Philip M. Bethke

Neogene geomorphic and climatic evolution of the central San Juan Mountains, Colorado: K/Ar age and stable isotope data on supergene alunite and jarosite from the Creede mining district

K/Ar age determinations on supergene alunite and jarosite, formed during Neogene weathering of the epithermal silver and base-metal ores of the Creede mining district, have been combined with geologic evidence to estimatethe timing of regional uplift of the southern Rocky Mountains and related canyon cutting. In addition, oxygen and hydrogen isotopic studies suggest climate changes in the central San Juan Mountains during the past 5 m.y. Alunite [ideally (K,Na)Al 3 (SO 4 ) 2 (OH) 6 ] and jarosite [ideally KFe 3 (SO 4 ) 2 (OH) 6 ] can be dated by K/Ar or 4 0 Ar/ 3 9 Ar techniques and both contain OH and SO 4 sites that enable four stable isotope analyses (δD, δ 1 8 O S O 4 , δ 1 8 O O H , and δ 3 4 S) to be made. Thus supergene alunite and jarosite formed by weathering of sulfide-rich ore bodies may record the evolution of the chemical and hydrologic processes affecting ancient oxidized acid ground waters, as well as details of climate history and geomorphic evolution. Fine-grained (1-10μm) supergene alunite and jarosite occur in minor fractures in the upper, oxidized parts of the 25 Ma sulfide-bearing veins of the Creede mining district, and jarosite also occurs in adjacent oxidized Ag-bearing clastic sediments. K/Ar ages for alunite range from 4.8 to 3.1 Ma, and for jarosite range from 2.6 to 0.9 Ma. The δD values for alunite and jarosite show opposite correlations with elevation, and values for jarosite correlate with age. Calculated δD H 2 O values of alunite fluids approach but are larger than those of present-day meteoric water. Calculated δD H 2 O values for jarosite fluids are more variable; the values of the youngest jarosites are lowest and are similar to those of present-day meteoric water in the district. The narrow range for δD-δ 1 8 O S O 4 values of alunites reflects oxidation of sulfide below the water table. The greater range in these values for jarosites reflects oxidation of sulfide under vadose conditions. The ages of alunite mark the position of the paleo-water table at the end of a period of moderate erosion from ca. 25 to 5 Ma that exposed the tops of the ore bodies to oxidation. The younger jarosite formed in the vadose zone during or following subsequent canyon cutting related to regional uplift of the southern Rocky Mountains. The δD values suggest that climates in the area were similar to those of the present day prior to regional uplift but went through a warm period before returning to present conditions during or after regional uplift. The results of this study indicate that the combined stable and radiogenic isotope analysis of supergene alunite and jarosite has broad application in understanding climate and geomorphic evolution of selected areas.

