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Robert O. Rye

Publications and source records attributed to Robert O. Rye.

At least 19 recordsLinked to original sources
USGS2022

40Ar/39Ar geochronology of magmatic-steam alunite from Alunite Ridge and Deer Trail Mountain, Marysvale Volcanic Field, Utah: Timing and duration of miocene hydrothermal activity associated with concealed intrusions

Porphyry and epithermal deposits are important sources of base and precious metals. Most actively mined deposits have been exhumed such that ore bodies are relatively close to the surface and are therefore locatable and economic to extract. Identifying and characterizing concealed deposits, particularly more deeply buried porphyry deposits, represents a far greater challenge for mineral exploration, and will become progressively more important as near-surface resources are gradually exhausted over time. We report high-precision 40 Ar/ 39 Ar dates for coarsely crystalline alunite that precipitated from magmatic steam in open fractures in Oligocene dacitic volcanic rocks, and a SHRIMP 206 Pb/ 238 U zircon date for one of several rhyolite dikes present at Alunite Ridge and Deer Trail Mountain, Utah. Both the magmatic-steam alunite and rhyolite dikes are related to concealed intrusions. The rhyolite dike yielded an age of 30.72 ± 0.36 Ma, which is older than a commonly cited 27.1 Ma age estimate for the Three Creeks Tuff Member of the Bullion Canyon Volcanics that is cut by the dike. 40 Ar/ 39 Ar data for samples of magmatic-steam alunite and sericite from six mines and prospects provide evidence for at least two periods of episodic hydrothermal activity at ca. 15.7–15.1 Ma and ca. 14.7–13.8 Ma, with the older and younger pulses of activity recorded at the more eastern and western sites, respectively. These two periods of hydrothermal activity are consistent with previous interpretations that Alunite Ridge and Deer Trail Mountain are underlain by two concealed porphyry stocks. 40 Ar/ 39 Ar analyses of individual bands in a sample of massive, centimeter-scale banded vein alunite yield indistinguishable ages with a weighted mean of 13.98 ± 0.12 Ma, consistent with a short-lived (≲250 ka) magmatic event with episodic vapor discharge recurring on short timescales (≲36 ka). 40 Ar/ 39 Ar geochronology of magmatic-steam alunite is a valuable tool to constrain the timing and duration of magmatic hydrothermal activity associated with unexposed intrusions and potentially porphyry deposits, and therefore may be useful in exploration.

Utah↗
USGS2016

Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ 18 O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ 18 O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes. Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ 34 S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition of copper or was cotransported with copper, and (2) sulfur isotope analysis may be useful in evaluating southeast Missouri iron deposits for copper and possibly for gold.

Missouri↗
USGS2012

Mineralogical, chemical, and crystallographic properties of supergene jarosite-group minerals from the Xitieshan Pb-Zn sulfide deposit, northern Tibetan Plateau, China

Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K 2 O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K 0.29 Na 0.19 Pb 0.31 Fe 2.66 Al 0.22 (SO 4 ) 1.65 (PO 4 ) 0.31 (AsO 4 ) 0.04 (OH) 7.37 . The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO, 4/sub> at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO 4 ) 2 and minor hematite. The decomposition products of NaFe(SO 4 ) are hematite and Na, 2 SO 4 . Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a =7.315 ä and c =016.598 ä. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c , but only slightly increase a . The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site.

Tibetan Plateau↗
USGS2012

The Spar Lake strata-Bound Cu-Ag deposit formed across a mixing zone between trapped natural gas and metals-bearing brine

