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The Fe-Sb-S system

The phase relations in the Fe-Sb-S system from 300 ° to 800 ° C have been determined using new experimental data on phase assemblages and univariant equilibria in conjunction with information from the literature. Estimates have been made for the standard free energies of formation as a function of temperature for stibnite, berthierite, gudmundite, and FeSb 2 . Comparison of calculated mineral stabilities with published information on mineral assemblages suggests that apparently contradictory mineral associations may well represent equilibration at different (but all low) temperatures with subsequent lack of reaction as temperature fell to the temperature of observation. Resolution of the complicated, low-temperature phase relations will require additional thermochemical data of unusually high accuracy that might well be supplemented by careful study of natural materials. Berthierite, gudmundite, and aurostibite are clearly stable only under conditions of relatively low sulfur activity. FeSb 2 requires such low sulfur activity for its stable existence that it is seldom, if ever, to be expected as a mineral. The tendency for the common ore mineral galena to react with berthierite to yield pyrrhotite plus a lead sulfantimonide operates to make berthierite a rather uncommon mineral.

Economic Geology↗

Residual enrichment and supergene transport of gold, Calhoun mine, Lumpkin County, Georgia

Gold is present in weathered wall rock and quartz veins of the opencut of the Calhoun mine, Lumpkin County, Georgia. Eleven samples of mica schist saprolite contain 0.02 to 0.1 parts per million (ppm) gold and three samples of weathered vein quartz, 0.04 to 0.6 ppm (limit of detection is 0.02 ppm). Gold was not found in any of the 18 samples of fresh mica schist and was found in only 3 of 16 samples of fresh vein quartz from underground workings 40-100 feet below the opencut. Whole-rock chemical analyses of the unweathered schist and schist saprolite show large losses of minor elements and addition of water during weathering. The average specific gravity of the unweathered schist is 2.8 and of the schist saprolite, 1.65. The chemical analyses recalculated to weight per volume show a loss during weathering of large amounts of all major constituents including silica, alumina, and total iron. Of the minor elements, gold and arsenic show the most residual enrichment, but boron, beryllium, cobalt, lanthanum, niobium, nickel, lead, zinc, and zirconium show some enrichment in the saprolite as compared with the fresh rock. Most of the other minor elements have been at least partly removed, the greatest loss being shown by calcium, potassium, magnesium, sodium, and strontium. Fresh limonite coating the wall of the adit contains 2.9 ppm gold and appreciable amounts of these elements leached from the schist, particularly barium, calcium, and manganese. Some layers of unweathered schist contain as much as 1 percent gold-bearing pyrite and may have a gold content of 0.01 and 0.02 ppm, or just at or below the limit of detection. Loss of 30 to 45 percent of the rock during weathering increases the gold content above the lower limit of detection. The gold in recently deposited limonite shows that some gold is also being transported with iron during weathering. If a concentration of limonite were found near the water table, it might be expected to show supergene enrichment in gold.

Georgia↗

Sulfur isotope study of the "B" limestone and Galena fissure ore deposits of the U.S. mine, Bingham mining district, Utah

The delta S 34 values for 261 sulfide concentrates from the "B" limestone replacement and Galena fissure deposits of the U. S. mine range from +3.8 to --8.0 permil; the mean is +0.56 permil. The data indicate that (1) sulfides of the "B" limestone ore deposits are depleted in S 34 by 0.4 to 0.7 permil relative to those of the Galena fissure ore deposits; (2) sulfides of both deposits exhibit a primary fractionation trend characterized by increasing S 34 depletion in the sequence pyrite, sphalerite, tetrahedrite, and galena; (3) delta values for coexisting sulfide pairs of the "B" limestone deposit increase with increasing altitude; (4) sulfides of both deposits are increasingly depleted in S 34 with increasing altitude; (5) the paragenetic order of sulfide deposition is accompanied by an apparent depletion of S 34 that is independent of mineral species; and (6) pyrite disseminated in wall rocks is depleted in S 34 relative to pyrite from adjacent ore deposits. The similarity of delta S 34 values and isotopic trends to those of the central porphyry-type deposit at Bingham (Field, 1966) suggests that the hydrothermal deposits of the district were formed by fluids that originated from a common source during one episode of sequential mineralization. Gross isotopic differences between the deposits, consistent differences between coexisting sulfides, and systematic variations of delta values are attributed to temperature effects imposed upon sulfide exchange equilibria; isotopic temperatures suggest a lateral gradient between the "B" limestone and adjacent Galena fissure deposits and a possible vertical gradient within the "B" limestone deposit. The vertical zonation of delta S 34 values and trends related to pyrite physical occurrence and sulfide paragenesis are provisionally attributed to a pH-Eh control. Although the apparent trends are imperfectly resolved because of textural complexities, the marked depletion of S 34 in pyrite disseminated in country rocks warrants additional study as a potential exploration method.

