Search USGS⌕ Search

Geology topics

P. M. Bethke

Publications and source records attributed to P. M. Bethke.

13 recordsLinked to original sources
USGS2005

Evolution of the magmatic-hydrothermal acid-sulfate system at Summitville, Colorado: Integration of geological, stable-isotope, and fluid-inclusion evidence

The Summitville Au-Ag-Cu deposit is a classic volcanic dome-hosted high-sulfidation deposit. It occurs in the Quartz Latite of South Mountain, a composite volcanic dome that was emplaced along the coincident margins of the Platoro and Summitville calderas at 22.5??0.5 Ma, penecontemporaneous with alteration and mineralization. A penecontemporaneous quartz monzonite porphyry intrusion underlies the district and is cut and overlain by pyrite-quartz stockwork veins with traces of chalcopyrite and molybdenite. Alteration and mineralization proceeded through three hypogene stages and a supergene stage, punctuated by at least three periods of hydrothermal brecciation. Intense acid leaching along fractures in the quartz latite produced irregular pipes and lenticular pods of vuggy silica enclosed sequentially by alteration zones of quartz-alunite, quartz-kaolinite, and clay. The acid-sulfate-altered rocks host subsequent covellite+enargite/luzonite+chalcopyrite mineralization accompanied by kaolinite, and later barite-base-metal veins, some containing high Au values and kaolinite. The presence of both liquid- and vapor-rich fluid inclusions indicates the episodic presence of a low-density fluid at all levels of the system. In the mineralized zone, liquid-rich fluid inclusions in healed fractures in quartz phenocrysts and in quartz associated with mineralization homogenize to temperatures between 160 and 390 ??C (90% between 190 and 310 ??C), consistent with the range (200-250 ??C) estimated from the fractionation of sulfur isotopes between coexisting alunite and pyrite. A deep alunite-pyrite pair yielded a sulfur-isotope temperature of 390 ??C, marking a transition from hydrostatic to lithostatic pressure at a depth of about 1.5 km. Two salinity populations dominate the liquid-rich fluid inclusions. One has salinities between 0 and 5 wt.% NaCl equivalent; the other has salinities of up to 43 wt.% NaCl equivalent. The occurrence of high-salinity fluid inclusions in vein quartz associated with mineralization, as well as in the deep stockwork veins, suggests that brines originating deep in the system transported the metals. The ??34S values of sulfides in magnetite (-2.3???) and of sulfate in apatite (5.4???) in unaltered quartz latite indicate that ??34S???S was near 0???. The ??34S values of coexisting alteration alunite and pyrite are 18.2??? to 24.5??? and -8.1??? to -2.2???, respectively. Deep in the system, most of the change in ??34S values occurs in the sulfates, indicating that the fluids were initially H2S-dominant, their redox state buffered at depth by equilibration with igneous rocks. However, in the main alteration zone, most of the change in ??34S values occurs in pyrite, indicating that the fluids moved off the rock buffer and became SO42- -dominant as pyrite precipitated and SO2 disproportionation produced the sulfuric acid requisite for acid leaching. The ??34S values of the late-stage barite and sulfides indicate that the system returned to high H2S/SO42- ratios typical of the original rock-buffered fluid. The ??DH2O of alunite parent fluids was near -45??? and their ??18O ranged from 7??? to -1???, depending on the degree of exchange in the alteration zone at low water-rock ratio, or mixing with unexchanged meteoric water. The low ??D values of some alunite samples are interpreted to result from postdepositional exchange with later ore fluids. Fluid exsolved fr om the magma at depth had ??DH2O and ??18OH2O values near -70??? and 10???, respectively. During and following migration to the top of the magma chamber, the fluid underwent isotopic exchange with the partially crystallized magma and its solid and cooler, but still plastic, carapace just below the transition from a lithostatic to hydrostatic pressure regime. These evolved magmatic fluids had ??DH2O and ??18OH2O values close to -40??? and 5???, respectively, prior to release into the superjacent hydrostatically pressured fracture zone, wherein the fluids separat

