Homogenization temperature and salinity data for fluid inclusions from the Summitville, Colorado, Cu-Au-Ag deposit
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Open-File Report↗
Geology topics
Philip M. Bethke
Publications and source records attributed to Philip M. Bethke.
Overview: Ancient Lake Creede
Lake Creede was moderately saline closed-basin lake that developed in the 26.9 Ma Creede caldera in the San Juan Mountains in the southwest Colorado. The volcaniclastic sediments deposited within the late Oligocene lake were first described and named as the Creede Formation by Emmons and Larsen (1923). The lake and its sedimentary fill are of interest first as representatives of a caldera-hosted lake in a silicic volcanic terrane, and second because of the likely involvement of lake fluids or related pore waters in the deposition of the 25 Ma silver and base-metal ores of the Creede mining district north of the Creede caldera (Fig. 1), as proposed Bethke and Rye (1979). Much of the material presented in this volume is based on observation of core samples and on downhole geophysical measurements obtained as part of a U.S. Continental Scientific Drilling Program in the moat of the Creede caldera. These core and downhole studies are supplemented by outcrop studies, some initiated in support of the drilling program (Bethke and Lipman, 1987), and by conceptual studies of the evolution of the Creede caldera and its surrounding landscape. Not surprisingly, not all authors agree on all interpretation. Most disagreements are pointed out in this overview chapter, and may present opportunities for future study.
Colorado↗
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 δ18O 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 interfinger 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 (CaCO3 ·6H2O) 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 δ18O-δ13C 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 δ18O values on CCM-2 samples range from 10.4‰ to 37.3‰ and δ13C 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 δ18O and δ13C values. The negative covariance is opposite that normally reported for lacustrine carbonates. The large range of δ18O and δ13C values requires that the carbonates precipitated from waters have a large range of temperature and carbon and oxygen isotopic composition. The invariant group has a narrow range of large δ18O values (35‰ ± 2‰) and a wide range of δ13C values (–10.8‰ to 9.6‰), indicating precipitation from waters with a narrow range of temperature and δ18O but a wide range in δ13C of aqueous carbon. The ranges of isotope values for microsparite and peloid samples are virtually identical; two-thirds are in the covariant group. By contrast, the values for almost all rice grain samples are in the invariant group. The range in δ18O for all samples reflects precipitation from waters having varying proportions of deep, cold evaporated lake water and shallow, warmer meteoric water. The range for δ13C reflects varying proportions of organic carbon and carbon of volcanic or atmospheric origin, probably dominantly volcanic, in the aqueous carbon. Changes in the detailed carbon-oxygen isotope systematics with stratigraphic position define three periods of isotopic evolution of Lake Creede. Period I is represented by the lowest ~200 m of Creede Formation core in CCM-2. Analyses of individual microsparite and peloidal carbonate laminae within single thin sections of samples from that interval are tightly grouped. The data set as a whole shows a negative covariance. Rice grains are not found in this interval. Period II is represented by the succeeding 120 m of core in CCM-2. In that interval, δ13C-δ18O values for individual microsparite and peloidal carbonate laminae within single thin sections show strong negative covariance, and the set of values for the entire interval also shows strong negative covariance. Rice grains occur near the top of the interval. Period III is represented by the upper 225 m of CCM-2 core. In this interval, rice grains are abundant and δ13C-δ18O values for microsparite and peloidal laminae as well as rice grains fall in the invariant group. During Period I the lake was well mixed and the oxygen isotopic composition of the lake in the productive zone was only slightly influenced by short-term (e.g., annual) variations in the water budget of the lake. In Period II the lake was stratified, possibly with annual overturn. The productive zone included the mixolimnion and the isotopic composition of the microsparites and peloids reflected mixtures of shallow surface (meteoric) water containing volcanic or atmospheric CO2 (epilimnion) and cold underlying waters, the oxygen isotopic compositions of which had evolved through evaporation and were dominated by CO2 produced by the oxidation of organic matter (hypolimnion). During Period III the lake remained stratified. The productive zone was in the hypolimnion, probably due to a thinning of the epilimnion resulting from an increase in the surface area of the lake or a decrease in input waters reflecting a climate change. An upsection increase in values of δ18O for the heaviest samples during Periods I and II indicates evaporative concentration of 18O and, by analogy, salinity in the hypolimnion. The δD-δ18O evolution of the lake is inferred on theoretical evaporation trends, comparison to Mono Lake, and measurement of the δD in fluid inclusions in a calcite pseudomorph after ikaite. The δD-δ18O composition of the lake water followed a curved path that eventually hooked over at a nearly constant δ18O value for the lake of 2‰ ± 2‰ Travertine (tufa) mounds formed along the inner and outer margins of the lake in a zone of mixing of warm, volcanic CO2-bearing, meteoric waters and lake water. Ikaite crystals formed on the mounds from unmixed saline lake water, probably below the thermocline. As the position of the thermocline deepened, likely following the spring runoff, the ikaite was replaced by calcite and the resulting “pearls” were covered with travertine deposited from mixed meteoric and lake waters. The upsection increase in δ18O values of the carbonates, the long period of invariance of large δ18OH2O values, the presence of brine shrimp fecal pellets, and the inferred hooked δD-δ18O path are consistent with evidence from other studies that Lake Creede obtained significant salinity rather early in its history and certainly by the time the lake became permanently stratified.
