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Robert O. Rye

Publications and source records attributed to Robert O. Rye.

32 records · Page 2Linked to original sources
USGS1994

Experimental studies of alunite: I. 18 O- 16 O and D-H fractionation factors between alunite and water at 250-450°C

We have determined oxygen and hydrogen isotope fractionation factors between alunite and water over a temperature range of 250-450??C by reacting synthetic natroalunite with 0.7 m K2SO4 -0.1 to 0.65 m H2SO4 solutions to produce K-rich alunite. From 88 to 95% alkali and isotope exchange were observed in most of these experiments, and the partial equilibrium method was used to compute equilibrium fractionation factors. Least-squares fits of the data give 103 In ??alunite(so4)-H2O = 3.09 ( 106 T2 (K)) - 2.94 and 103 In ??alunite(OH)-H2O = 2.28 ( 106 T2 (K)) - 3.90. The intramineral 18O- 16O fractionation factor 103 In ??alunite(so4-OH site) is given by the expression 0.8 ( 106 T2 (K)) + 0.96. The alunite-water D-H fractionation factor ranges from -19 at 450??C to -6 at 250??C and does not appear to be strongly dependent on temperature. Runs with alkali exchange in the opposite direction were used to obtain 18O- 16O and D-H fractionation factors between natroalunite (mol% Na = 70-75) and water at 350-450??C. These indicate that mol% Na has negligible effect on the fractionation factors over this temperature range. Measured 18O-16O and D-H fractionation factors between alunite and 1.0 m KCl -0.5 m H2SO4 fluids also agree within 2?? with the values obtained from the K2SO4-H2SO4 fluids. However, experiments with alunite and distilled water at 400??C gave a value of 103 In ??alunite(SO4)-H2O of 0.0, compared with a value of 3.9 obtained at this temperature with K2SO4- and H2SO4-bearing fluids. This suggests that changes in fluid composition can affect alunite-water 18O-16O fractionation factors. Reconnaissance experiments with fine-grained natural natroalunite demonstrate that alunite-water D-H exchange can occur by hydrogen diffusion, although this process is generally not significant in the experiments with coarser grained synthetic alunites. ?? 1994.

Geochimica et Cosmochimica Acta↗
USGS1989

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↗
USGS1985

Geologic characteristics of sediment- and volcanic-hosted disseminated gold deposits - Search for an occurrence model

The current expansion of resource information, particularly on "disseminated" gold, and the improved technologies now available for resource investigations should place us in an enhanced position for developing a better predictive methodology for meeting one of the important responsibilities of the U.S. Geological Survey-to examine and assess the mineral resources of the geologic terranes composing the public (and privately owned) lands of the United States. The first step is systematic organization of these data. Geologic-occurrence models are an effective systematic method by which to organize large amounts of resource information into a logical sequence facilitating its use more effectively in meeting several industry and Survey objectives, which include the exploration for resources and the assessment of resource potential for land-use decisions. Such models also provide a scientific basis for metallogenesis research, which considers the observable features or attributes of ore occurrence and their "fit" into the Earth's resource puzzle. The use of models in making resource assessments/appraisals was addressed by Shawe (1981), who reported the results of a workshop on methods for resource appraisal of Wilderness and Conterminous United States Mineral Appraisal Program (CUSMAP; 1:250,000-scale quadrangles) areas. The Survey's main objective in the 1982 workshop was to evaluate the status of knowledge about disseminated or very fine grained gold deposits and, if possible, to develop an occurrence model(s). This report on the workshop proceedings has three main objectives: (1) Education through the publication of a summary review and presentation of new thinking and observations about the scientific bases for those geologic processes and environments that foster disseminated gold-ore formation; (2) systematic organization of available geologic, geochemical, and geophysical information for a range of typical disseminated gold deposits (including recognition of gaps in those data); and (3) assessment of current understanding (as presented in objective 2) toward formulating an empirical ore-occurrence model for this type of deposit. As such, this volume represents a preliminary first step at classification and provides a source of pertinent background information. Readers of this volume will soon discover, however, that full agreement has not yet been achieved in the interpretation of some of the geologic evidence. The resulting variations in tentative occurrence models for these controversial deposits ultimately will be resolved by filling the gaps in information that have already been identified. Thus, this volume does not report a U.S. Geological Survey consensus; the conclusions expressed in each chapter represent the particular interpretations of the various workshop participants.