Ore formation at the Spar Lake red bed-associated strata-bound Cu deposit took place across a mixing and reaction zone between a hot oxidized metals-transporting brine and a reservoir of “sour” (H 2 S-bearing) natural gas trapped in the host sandstones. Fluid inclusion volatile analyses have very high CH 4 concentrations (≥1 mol % in most samples), and a sample from the fringe of the deposit has between 18 and 36 mol % CH 4 . The ratio of CH 4 /CO 2 in fluid inclusions appears to vary regularly across the deposit, with the lowest CH 4 /CO 2 ratios from high-grade chalcocite-bearing ore, and the highest from the chalcopyrite-bearing fringe. The helium R/R a isotope ratios (0.23–0.98) and concentrations define a mixture between crustal and atmospheric helium. The volatiles in fluid inclusions (CH 4 , CO 2 , H 2 S, SO 2 , H 2 , H 2 O, and other organic gases) and values of f O 2 and temperature calculated from the volatiles data all show gradations across the deposit that are completely consistent with such a mixing and reaction zone. Other volatiles from the fluid inclusions (HCl, HF, 3 He, Msup>4 He, N 2 , Ar) characterize the brine and give evidence for only shallow crustal fluids with no magmatic influences. The brine entered the gas reservoir from below and along the axis of the deposit and migrated out along bedding to the southwest, northeast, and northwest. Metals-transporting brines may have been fed into the host sandstones from the East Fault, but that remains uncertain. Abundant ore-stage Fe and Mn calcite cements from the reduced fringe have δ 13 C values as low as −18.4‰, and many values less than −10‰, which indicate that significant carbonate was generated by oxidation of organic carbon from the natural gas. The zone of calcite cements with very low δ 13 C values approximately envelopes chalcocite-bearing ore. Sulfur isotope data of Cu, Pb, and Fe sulfides and barite indicate derivation of roughly half of the orebody sulfide directly from sour gas H 2 S. That sour gas H 2 S had developed in steps known from other sedimentary basins, starting with (1) bacterial sulfate reduction (BSR) of seawater sulfate having δ 34 S of about 20‰ and sequestering of the sulfide in organic matter in source rocks stratigraphically below the deposit host rocks, followed by (2) maturation of the sulfide-bearing organic matter into liquid petroleum with relatively homogeneous sulfide having δ 34 S of 5 ± 5‰, then by (3) thermal cracking of the oil to CH 4 and H 2 S with relatively homogeneous sulfide having δ 34 S closely distributed, about 6‰. The CH 4 and H 2 S migrated and were trapped in sandstones of the upper member of the Revett Formation, where they were later met by the 200°C metals-transporting brine. There was additional contribution of sulfide to ore from later thermochemical sulfate reduction (TSR) operating on sulfate δ 34 S of 20 to 29‰ in both formation waters and metals-transporting solutions. A large range of δ 34 S in sulfides resulted as the 6‰ sour gas sulfide was supplemented with varying proportions of 20 to 29‰ sulfide from TSR.

Economic Geology↗
USGS2010

Evolution of Ore Deposits and Technology Transfer Project: Isotope and Chemical Methods in Support of the U.S. Geological Survey Science Strategy, 2003-2008

Principal functions of the U.S. Geological Survey (USGS) Mineral Resources Program are providing assessments of the location, quantity, and quality of undiscovered mineral deposits, and predicting the environmental impacts of exploration and mine development. The mineral and environmental assessments of domestic deposits are used by planners and decisionmakers to improve the stewardship of public lands and public resources. Assessments of undiscovered mineral deposits on a global scale reveal the potential availability of minerals to the United States and other countries that manufacture goods imported to the United States. These resources are of fundamental relevance to national and international economic and security policy in our globalized world economy. Performing mineral and environmental assessments requires that predictions be made of the likelihood of undiscovered deposits. The predictions are based on geologic and geoenvironmental models that are constructed for the diverse types of mineral deposits from detailed descriptions of actual deposits and detailed understanding of the processes that formed them. Over the past three decades the understanding of ore-forming processes has benefited greatly from the integration of laboratory-based geochemical tools with field observations and other data sources. Under the aegis of the Evolution of Ore Deposits and Technology Transfer Project (referred to hereinafter as the Project), a 5-year effort that terminated in 2008, the Mineral Resources Program provided state-of-the-art analytical capabilities to support applications of several related geochemical tools to ore-deposit-related studies. The analytical capabilities and scientific approaches developed within the Project have wide applicability within Earth-system science. For this reason the Project Laboratories represent a valuable catalyst for interdisciplinary collaborations of the type that should be formed in the coming years for the United States to meet its natural-resources and natural-science needs. This circular presents an overview of the Project. Descriptions of the Project laboratories are given first including descriptions of the types of chemical or isotopic analyses that are made and the utility of the measurements. This is followed by summaries of select measurements that were carried out by the Project scientists. The studies are grouped by science direction. Virtually all of them were collaborations with USGS colleagues or with scientists from other governmental agencies, academia, or the private sector.