Chemical Geology↗
USGS1992

The stable isotope geochemistry of acid sulfate alteration

Acid sulfate wall-rock alteration, characterized by the assemblage alunite + kaolinite + quartz + or - pyrite, results from base leaching by fluids concentrated in H 2 SO 4 . Requisite amounts of H 2 SO 4 can be generated by different mechanisms in three principal geologic environments: (1) by atmospheric oxidation of sulfides in the supergene environment, (2) by atmospheric oxidation at the water table in the steam-heated environment of H 2 S released by deeper, boiling fluids, and (3) by the disproportionation of magmatic SO 2 to H 2 S and H 2 SO 4 during condensation of a magmatic vapor plume at intermediate depths in magmatic hydrothermal environments in silicic and andesitic volcanic terranes. In addition, coarse vein alunite may form in a magmatic steam environment from rapid release of an SO 2 -rich magmatic vapor phase at high temperature and low pressure or from the oxidation of a more reduced magmatic vapor by entrained atmospheric oxygen in the carapace of a volcanic edifice.Alunite [KAl 3 (SO 4 ) 2 (OH) 6 ] contains four stable isotope sites and complete analyses (delta D, delta 18 O (sub SO 4 ) , delta 18 O OH , and delta 34 S) are now possible. Except for delta 18 O OH in magmatic hydrothermal alunites, primary values are usually retained. In cooperation with many colleagues, over 500 measurements have been made on nearly 200 samples of alunite and associated minerals from 23 localities, and 55 additional analyses have been taken from the literature. This survey confirms that kinetic factors play an important role in the stable isotope systematics of alunite and acid sulfate alteration. To a very large extent they form the isotopic basis for distinguishing between environments of acid sulfate alteration, and they provide important insights into attendant processes. Stable isotope analyses of alunite, often in combination with those on associated sulfides and kaolinite, permit recognition of environments of formation and provide information on origins of components, processes (including rates), physical-chemical environments, and temperatures of formation.Supergene acid sulfate alteration may form over any sulfide zone when it is raised above the water table by tectonics or exposed by erosion. It may overprint earlier acid sulfate assemblages, particularly the magmatic hydrothermal assemblages which are pyrite rich such as at El Salvador, Chile; Rodalquilar, Spain; and Goldfield, Nevada. Supergene alunite normally has delta 34 S values virtually identical to precursor sulfides unless bacteriogenic reduction of aqueous sulfate takes place in standing pools of water. delta D values are close to that of local meteoric water unless extensive evaporation occurs. delta D and delta 18 O OH values of supergene alunites from a range of latitudes fall in a broad zone parallel to the meteoric water line much the way delta D and delta 18 O values of associated halloysite-kaolinite fall near the kaolinite line of Savin and Epstein (1970). delta 18 O (sub SO 4 ) values are kinetically controlled and will reflect the hydro-geochemistry of the environment. delta 18 O (sub SO 4 -OH) alues are grossly out of equilibrium and large negative values are definitive of a supergene origin.In steam-heated environments, such as those at the Tolfa district, Italy, and Marysvale, Utah, and numerous modern geothermal systems, acid sulfate alteration zones are characterized by pronounced vertical zoning. Such acid sulfate alteration may occur over adularia-sericite-type base and precious metal ore deposits such as the one at Buckskin, Nevada. Initial delta 18 O (sub SO 4 ) and delta 34 S values are kinetically controlled, but delta 18 O (sub SO 4 ) values usually reach equilibrium with fluids, and even delta 34 S values may reflect partial exchange with H 2 S where the residence time of aqueous sulfate is sufficient. Most alunites of steam-heated origin have delta 34 S values the same as those of precursor H 2 S (and as related sulfides, if present) and delta D values similar to that of local meteoric water. In the samples analyzed, most delta 18 O (sub SO 4 -OH) values give reasonable temperatures of 90 degrees to 160 degrees C, indicating that delta 18 O (sub SO 4 ) and delta 18 O OH values reflect a close approach to equilibrium with the fluid. The delta 18 O (sub SO 4 ) and delta 18 O OH values also reflect the degree of exchange of the meteoric fluids with wall rock. Coeval kaolinites typically have delta 18 O and delta D values to the left of the kaolinitc line.Magmatic hydrothermal, acid sulfate alteration zones in near-surface epithermal deposits such as Summitville, Colorado. Julcani, Peru, and Red Mountain and Lake City, Colorado, are characterized by vertical orientation and horizontal zoning, the presence of coeval pyrite, PO 4 analogues of alunite, zunyite, and later gold, pyrite and enargite, and often other Cu-As-Sb-S minerals. Acid sulfate alteration assemblages also occur as late stages in the porphyry-copper deposit at E1 Salvador, Chile. In the examples studied, magmatic hydrothermal alunites have delta D values close to those for magmatic water. delta 34 S values are 16 to 28 per mil larger than those for associated pyrite, reflecting equilibrium between aqueous H 2 S and SO 4 formed by the disproportionation of magmatically derived SO 2 . delta 18 O (sub SO 4 ) values are usually 8 to 18 per mil and vary systematically with delta 34 S values, reflecting variations in temperature and/or H 2 S/SO 4 fluid ratios. Further variation in delta 18 O (sub SO 4 ) values may result if SO 2 condenses in mixed magmatic meteoric water fluids. delta 18 O (sub SO (sub 4-) OH) values of magmatic hydrothermal alunites are generally unsuitable for temperature determinations because of retrograde exchange in the OH site, but delta 34 S (sub alunite-pyrite) values provide reliable temperature estimates.Magmatic steam environments appear to occur over a range of depths and are characterized by monomineralic veins of coarse alunite in variably alunitized and kaolinized wall rocks containing minor pyrite. Alunite formed in the magmatic steam environment can usually be recognized by delta 34 S near delta 34 S (sub Sigma S) values and delta D and delta 18 O (sub SO 4 ) values near magmatic values. Magmatic steam alunite differs from magmatic hydrothermal alunite by having delta 34 S close to delta 34 S (sub Sigma S) values of the system. delta 18 O (sub SO (sub 4-) OH) values of most magmatic steam alunite give temperatures ranging from 90 degrees to 210 degrees C but, for reasons which are not understood, some temperatures as well as calculated delta 18 O (sub H 2 O) values are too low for presumed precipitation from a magmatic vapor phase. Magmatic steam environments may occur over porphyry-type mineralization as at Red Mountain, Colorado, and Alunite Ridge, Utah, and over or adjacent to adularia-sericite-type deposits in volcanic domes as at Cactus, California.