Arizona, California, Idaho, Nevada, Utah↗
USGS1979

Formation and resulfidization of a South Texas roll-type uranium deposit

Core samples from a roll type uranium deposit in Live Oak County, south Texas have been studied and results are reported for Se, Mo, FeS2 and organic-carbon distribution, sulfide mineral petrology, and sulfur isotopic composition of iron-disulfide phases. In addition, sulfur isotopic compositions of dissolved sulfate and sulfide from the modern ground water within the ore bearing sand have been studied. The suite of elements in the ore sand and their geometric relationships throughout the deposit are those expected for typical roll-type deposits with well-developed oxidation-reduction interfaces. However, iron-disulfide minerals are abundant in the altered tongue, demonstrating that this interval has been sulfidized after mineralization (resulfidized or rereduced). Iron disulfide minerals in the rereduced interval differ mineralogically and isotopically from those throughout the remainder of the deposit. The resulfidized sand contains dominantly pyrite that is enriched in 34S, whereas the sand beyond the altered tongue contains abundant marcasite that is enriched in the light isotope, 32S. Textural relationships between pyrite and marcasite help to establish relative timing of iron disulfide formation. In reduced rock outside the altered tongue, three distinct generations of iron disulfide are present. The oldest of these generations consists largely of pyrite with lesser amounts of marcasite. A major episode of marcasite formation contemporaneous with ore genesis postdates the oldest pyrite generation but predates a younger pyrite generation. Resulfidization probably led to the final pyrite stage recognized beyond the altered tongue. Stable isotope data establish that the source of sulfur for the resulfidization was fault-leaked H2S probably derived from the Edwards Limestone of Cretaceous age which underlies the deposit. The deposit formed in at least two stages: (1) a pre-ore process of host rock sulfidization which produced disseminated pyrite as the dominant iron disulfide phase; and (2) an ore-stage process which led to the development of the uranium roll with emplacement of the characteristic suite of minor and accessory elements and which produced abundant isotopically light marcasite. The host rock was modified by a post-ore stage of resulfidization which precipitated isotopically heavy pyrite. Sulfur isotopic compositions of sulfide and sulfate present in modern ground water within the host sand differ greatly from sulfur isotopic composition of iron disulfides formed during the resulfidization episode. Iron disulfide minerals formed from the sulfur species of modern ground water have not been unequivocally identified.

Open-File Report↗
USGS1978

Origin of a South Texas roll-type deposit; II, Sulfide petrology and sulfur isotope studies

Petrologic and sulfur isotopic studies have been carried out on drill core samples from a roll-type uranium deposit in the mid-Tertiary Catahoula Tuff, Webb County, south Texas. Epigenetic iron disulfide minerals formed in two distinct stages. The first stage involved sulfidization of the host rock by sulfide (H 2 S, HS-)-bearing solutions that emanated from a fault about 1.5 km downdip from and subparallel to the orebody. Pyrite was the dominant iron disulfide mineral formed from this fault sulfide. The isotopic composition (delta 34 S) of first-stage iron disulfide is quite heavy (>0 per mil), in part because the fault-derived H 2 S was isotopically heavy. The development of the second-stage sulfides was related to processes that formed the uranium roll. Iron disulfide minerals produced during this second stage commonly occur as rims around the first-stage sulfides. The rims are exclusively marcasite in and adjacent to ore, but the pyrite content in these rims increases with increasing distance from ore. The sulfur of the second-stage sulfides in the vicinity of the roll front is isotopically light (--25 to --40 per mil). The virtual absence of organic carbon in the host sand precludes a bacterial origin for the ore-stage iron disulfide minerals and, therefore, eliminates bacterial metabolism as the mechanism for isotopic fractionation. Instead, the sulfur source for ore-stage sulfides was preore (first stage) sulfides, remobilized via partial oxidation to soluble metastable sulfur oxyanions.

Texas↗
USGS1978

Wood River mining district, Idaho - intrusion-related lead-silver deposits derived from country rock source

Lead-silver deposits in the Wood River mining district occur in shear zones in hornfelsed argillite of the Devonian Milligen Formation near granitic plutons and under the Wood River thrust fault. The principal ore minerals are argentiferous galena and sphalerite; siderite is the principal gangue. The δ 34 S values of the sulfide minerals range from +2.2 to +15.0 permil, indicating that the sulfur had a shallow crustal source. Δ 34 S values between sphalerite and galena range from +2.3 to +3.4 permil, corresponding to sulfur isotope temperatures between 280° and 182 °C. Hydrothermal barite has a δ 34 S of +13.2 permil. Lead isotope ratios are radiogenic, also pointing to a shallow crustal source. Quartz gangue has δ 18 O of +16.4 permil and a calculated δ 18 O H20 at 270°C of +8.4 permil. This value is reasonable for a hydrothermal fluid that had reached equilibrium with the argillite country rock. The siderite gangue has δ 18 O and δ 13 C values of +14.0 and -5.5 permil, respectively. Fluid inclusions have homogenization temperatures of 244°-307°C and average 270°C. Freezing-stage measurements ranged from -1.85 to -2.8°C, suggesting salinities of 3.2 to 4.8 weight percent. The δD values of inclusion fluid in ore and gangue minerals are -110 to -120 permil. The geology, isotope, and fluid-inclusion data are consistent with a model of hydrothermal systems of meteoric water in faulted and shattered Paleozoic rocks near plutonic masses. This environment permitted deep circulation of the hydrothermal fluids, which dissolved the metals and sulfur from the Paleozoic host rocks and deposited ore in favorable beds or structures under the regional Wood River thrust fault.