Stable isotope evolution and paleolimnology of ancient Lake Creede

The lacustrine carbonate and travertine (tufa) deposits of ancient Lake Creede preserve a remarkable record of the isotopic evolution of the lake. That record indicates that the δ 1 8 O of the lake water, and by analogy its salinity, evolved through evaporation. Limited and less reliable data on hydrous minerals and fluid inclusions in early diagenetic carbonates indicate that the δD of the lake waters also evolved through evaporation. The isotope data place restrictions on models of the physical limnology of the lake and its evolution. The closed-basin Lake Creede formed shortly after collapse of the 26.9 Ma Creede caldera. Throughout most of its history it occupied the northern three quarters of the moat between the resurgent dome and wall of the caldera. The Creede Formation was deposited in the basin, dominantly as lacustrine sediments. Travertine mounds inter-finger with Creede Formation sediments along the inner and outer margins of the lake basin. An estimated one-half of the original thickness of the Creede Formation has been lost mainly to erosion although scattered remnants of the upper portion remain on the caldera walls. Two diamond core holes (CCM-1 and CCM-2) sampled the uneroded portion of the Creede Formation as part of the U.S. Continental Drilling Program. Volcaniclastic material, including tuff units deposited directly into the lake and ash washed in from the watershed, compose the main lithologies of the Creede Formation. These volcaniclastic strata were produced by episodic ring-fracture volcanism. Lacustrine carbonates make up about 15% of the section sampled by drill core. They occur as 1 mm to 2 cm low-Mg calcite laminae alternating with siliciclastic laminae in scattered intervals throughout the preserved section. The carbonate laminae are accumulations of 5-20 μm crystallites (microsparites) and brine shrimp fecal pellets (peloids) composed mainly of microsparite particles. Low-Mg calcite also occurs as an early diagenetic replacement of gypsum or ikaite (CaCO 3 .6H 2 O) crystals grown displacively in the muds and silts near the water-sediment interface (rice grains). Other studies indicate that aragonite was the original CaCO3 precipitate forming the microsparite and peloidal laminae and that it converted to calcite during burial diagenesis. Samples from CCM-2 and nearby outcrop do not appear to have undergone significant isotope exchange during recrystallization. Samples from CCM-1 and nearby outcrop, however, appear to have undergone extensive oxygen isotope exchange with meteoric water-dominated fluids possibly during a local 17.6 Ma hydrothermal event. The δ 1 8 O-δ 1 3 C data set produced by microsampling of individual carbonate lamellae and rice grains is exceptional in several aspects and provides important clues concerning the evolution of limnologic structure of the lake and its chemical and isotopic composition. Travertine and ikaite pseudomorphs in travertine deposits extend the record an additional 330 m above the collar of CCM-2. The δ 1 8 O values on CCM-2 samples range from 10.4‰ to 37.3‰ and δ 1 3 C values range from -10.8‰ to 9.6‰. The data fall into two distinct groups, a covariant group and an invariant group. The covariant group shows a strong negative covariance and a large range of δ 1 8 O and δ 1 3 C values. The negative covariance is opposite that normally reported for lacustrine carbonates.

Evolution of the Creede caldera and its relation to mineralization in the Creede mining district, Colorado

At 25 Ma a major epithermal silver and base metal deposit formed in rhyolitic welded tuff near Creede, Colorado. Nearly 2400 metric tons of silver, appreciable lead, and small amounts of zinc, copper, and gold, have been produced from large, crustified veins under Bachelor and Bulldog Mountains north and northwest of Creede. Prior geologic, hydrologic, and stable-isotope studies showed that ore deposition was associated with the mixing and boiling of waters from diverse sources and suggested that a critical part of the ore-forming fluid may have originated within the ancient lake and sediments of the lacustrine Creede Formation that filled the Creede caldera. Two drill holes that sampled the heretofore hidden lower half of the Creede Formation are the focus of this book. The Creede caldera formed at 26.9 Ma within a high constructional plateau of silicic ashflows that covered and were sporadically interlayered with, intermediate lavas and lahars from large stratovolcanoes. The Creede caldera lake had an inflow evaporation balance that did not permit rapid filling to create a brim-full deep lake. Thus salts were evaporatively concentrated; but, with the exception of possible gypsum, no evaporite minerals are preserved. Cool springs deposited travertine as mounds and contributed to limestone interlaminations within the sediment. The lake bottom was anoxic, and bacterial reduction of sulfate led to extreme sulfur isotopic fractionation in diagenetic pyrite. The caldera gradually resurged, converting the initial equant lake into an arcuate moat. Resurgent doming, alluvial fans, lacustrine sediments, ashfalls, and lava domes displaced water, lifted the lake so that it overlapped what later became the southern edge of the mineralized area, and eventually filled the basin. At ∼25.1 Ma an unseen pluton intruded beneath the northern part of the Creede district and created a convecting plume that drew in brine from the Creede caldera fill, meteoric water from highlands to the north, and possibly a fluid carrying radiogenic lead. These waters mixed and boiled as they approached the surface and moved southward, deposited a zoned epithermal deposit a few hundred meters below the paleosurface, and finally discharged into the top of the Creede Formation. The sulfide in the ores was of igneous derivation, but the sulfate was a mixture of biogenic sulfur from the Creede Formation, oxidized igneous sulfide, and thermochemically reduced and partially oxygen exchanged sulfate. The studies of the Creede caldera provide key observational and conceptual elements for the generalized model of the Creede ore deposit. The relation of the Creede ore deposit to a brine reservoir has broad significance because other brine accumulations (as in the Great Basin, the Green River Basin, or the playas of the Altiplano) offer similar settings and exploration opportunities.

