackish groundwater in the shallow Cretaceous Burro Canyon Formation contains low Cu and high SO4 concentrations and shows oxidation of sulfides by meteoric water, while U concentrations are higher than within other formation waters. Deeper brines in the Pennsylvanian Honaker Trail Formation were derived from evaporated paleo-seawater mixed with meteoric water that oxidized sulfides and dissolved gypsum and have high 87Sr/86Sr indicating interaction with radiogenic siliciclastic minerals. Upward migration of reduced (hydrocarbon- and H2S-bearing) saline fluids from the Pennsylvanian Paradox Formation along faults likely bleached sandstones in shallower sediments and provided a reduced trap for later Cu and U deposition. The distribution of existing fluids in the Paradox Basin provides important constraints to understand the rock record over geological time. 
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  2. Abstract

    Extensive regions of yellow and white (“bleached”) sandstones within the terrestrial Jurassic red bed deposits of the Colorado Plateau reflect widespread interaction with subsurface reduced fluids which resulted in the dissolution of iron‐oxide grain coatings. Reduced fluids such as hydrocarbons, CO2, and organic acids have been proposed as bleaching agents. In this study, we characterize an altered section of the Slick Rock member of the Jurassic Entrada Sandstone that exposes bleached sandstone with bitumen‐saturated pore spaces. We observe differences in texture, porosity, mineralogy, and geochemistry between red, pink, yellow, and gray facies. In the bleached yellow facies we observe quartz overgrowths, partially dissolved K‐feldspar, calcite cement, fine‐grained illite, TiO2‐minerals, and pyrite concretions. Clay mineral content is highest at the margins of the bleached section. Fe2O3concentrations are reduced up to 3× from the red to gray facies but enriched up to 50× in iron‐oxide concretions. Metals such as Zn, Pb, and rare‐earth elements are significantly enriched in the concretions. Supported by a batch geochemical model, we conclude the interaction of red sandstones with reduced hydrocarbon‐bearing fluids caused iron‐oxide and K‐feldspar dissolution, and precipitation of quartz, calcite, clay, and pyrite. Localized redistribution of iron into concretions can account for most of the iron removed during bleaching. Pyrite and carbonate stable isotopic data suggest the hydrocarbons were sourced from the Pennsylvanian Paradox Formation. Bitumen in pore spaces and pyrite precipitation formed a reductant trap required to produce Cu, U, and V enrichment in all altered facies by younger, oxidized saline brines.

     
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  3. Abstract

    Fe‐ and Mn‐oxides are common secondary minerals in faults, fractures, and veins and potentially record information about the timing of fluid movement through their host rocks. These phases are difficult to date by most radioisotopic techniques, but relatively high concentrations of U and Th make the (U‐Th)/He system a promising approach. We present new petrographic, geochronologic and thermochronologic analyses of secondary oxides and associated minerals from fault zones and fractures in southeastern Arizona. We use these phases in attempt to constrain the timing of fluid flow and their relationship to magmatic, tectonic, or other regional processes. In the shallowly exhumed Galiuro Mountains, Fe‐oxide (U‐Th)/He dates correspond to host‐rock crystallization and magmatic intrusions from ca. 1.6 to 1.1 Ga. Step‐heating4He/3He experiments and polydomain diffusion modeling of3He release spectra on these samples are consistent with a crystallite size control on He diffusivity, and little fractional loss of radiogenic He since formation in coarse‐grained hematite, but large losses from fine‐grained Mn‐oxide. In contrast to Proterozoic dates, Fe‐ and Mn‐oxides from the Catalina‐Rincon and Pinaleño metamorphic core complexes are exclusively Cenozoic, with dates clustering at ca. 24, 15, and 9 Ma, which represent distinct cooling or fluid‐flow episodes during punctuated periods of normal faulting. Finally, a subset of Fe‐oxides yield dates of ca. 5 Ma to 6 ka and display either pseudomorphic cubic forms consistent with oxidative retrogression of original pyrite or magnetite, or fine‐grained botryoidal morphologies that we interpret to represent approximate ages of recrystallization or pseudomorphic replacement at shallow depths.

     
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