Idaho↗
USGS1974

Carbon, hydrogen, oxygen, and sulfur isotope study of the Darwin lead-silver-zinc deposit, Southern California

The ores at Darwin occur as massive replacement bodies in silicated limestones of Pennsylvanian and Permian age adjacent to a Jurassic quartz monzonite stock. Three types of ore have a definite spatial relationship to the quartz monzonite: (1) pyrite-sphalerite-galena ores, (2) pyrite-pyrrhotite-magnetite-sphalerite-galena ores, and (3) galena-Ag-Bi-Se ores.The delta 34 S values of all sulfide minerals range from +4.4 to --5.7 permil. The delta 34 S values for individual minerals tend to decrease with respect to both space and paragenetic time. The delta (sub sl-gn) values range from 1.5 to 2.5 permil and correspond to a temperature range of 325 degrees + or - 55 degrees C. The sphalerite-galena sulfur isotope temperatures at a given locality are reproducible to + or -30 degrees C and are consistent with temperatures determined by other means.Analyses of water in three samples of fluid inclusions in sphalerite indicate that the ore fluids had delta D values of --66 + or - permil, a total salinity that reached at least 20 percent, and K/Na atomic ratios of 0.23 + or - 0.03. Isotopic and thermochemical data indicate that the ore fluids had average values of delta 34 S (sub Sigma S) = 3 permil, delta 13 C (sub Sigma O) = -- 3.5 permil, Sigma S = 0.01 mole/Kg H 2 O, f (sub CO 2 ) = 12 + or - 8 bars, and Sigma C = 0.15 + or - 0.06 mole/Kg H 2 O.The delta 18 O values of postsulfide calcites have a range of 12.8 + or - 1.5 permil in the pyrite ores and 17 + or - 2 permil in the pyrrhotite ores. Similar values for relict limestone host rock in these areas indicate that oxygen isotopic equilibrium was established between the calcite precipitating fluids and the wall rock. The delta 13 C values of the calcites, however, range from --5.8 to --3.6 permil and are considerably more negative than the limestone in the host rock, indicating that carbon isotopic equilibrium was not established between the fluids and the wall rock.Thermochemical data indicate that the pH of the ore fluids was about 4.8 as they traveled through the quartz monzonite at T nearly equal 350 degrees C. When the fluids completely equilibrated with the relict limestone and calc-silicate host rock, the pH increased to 6.7. This increase in pH as the fluids traveled upward and away from the quartz monzonite was responsible for the spatial distribution of iron sulfide assemblages, for variations in delta 34 S values of sulfides, and probably caused precipitation of the ore.

California↗
USGS1969

Chemical composition of the hydrothermal fluids responsible for the lead-zinc deposits at Providencia, Zacatecas, Mexico

The chemical composition of 22 samples of primary fluid inclusions in quartz, calcite, and sphalerite from Providencia, Mexico, has been determined. Samples were prepared, crushed, and leached as described by Roedder et al. (1963). Cation analyses of leachates were made by atomic absorption spectroscopy, and the anions were analyzed by a special X-ray fluorescence technique. The Na, K, Ca, and C1 concentrations show a considerable range that reflects the widespread salinity variations in the hydrothermal fluids observed by Sawkins (1964). The K/Na atomic ratios of most samples range from 0.18 to 0.43 and the ratios tend to increase with the salinity of the inclusions. The temperatures indicated by the K/Na ratios from the published curves of K/Na ratios vs. temperature are mostly at least 100 ø C greater than corresponding filling temperatures. The Ca/Na atomic ratios of inclusions in sphalerite range from 0.12 to 0.61. The K/Na and Ca/Na data agree well with previous δO¹⁸ data (Rye, 1966; Rye and O'Neil. 1968) which indicate that the hydrothermal fluids were derived from the magma related to the Providencia granodiorite stock and that the fluids reacted only slightly with the crystalline stock during the late phases of ore deposition. The data also indicate that the salinity variations in the hydrothermal fluids probably occurred at the source of the fluids and may have resulted from boiling in the magma chamber. Mg concentrations are generally no more than a few hundred parts per million. Most of the Mg in the hydrothermal fluids was evidently removed during the formation of calcium-magnesium silicates in the lower levels of the ore pipes. Mg/Ca atomic ratios are generally less than 0.08 and are consistent with the paucity of dolomite in the area. Zn and Cu concentrations in water leaches of inclusions in calcite are generally less than 50 ppm. Maximum base-metal concentrations from water leaches of two samples of inclusions in quartz are 890 ppm Zn and 530 ppm Cu. Chloride is the major anion in the fluids, and C1 concentrations vary with corresponding cation concentrations. With two exceptions, sulfur concentrations of the inclusions in calcite and quartz, analyzed as SO₄, are below the level of detection

Zacatecas↗