Circular↗
USGS2008

Cyanide speciation at four gold leach operations undergoing remediation

Analyses have been made of 81 effluents from four gold leach operations in various stages of remediation to identify the most-persistent cyanide species. Total cyanide and weak acid-dissociable (WAD) cyanide were measured using improved methods, and metals known to form stable cyanocomplexes were also measured. Typically, total cyanide greatly exceeded WAD indicating that cyanide was predominantly in strong cyanometallic complexes. Iron was generally too low to accommodate the strongly complexed cyanide as Fe(CN) 6 3- or Fe(CN) 6 4- , but cobalt was abundant enough to implicate Co(CN) 6 3- or its dissociation products (Co(CN) 6-x (H 2 O) x (3-x)- ). Supporting evidence for cobalt-cyanide complexation was found in tight correlations between cobalt and cyanide in some sample suites. Also, abundant free cyanide was produced upon UV illumination. Iron and cobalt cyanocomplexes both photodissociate; however, the iron concentration was insufficient to have carried the liberated cyanide, while the cobalt concentration was sufficient. Cobalt cyanocomplexes have not previously been recognized in cyanidation wastes. Their identification at four separate operations, which had treated ores that were not especially rich in cobalt, suggests that cobalt complexation may be a common source of cyanide persistence. There is a need for more information on the importance and behavior of cobalt cyanocomplexes in ore-processing wastes at gold mines.

California;Nevada;New Mexico↗
USGS2008

Environmental factors affecting mercury in Camp Far West Reservoir, California, 2001-03

This report documents water quality in Camp Far West Reservoir from October 2001 through August 2003. The reservoir, located at approximately 300 feet above sea level in the foothills of the northwestern Sierra Nevada, California, is a monomictic lake characterized by extreme drawdown in the late summer and fall. Thermal stratification in summer and fall is coupled with anoxic conditions in the hypolimnion. Water-quality sampling was done at approximately 3-month intervals on eight occasions at several stations in the reservoir, including a group of three stations along a flow path in the reservoir: an upstream station in the Bear River arm (principal tributary), a mid-reservoir station in the thalweg (prereservoir river channel), and a station in the deepest part of the reservoir, in the thalweg near Camp Far West Dam. Stations in other tributary arms of the reservoir included those in the Rock Creek arm of the reservoir, a relatively low-flow tributary, and the Dairy Farm arm, a small tributary that receives acidic, metal-rich drainage seasonally from the inactive Dairy Farm Mine, which produced copper, zinc, and gold from underground workings and a surface pit. Several water-quality constituents varied significantly by season at all sampling stations, including major cations and anions, total mercury (filtered and unfiltered samples), nitrogen (ammonia plus organic), and total phosphorus. A strong seasonal signal also was observed for the sulfurisotope composition of aqueous sulfate from filtered water. Although there were some spatial differences in water quality, the seasonal variations were more profound. Concentrations of total mercury (filtered and unfiltered water) were highest during fall and winter; these concentrations decreased at most stations during spring and summer. Anoxic conditions developed in deep parts of the reservoir during summer and fall in association with thermal stratification. The highest concentrations of methylmercury in unfiltered water were observed in samples collected during summer from deepwater stations in the anoxic hypolimnion. In the shallow (less than 14 meters depth) oxic epilimnion, concentrations of methylmercury in unfiltered water were highest during the spring and lowest during the fall. The ratio of methylmercury to total mercury (MeHg/HgT) increased systematically from winter to spring to summer, largely in response to the progressive seasonal decrease in total mercury concentrations, but also to some extent because of increases in MeHg concentrations during summer. Water-quality data for Camp Far West Reservoir are used in conjunction with data from linked studies of sediment and biota to develop and refine a conceptual model for mercury methylation and bioaccumulation in the reservoir and the lower Bear River watershed. It is hypothesized that MeHg is produced by sulfate-reducing bacteria in the anoxic parts of the water column and in shallow bed sediment. Conditions were optimal for this process during late summer and fall. Previous work has indicated that Camp Far West Reservoir is a phosphate-limited system - molar ratios of inorganic nitrogen to inorganic phosphorus in filtered water were consistently greater than 16 (the Redfield ratio), sometimes by orders of magnitude. Therefore, concentrations of orthophosphate were expectedly very low or below detection at all stations during all seasons. It is further hypothesized that iron-reducing bacteria facilitate release of phosphorus from iron-rich sediments during summer and early fall, stimulating phytoplankton growth in the fall and winter, and that the MeHg produced in the hypolimnion and metalimnion is released to the entire water column in the late fall during reservoir destratification (vertical mixing). Mercury bioaccumulation factors (BAF) were computed using data from linked studies of biota spanning a range of trophic position: zooplankton, midge larvae, mayfly nymphs, crayfish, threadfin shad, bluegill,