Colorado↗
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 Snowshow Mountain Tiff 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 34 S for the veinlets is interpreted to be the result of continued fractionation of the already 34 S-depleted pore water. 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 petrographic observations. The 40 Ar/ 39 Ar dating of K-feldspar, concorfance of K-feldspar, kaolinite, and calcite δ 18 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 oxygen-shifted meteoric waters with δ 18 O values of ~-9% Smecities 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 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 18 O waters, whereas those at CCM-2 underwent little, if any, exchange. The δ 13 C-δ 18 O values for calcite veinlets in the Creede Formation are similar to those for authegenic calcites. Fluid-inclusion temperatures and δ 18 O 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 hydrotermal system with Lake Creede pore of lake waters. The silicate and carbonate isotope data indicate that the pores of the Creede Formation were occupied by at least three isotopically distinct water since the time of deposition. The original pore fluids were probably shifted to lower δ 18 O values during burial diagensis as a result of the hydrolysis of the volcanic glass to for 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. Later, the Creede Formation was again flushed, this time with unexchanged meteoric water with δD-δ 18 O values of present-day waters, possibly during the incision of the Rio Grande drainage during uplifting of the southern Rocky Mountains beginning about 5 Ma.
GSA Special Papers↗
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 24000 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 suggester 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 interlayed 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 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 are, and eventually filled the basin. At 25.1 Ma an unseen pluton intruded beneath the northen part of the Creede district and created a convecting olume that drew in brine from the Creede caldera fill, meteotic 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 the 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 Creed 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 setting and exploration opportunities.
Colorado↗
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 or 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 estimate the 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 40 Ar/ 39 Ar techniques and both contain OH and SO 4 sites that enable four stable isotope analyses (δD, δ 18 O OH , and δ 34 S) to be made. This 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 water, as well as details of climate history and geomorphic evolution. Fine-grained (1-10 μm) 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 H2O values of alunite fluids approach but are larger than those of present-day meteoric water. Calculated δD H2O 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 δD-δ 18 O SO4 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.
Colorado↗
A reinterpretation of the δD H 2 O of inclusion fluids in contemporaneous quartz and sphalerite, Creede mining district, Colorodo: a generic problem for shallow orebodies?
Water extracted from fluid inclusions in quartz from shallow epithermal ore deposits often has a hydrogen isotope composition (δD) different from that of water extracted from inclusions in associated minerals. This difference is usually attributed to the involvement of primary fluids from multiple sources. Isotopic and homogenization and freezing temperature determinations on fluid inclusions from contemporaneous quartz and sphalerite from the epithermal, silver and base metal orebodies of the OH vein, Creede district, Colorado, suggest an alternative explanation. In near-surface deposits, differences between δD H 2 O of inclusion fluids in ore minerals and quartz may result, instead, from contamination during extraction of the fluids contained in primary inclusions by shallow ground water trapped in pseudosecondary inclusions in quartz. Quartz from the OH vein contains two principal petrographically distinct populations of fluid inclusions: primary and pseudosecondary. The primary inclusions have salinities ranging from 5 to 10 equiv wt percent NaCl, and the salinities of pseudosecondary inclusions cluster between 0 and 1 percent. Primary inclusions in quartz from one locality have a measured δD H 2 O value of -69 per mil, while pseudosecondary inclusions at the same locality have a δD H 2 O value of -102 per mil. Both salinity and isotopic values for primary inclusions in quartz are similar to those for primary inclusions in contemporaneous sphalerite. Homogenization temperatures for primary and pseudosecondary inclusions in quartz range from 191° to 280° C and from 199° to 278° C, respectively. The δD H 2 O value measured on fluid inclusions from bulk crystals ranges between -97 and -85 per mil and represents a mixture of fluids from both primary and pseudosecondary inclusions. We interpret the data to indicate that one or more episodes of abrupt incursion of cooler, overlying ground water into the ore zone caused thermal cracking of the quartz crystals during the time interval of mineralization. Subsequent healing of the fractures trapped heated, low-salinity ground water in pseudosecondary inclusions. The abrupt incursions of overlying ground water are speculated to have resulted from either collapse of a transient vapor-dominated region of the ore zone, or catastrophic venting of the system through hydrothermal eruption(s). The unusually high contrast between the salinities of the ore-depositing fluids and the ground water overlying the ore zone allowed recognition of this phenomenon at Creede. It is likely, however, that Creede is not unique. Similar phenomena may be common in shallow ore zones where rapid fluctuation of an interface between a deep, high-temperature thermal plume and an overlying, cooler ground water may be expected to occur. Careful study of the origins of fluid inclusions, particularly in quartz, is essential to characterize the primary ore fluids and to assess the role of ground water in the hydrology of shallow ore deposits.
Colorado↗
Distribution of some minor elements between coexisting sulfide minerals
No abstract available.
Economic Geology↗
X-ray crystallographic data for minerals
X-ray crystallographic data are of particular importance to the mineralogist. Beyond the considerations of structural chemistry they provide. one of the most accurate methods for phase and/or compositional determination and for obtaining _the molar volumes and densities of minerals {Robie and Bethke, 1962).
Trace Elements Investigations↗
Molar volumes and densities of minerals
These tables present critically chosen "best values" for the density and molar volume of selected mineral compounds. No attempt was made to be all-inclusive; rather we have tried to present data for chemically and physically well-defined phases for which the molar volume and/or density was knovvn to the order of 0. 2 percent.
Trace Elements Investigations↗