Economic Geology↗
USGS1987

Chalcopyrite disease in sphalerite: pathology and epidemiology.

This descriptive paper identifies three widely occurring textures designated as 'watermelon', 'dusting' and 'bimodal' that characterize the replacement of original Fe-bearing sphalerite by an aggregate of chalcopyrite and low-Fe sphalerite as an integral part of the mineralization process. Replacement probably predominates over alternative modes of origin for small chalcopyrite blebs in sphalerite from most vein and sea-floor massive sulphide deposits that formed in the 200-400oC temperature range and that have not been subsequently subjected to higher T. Sphalerite from the epithermal Ag-Pb-Zn deposit at Creede, Colorado, displays a rich variety of features ("bead chains') that are primary crystal dislocations decorated by exsolved chalcopyrite.-J.A.Z.

American Mineralogist↗
USGS1985

PRE-ORE POTASSIUM METASOMATISM, CREEDE MINING DISTRICT, COLORADO.

Rhyolitic welded-tuff wallrocks of the epithermal base and precious metal veins of the Creede district were pervasively altered by the addition of more than two billion metric tons of potassium some 1. 5-2 million years before mineralization. Sodium, calcium and magnesium were strongly depleted, yielding a nearly binary quartz plus potassium feldspar assemblage containing as much as 13 weight percent K//2O. This large-scale metasomatism, originally noted by Steven and Rattle (1965), took place progressively by initial alteration of plagioclase phenocrysts to orthoclase or microcline followed by alteration of the groundmass feldspar to orthoclase and gradual change of the sanidine phenocrysts to more Or-rich compositions. Oxygen isotope and chemical studies show that the metasomatism resulted from the interaction of the tuffs with deeply circulating heated ground water and suggest that the potassium metasomatism of rhyolitic rocks is the facies equivalent of propylitization of volcanic rocks of more basic composition.

Conference Paper↗
USGS1982

Fluid-inclusion data on samples from Creede, Colorado, in relation to mineral paragenesis