California↗
USGS2007

The question of recharge to the deep thermal reservoir underlying the geysers and hot springs of Yellowstone National Park: Chapter H in Integrated geoscience studies in Integrated geoscience studies in the Greater Yellowstone Area—Volcanic, tectonic, and hydrothermal processes in the Yellowstone geoecosystem

The extraordinary number, size, and unspoiled beauty of the geysers and hot springs of Yellowstone National Park (the Park) make them a national treasure. The hydrology of these special features and their relation to cold waters of the Yellowstone area are poorly known. In the absence of deep drill holes, such information is available only indirectly from isotope studies. The δD-δ18O values of precipitation and cold surface-water and ground-water samples are close to the global meteoric water line (Craig, 1961). δD values of monthly samples of rain and snow collected from 1978 to 1981 at two stations in the Park show strong seasonal variations, with average values for winter months close to those for cold waters near the collection sites. δD values of more than 300 samples from cold springs, cold streams, and rivers collected during the fall from 1967 to 1992 show consistent north-south and east-west patterns throughout and outside of the Park, although values at a given site vary by as much as 8 ‰ from year to year. These data, along with hot-spring data (Truesdell and others, 1977; Pearson and Truesdell, 1978), show that ascending Yellowstone thermal waters are modified isotopically and chemically by a variety of boiling and mixing processes in shallow reservoirs. Near geyser basins, shallow recharge waters from nearby rhyolite plateaus dilute the ascending deep thermal waters, particularly at basin margins, and mix and boil in reservoirs that commonly are interconnected. Deep recharge appears to derive from a major deep thermal-reservoir fluid that supplies steam and hot water to all geyser basins on the west side of the Park and perhaps in the entire Yellowstone caldera. This water (T ≥350°C; δD = –149±1 ‰) is isotopically lighter than all but the farthest north, highest altitude cold springs and streams and a sinter-producing warm spring (δD = –153 ‰) north of the Park. Derivation of this deep fluid solely from present-day recharge is problematical. The designation of source areas depends on assumptions about the age of the deep water, which in turn depend on assumptions about the nature of the deep thermal system. Modeling, based on published chloride-flux studies of thermal waters, suggests that for a 0.5- to 4-km-deep reservoir the residence time of most of the thermal water could be less than 1,900 years, for a piston-flow model, to more than 10,000 years, for a well-mixed model. For the piston-flow model, the deep system quickly reaches the isotopic composition of the recharge in response to climate change. For this model, stable-isotope data and geologic considerations suggest that the most likely area of recharge for the deep thermal water is in the northwestern part of the Park, in the Gallatin Range, where major north-south faults connect with the caldera. This possible recharge area for the deep thermal water is at least 20 km, and possibly as much as 70 km, from outflow in the thermal areas, indicating the presence of a hydrothermal system as large as those postulated to have operated around large, ancient igneous intrusions. For this model, the volume of isotopically light water infiltrating in the Gallatin Range during our sampling period is too small to balance the present outflow of deep water. This shortfall suggests that some recharge possibly occurred during a cooler time characterized by greater winter precipitation, such as during the Little Ice Age in the 15th century. However, this scenario requires exceptionally fast flow rates of recharge into the deep system. For the well-mixed model, the composition of the deep reservoir changes slowly in response to climate change, and a significant component of the deep thermal water could have recharged during Pleistocene glaciation. The latter interpretation is consistent with the recent discovery of warm waters in wells and springs in southern Idaho that have δD values 10–20 ‰ lower than the winter snow for their present-day high-level recharge. These waters have been interpreted to be Pleistocene in age (Smith and others, 2002). The well-mixed model permits a significant component of recharge water for the deep system to have δD values less negative than –150 ‰ and consequently for the deep system recharge to be closer to the caldera at a number of possible localities in the Park.