Isotopic studies of authigenic sulfides, silicates, and carbonates, and calcite and pyrite veinlets in the Creede Formation, San Juan Mountains, Southwest Colorado

Sulfur isotope analysis of authigenic pyrite in the Creede Formation documents its precipitation by the reaction between iron in the volcaniclastic sediments and H 2 S formed through bacteriogenic reduction of sulfate added to the lake during and immediately following repeated volcanic eruptions during sedimentation. Pyrite veinlets in the underlying Snowshoe Mountain Tuff were formed by the percolation of H 2 S-bearing pore waters into fractures in the tuff. Conventional analyses of bulk samples of authigenic pyrite range from -20.4‰ to 34.5‰, essentially equivalent to the range of -30‰ to 40‰ determined using SHRIMP microprobe techniques. Conventional analyses of bulk samples of pyrite from veinlets in the Snowshoe Mountain Tuff range from -3.5‰ to 17.6‰, much more limited than the ranges of -23‰ to 111‰ and -15.6‰ to 67.0‰ determined by SHRIMP and laser ablation microbeam techniques, respectively. The extreme range of δ 3 4 S for the veinlets is interpreted to be the result of continued fractionation of the already 3 4 S-depleted pore waters. Oxygen isotope analysis of authigenic smectite, kaolinite, and K-feldspar together with fluid-inclusion temperatures and oxygen isotope analysis of calcite coexisting with kaolinite indicate that the smectites formed early during burial diagenesis, in accord with the petrographic observations. The 4 0 Ar/ 3 9 Ar dating of K-feldspar, concordance of K-feldspar, kaolinite, and calcite δ 1 8 O values, and fluid-inclusion temperatures in calcite, indicate that the sediments at core hole CCM-1 were subjected to a hydrothermal event at 17.6 Ma. The minerals formed from oxygen-shifted meteoric waters with δ 1 8 O values of ∼-9‰. Smectites at CCM-1 at least partially exchanged with these waters. Carbon and oxygen isotope analysis of authigenic calcites in the Creede Formation show that they formed over a wide range of temperatures from fluids having a wide range of isotopic composition, presumably over an extended period of time. Some of the cements apparently formed very late from unexchanged meteoric water. Concretions and possibly some cements at CCM-1 appear to have exchanged with the 17.6 Ma oxygen-shifted hydrothermal fluids. Such exchange is consistent with evidence that lacustrine carbonates at CCM-1 exchanged with low 1 8 O waters, whereas those at CCM-2 underwent little, if any, exchange. The δ 1 3 C-δ 1 8 O values for calcite veinlets in the Creede Formation are similar to those for authigenic calcites. Fluid-inclusion temperatures and δ 1 8 O values indicate that some were deposited during the 17.6 Ma hydrothermal event and others from unexchanged meteoric water at a later date. The isotope studies confirm that part of the model of Rye et al., proposing that the barites in the southern end of the Creede Mining District were formed by mixing of the Creede hydrothermal system with Lake Creede pore or lake waters. The silicate and carbonate isotope data indicate that the pores of the Creede Formation were occupied by at least three isotopically distinct waters since the time of deposition. The original pore fluids probably shifted to lower δ 1 8 O values during burial diagenesis as a result of the hydrolysis of the volcanic glass to form smectites and other hydrous silicates. During or prior to a 17.6 Ma hydrothermal event in the vicinity of CCM-1, the Creede Formation was flushed with oxygen-shifted meteoric water, possibly related to the breaching of the east side of the caldera wall sometime between 20 and 22 Ma.