Published and unpublished data on 2575 fluid inclusions in ore and gangue minerals from the Creede, Colorado, Ag-Pb-Zn-Cu vein deposit collected in our laboratories from 1959 to 1981 have shown that the average salinity (wt. % NaCl equivalent, hereinafter termed wt.% eq.) and homogenization temperature (Th), and the ranges of these two parameters for fluid inclusions in sphalerite, quartz, fluorite, and rhodochrosite, respectively, are 8.1 (4.6 - 13.4), 239?C (195-274?C); 6.1 (1.1-10.0), 260?C (190->400?C); 10.7 (6.1-11.1), 217?C (213-229?C) and 260?C (247-268?C) (bimodal distribution of Th); and 9.9 (9.3 - 10.6), 214?C (185-249?C). Inclusions have been measured in minerals from four of the five stages of mineralization previously recognized at Creede. The few inclusions of fluids depositing rhodochrosite (A-stage, earliest in the paragenesis) yield Th and salinity values more similar to those of the low-temperature (average Th 217?C) fluids forming some of the much later fluorite (C-stage) than to any of the other fluids. Th measurements on A-stage quartz range from 192?C to 263?C and average 237?C. The early, fine-grained, B-stage sphalerites yielded Th of 214 to 241?C and salinities of 6.1 to 10.2 wt. % eq. D-stage sphalerite (late in the paragenesis) has been studied in detail (growth-zone by growth-zone) for several localities along the OH vein and reveals a generally positive correlation among Th, salinity and iron content of the host sphalerite. The deposition of D-stage sphalerite was characterized by repeated cycling through different regions of salinity/Th space, as Th and salinity generally decreased with time. Seventeen salinity-Th measurements were made on D-stage sphalerite from one locality on the Bulldog Mountain vein system, which, like the OH vein, is one of four major ore-producing vein systems at Creede. These data suggest a lower Th for a given salinity fluid from sphalerite on the Bulldog Mountain vein than on the OH vein. The very high values of Th for some quartz samples (mostly D-stage) are believed to be a result of the trapping of both gas and liquid from a boiling fluid in the upper levels of the vein system. Boiling of fluids depositing D-stage quartz is indicated by the presence of steam inclusions in quartz and the extreme variability of Th values measured on quartz. The pressure was low (< 125 kg/cm 2) throughout ore deposition. Three major growth zones in D-stage sphalerite are recognized throughout the OH vein. Deposition of the first major zone began from fluids having intermediate salinities and temperatures (7.8-9.2 wt. % eq., 240?C) but the characteristics of the fluids oscillated after that, ranging from 7.2 to 10.1 wt. % eq. and from 225?C to 270?C. Deposition of the second major, most Fe-rich zone began with the hottest, most saline fluids present during D-stage mineralization (. 270?C, 10.5-12.5 wt. % eq., 3 mole % FeS in sphalerite). The fluid then oscillated with respect to Th and salinity (213-274?C, 5.2-12.5 wt. % eq.) but showed a general decrease in both with time. Deposition of the youngest major zone began with a very Fe-poor sphalerite (0.25-0.75 mole % FeS), from the least saline, coolest fluids (5-6.5 wt. % eq., 200-212?C) and ended with a trend of increasing temperature at approximately constant salinity. The fluid-inclusion data can best be explained by a mixing model involving at least two fluids--one hot and saline, the other cool and fresher. Sudden changes in the mixing ratio, presumably from changes in the plumbing, punctuated long periods of remarkably uniform conditions of ore fluid flow and deposition. The effects of other processes such as convection and heat exchange with wall rocks must have been superimposed on this simple mixing model, however. In contrast to an earlier interpretation, several aspects of the inclusion data may be interpreted to suggest exceedingly slow ore deposition. Work in progress may resolve some of these ambiguities and refine

Open-File Report↗
USGS1979

Environment of ore deposition in the Creede mining district, San Juan Mountains, Colorado; Part IV, source of fluids, from oxygen, hydrogen, and carbon isotope studies

The hydrogen isotopic composition of fluids responsible for formation of the near-surface silver-base metal vein deposits at Creede was measured by direct analysis of inclusion fluids in sphalerite, quartz, and rhodochrosite and was estimated from analyses of illite and chlorite. The oxygen isotopic composition was determined directly on inclusion fluids in sphalerite and was estimated from analyses of quartz, illite, rhodochrosite, siderite, and adularia. The carbon isotopic composition was estimated from analyses of rhodochrosite and siderite. The ranges in isotopic composition for water and CO 2 in the fluids associated with the formation of each of the minerals is given below (number of determinations given in parentheses):Mineral delta D (sub H 2 ) O ppm delta 18 O (sub H 2 ) O ppm delta 13 C (sub CO 2 ) ppmSphalerite -81 to -54 (4) -10.1 to -4.5 (4)Quartz -97 to -86 (4) -5.9 to 1.8 (18)Illite -62 to -50 (8) -1.6 to 1.2(7)Chlorite -64 to -55 (10) -2.2 to 0.8 (10)Adularia 4.2 (1)Rhodochrosite -82 to -78 (2) 4.2 to 9.4 (9) -5.7 to -4.2 (9)Siderite 4.9 to 9.9 (6) -6.9 to -2.7 (6)The delta D (sub H 2 ) O and delta 18 O (sub H 2 ) O values of fluids associated with the formation of sphalerite, quartz, illite/chlorite, and carbonate minerals differ substantially from one another, and these differences appear to have been maintained throughout the depositional history, regardless of the positions of the minerals in the paragenetic sequence.The data suggest that waters from three coexisting reservoirs fed the vein system alternately and episodically during vein formation, and apparently there was little mixing of the fluids from the different reservoirs. The hydrogen, oxygen, and carbon isotope data suggest that the carbonate waters were deep seated, probably dominantly magmatic, in origin. The sphalerite and illite/chlorite waters must have been dominantly meteoric in origin and substantially oxygen shifted by exchange with the volcanic country rocks. The quartz waters were also oxygen shifted meteoric waters but were some 40 per mil lower in deuterium content than the sphalerite and illite/chlorite waters.We propose that the quartz fluids entered the vein system from reservoirs beneath the mountainous areas to the north in the vicinity of the present Continental Divide, but that the sphalerite and illite/chlorite fluids entered the vein system from a topographically low area to the south along the structural moat of the Creede caldera. The difference in delta D between the two meteoric waters may reflect differences in altitude of the recharge areas for the two reservoirs or may be clue to isotopic evolution of the closed-basin lake and interstitial waters in the moat surrounding the Creede caldera.

Colorado↗