Idaho, Montana, Wyoming↗
USGS2005

Paleoproterozoic high-sulfidation mineralization in the Tapajós gold province, Amazonian Craton, Brazil: geology, mineralogy, alunite argon age, and stable-isotope constraints

The Brazilian Tapajós gold province contains the first evidence of high-sulfidation gold mineralization in the Amazonian Craton. The mineralization appears to be in large nested calderas. The Tapajós–Parima (or Ventuari–Tapajós) geological province consists of a metamorphic, igneous, and sedimentary sequence formed during a 2.10 to 1.87 Ga ocean−continent orogeny. The high-sulfidation mineralization with magmatic-hydrothermal alunite is related to hydrothermal breccias hosted in a rhyolitic volcanic ring complex that contains granitic stocks ranging in age from 1.89 to 1.87 Ga. Cone-shaped hydrothermal breccias, which flare upward, contain vuggy silica and have an overlying brecciated cap of massive silica; the deposits are located in the uppermost part of a ring-structure volcanic cone. Drill cores of one of the hydrothermal breccias contain alunite, natroalunite, pyrophyllite, andalusite, quartz, rutile, diaspore, woodhouseite–svanbergite, kaolinite, and pyrite along with inclusions of enargite–luzonite, chalcopyrite, bornite, and covellite. The siliceous core of this alteration center is surrounded by advanced argillic and argillic alteration zones that grade outward into large areas of propylitically altered rocks with sericitic alteration assemblages at depth. Several occurrences and generations of alunite are observed. Alunite is disseminated in the advanced argillic haloes that envelop massive and vuggy silica or that underlie the brecciated silica cap. Coarse-grained alunite also occurs in branching veins and locally is partly replaced by a later generation of fine-grained alunite. Silicified hydrothermal breccias associated with the alunite contain an estimated reserve of 30 tonnes of gold in rock that grades up to 4.5 g t −1 Au. Seven alunite samples gave 40 Ar/ 39 Ar ages of 1.869 to 1.846 Ga, with various degrees of apparent minor Ar loss. Stable isotopic data require a magmatic-hydrothermal origin for the alunite, typical for high-sulfidation mineralization. The δ 34 S values of most samples of alunite range from 14.0‰ to 36.9‰. Sulfur isotopic alunite–pyrite and oxygen isotopic alunite SO 4 −OH temperatures range from 130 to 420 °C. The δD H 2 O and δ 18 O H 2 O values for alunite-forming hydrothermal fluids suggest a predominance of magmatic water, with a small meteoric contribution. A rare sample of supergene alunite has a δ 34 S value of 4.1‰ and an 40 Ar/ 39 Ar age of 51.3±0.1 Ma. Other than local foliation in the volcanic rocks and recrystallization of alunite near faults, the mineralization and associated alteration appears to have been remarkably undisturbed by later metamorphism and by supergene alteration. The Au mineralization was preserved because of burial by sediments and tuffs in taphrogenic basins that probably developed shortly after mineralization and were probably first exhumed at about 60 Ma. Because high-sulfidation mineralization forms at relatively shallow crustal levels, the discoveries in Tapajós province provide new perspectives for mineral exploration for the Amazonian and perhaps for other Precambrian cratons.

Chemical Geology↗
USGS2005

Supergene destruction of a hydrothermal replacement alunite deposit at Big Rock Candy Mountain, Utah: Mineralogy, spectroscopic remote sensing, stable-isotope, and argon-age evidences

Big Rock Candy Mountain is a prominent center of variegated altered volcanic rocks in west-central Utah. It consists of the eroded remnants of a hypogene alunite deposit that, at ∼21 Ma, replaced intermediate-composition lava flows. The alunite formed in steam-heated conditions above the upwelling limb of a convection cell that was one of at least six spaced at 3- to 4-km intervals around the margin of a monzonite stock. Big Rock Candy Mountain is horizontally zoned outward from an alunite core to respective kaolinite, dickite, and propylite envelopes. The altered rocks are also vertically zoned from a lower pyrite–propylite assemblage upward through assemblages successively dominated by hypogene alunite, jarosite, and hematite, to a flooded silica cap. This hydrothermal assemblage is undergoing natural destruction in a steep canyon downcut by the Sevier River in Marysvale Canyon. Integrated geological, mineralogical, spectroscopic remote sensing using AVIRIS data, Ar radiometric, and stable isotopic studies trace the hypogene origin and supergene destruction of the deposit and permit distinction of primary (hydrothermal) and secondary (weathering) processes. This destruction has led to the formation of widespread supergene gypsum in cross-cutting fractures and as surficial crusts, and to natrojarosite, that gives the mountain its buff coloration along ridges facing the canyon. A small spring, Lemonade Spring, with a pH of 2.6 and containing Ca, Mg, Si, Al, Fe, Mn, Cl, and SO 4 , also occurs near the bottom of the canyon. The 40 Ar/ 39 Ar age (21.32±0.07 Ma) of the alunite is similar to that for other replacement alunites at Marysvale. However, the age spectrum contains evidence of a 6.6-Ma thermal event that can be related to the tectonic activity responsible for the uplift that led to the downcutting of Big Rock Candy Mountain by the Sevier River. This ∼6.6 Ma event also is present in the age spectrum of supergene natrojarosite forming today, and probably dates the beginning of supergene alteration at Big Rock Candy Mountain. The δ 34 S value (11.9‰) of alunite is similar to those for replacement alunite from other deposits in the Marysvale volcanic field. The δ 34 S values of natrojarosite (0.7‰ to −1.2‰) are similar to those for aqueous sulfate in Lemonade Spring, but are larger than those in pyrite (0.4‰ to −4.7‰). The δ 34 S and δ 18 O SO 4 values of gypsum show an excellent correlation, with values ranging from 15.2‰ to −5.2‰ and 7‰ to −8.2‰, respectively. The stable-isotope data indicate that the aqueous sulfate for gypsum is a mixture derived from the dissolution of hypogene gypsum and alunite, and from the supergene oxidation of pyrite. The aqueous sulfate for the natrojarosite, however, is derived largely from the supergene oxidation of pyrite, with a minor contribution from the dissolution of alunite and gypsum. The exceptional detailed spectral mapping capabilities of AVIRIS led to the recognition of a small amount of jarosite that is probably the top of the steam-heated system that produced the primary hypogene alteration at Big Rock Candy Mountain.

Utah↗
USGS2003

Preliminary Mineralogic and Stable Isotope Studies of Altered Summit and Flank Rocks and Osceola Mudflow Deposits on Mount Rainier, Washington

About 5600 years ago part of Mount Rainier?s edifice collapsed with the resultant Osceola Mudflow traveling more than 120 km and covering an area of at least 505 km2. Mineralogic and stable isotope studies were conducted on altered rocks from outcrops near the summit and east flank of the volcano and samples of clasts and matrix from the Osceola Mudflow. Results of these analyses are used to constrain processes responsible for pre-collapse alteration and provide insight into the role of alteration in edifice instability prior to the Osceola collapse event. Jarosite, pyrite, alunite, and kaolinite occur in hydrothermally altered rock exposed in summit scarps formed by edifice collapse events and in altered rock within the east-west structural zone (EWSZ) of the volcano?s east flank. Deposits of the Osceola Mudflow contain clasts of variably altered and unaltered andesite within a clay-rich matrix. Minerals detected in samples from the edifice are also present in many of the clasts. The matrix includes abundant smectite, kaolinite and variably abundant jarosite. Hydrothermal fluid compositions calculated from hydrogen and oxygen isotope data of alunite, and smectite on Mount Rainier reflect mixing of magmatic and meteoric waters. The range in the dD values of modern meteoric water on the volcano (-85 to 155?) reflect the influence of elevation on the dD of precipitation. The d34S and d18OSO4 values of alunite, gypsum and jarosite are distinct but together range from 1.7 to 17.6? and -12.3 to 15.0?, respectively; both parameters increase from jarosite to gypsum to alunite. The variations in sulfur isotope composition are attributed to the varying contributions of disproportionation of magmatic SO2, the supergene oxidation of hydrothermal pyrite and possible oxidation of H2S to the parent aqueous sulfate. The 18OSO4 values of jarosite are the lowest recorded for the mineral, consistent with a supergene origin. The mineralogy and isotope composition of alteration minerals define two and possibly three environments of alteration. At deeper levels magmatic vapor, H2S, SO2 and other gases from venting magmas migrated upward and condensed into the meteoric water. Disproportionation of SO2 into aqueous sulfate and H2S resulted in acid-sulfate (alunite + kaolinite + pyrite) and related argillic and propylitic alteration envelopes in a magmatic hydrothermal environment. At shallow levels H2S reacted with andesite to form pyrite that is associated with smectite along fractures on both the flanks and upper edifice. It is not clear to what extent H2S was oxidized by atmospheric O2 to form aqueous sulfate in a steam-heated environment. Near the ground surface, pyrite is oxidized by atmospheric oxygen resulting in soluble iron-and aluminum-hydroxysulfates. These supergene hydroxysulfates, which may also form around fumaroles from the oxidation of H2S, are subject to continuous solution and redeposition.

Open-File Report↗
USGS2000

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↗
USGS2000

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↗
USGS2000

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↗
USGS2000

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↗