Utah↗

Fluid inclusion studies on the porphyry-type ore deposits at Bingham, Utah, Butte, Montana, and Climax, Colorado

Data are given on the composition, temperature, pressure, and density of the hydrothermal fluids present in the central Cu-Mo core of the deposit at Bingham, Utah, and in its related but not necessarily coeval peripheral Pb-Zn deposits. These data are based on a study of primary and secondary fluid inclusions in transparent ore and gangue minerals that included the use of freezing, heating, and crushing microscope stages. The composition of the hydrothermal fluids at various stages in the mineralization and repeated later fracturing and rehealing ranged from nearly fresh water to water containing more than 60 weight percent salts in solution--virtually a hydrous saline melt--in some quartz-molybdenite-chalcopyrite veins from the core. Most of these salts have crystallized out as daughter minerals on cooling, forming major amounts of halite and sylvite and minor amounts of anhydrite (?), hematite (?) and several unidentified phases. These highly saline fluids occur only in the core. Some of them have apparently boiled, forming bubbles of a relatively low density CO 2 -rich "steam" containing only a few percent NaCl. These low-density fluids have also been trapped as inclusions. The fluids that formed the peripheral deposits had low salinities, and some of these also have apparently boiled. A few were very high in hydrogen sulfide. Inclusions from a quartz pod and in the quartz-molybdenite-chalcopyrite veins from the core yield the highest temperatures, 640 ° -725 ° C; most inclusions from the core homogenize at temperatures above 400 ° C. Samples from the peripheral deposits were uniformly lower, in the range 294 ° -330 ° C. The abundant evidence of intermittent boiling of these solutions is important because it places limits on the pressure at the time of trapping, it results in there being little or no need for a pressure correction to the homogenization temperatures, and it indicates that the pressure has varied with time. Although some of the homogenization temperatures are very high, the high salinity causes the vapor pressures at homogenization to be relatively low, from about 80 to a maximum of about 1,100 atmospheres. The density of the hydrothermal fluids is of great concern in any consideration of flow patterns, and particularly in the inevitable mixing with possibly heated ground waters. Steam inclusions from the core had gross densities of 0.3 to 0.1 g · cm -3 , but many of the highly saline inclusions in the core contain fluids whose density at trapping was as high as 1.3 g · cm -3 . The fluids trapped in inclusions in the peripheral deposits had densities of 0.75-0.95 g · cm -3 , well below that of the surrounding cold ground water. Hydraulic pressure gradients from these density differences, and the vapor pressures involved, must also have varied with time in any given location, particularly when boiling occurred, and thus the circulation patterns could have been very complex. The more highly saline fluids are believed to be of truly magmatic origin, and not merely heated ground water from the area at the time of the intrusion. The great abundance throughout the core of planes of secondary inclusions in which individual planes are uniform but adjacent planes have widely varying composition, density, and homogenization temperature, is evidence of thorough and repeated fracturing of these rocks under hydrothermal conditions. Inclusions were also examined in some samples from Butte, Montana, Climax, Colorado, and several Arizona porphyry copper deposits. The ranges of temperature, composition, and density found were similar but smaller than at Bingham. This might be simply a result of insufficient sampling.

Arizona, Colorado, Montana, Utah↗

Correlation of uranium, thorium, and potassium with aeroradioaetivity in the Berea Area, Virginia

In the Berea area, a small quartz monzonite pluton intrudes chlorite-actinolite schist and is overlapped by Coastal Plain sand and gravel deposits. A detailed aeroradioactivity survey of the area shows unusually high radioactivity (1,150 counts per second) over the quartz monzonite. A total of 22 auger samples was taken across all formations to a depth of 2 to 3 feet, and radioelement concentrations were determined by gamma-ray spectrometry. There is a general direct correlation of high radioactivity with increase in radioelement concentrations. Abundances of uranium and particularly thorium in the quartz monzonite are two and three times the average for rocks of this type; a comparison is made with other granitic rocks high in uranium and thorium. © 1971 Society of Economic Geologists, Inc.

Virginia↗

Gold content of natural waters in Colorado

Neutron activation analysis of 67 samples of water draining from gold-barren and gold-enriched sedimentary, igneous, and metamorphic rocks of the Colorado Front Range reveals a relatively small range in total gold content (nondetectable to 150 nanograms per liter). "Solute" gold concentrations were generally higher than particulate gold concentrations and both were unrelated to rock or water types. The data suggest the occurrence of a spring flush out of "solute" gold in groundwater discharge during the snow-melt recharge period but indicate that direct hydrogeochemical prospecting for gold is unpromising.

Colorado↗

Fractionation of minor elements between galena and sphalerite, Darwin lead-silver-zinc mine, Inyo County, California and its significance in geothermometry

Minor element abundances were determined for galena and sphalerite from the Darwin mine, Inyo County, California. The temperature of deposition was calculated from the distribution coefficients determined experimentally by Bethke and Barton (1971) for cadmium and manganese in coexisting galena and sphalerite. The fractionation of cadmium between coexisting sphalerite and galena indicates a temperature of deposition of 416 degrees C+ or -20 degrees , the fractionation of manganese between the same mineral pair a temperature of 377 degrees C+ or -32 degrees . The fractionation of selenium gave unreasonably high temperatures. Three pairs gave temperatures between 568 degrees and 625 degrees C, the fourth pair a temperature of 889 degrees C. The reason for this descrepancy is not known.

California↗

Primary and secondary sulfates at Goldfield, Nevada

High S-34 values for primary alunites (formed during hydrothermal phase) replacing plagioclase and groundmass of altered volcanic rocks, secondary alunite veins (formed during supergene alteration) with S-34 values near zero permil

Nevada↗

A geochemical hypothesis for dolomitization by ground water

Most modern disordered dolomite has been found in dynamic environments. However, solutions associated with modern dolomite formation do not have a common Mg/Ca ratio; the ratio ranges from about 3 to 100. Ground-water circulation may have a significant role in formation of regional dolomites; one of the primary requirements for regional dolomite formation is a large supply of magnesium ions. An X-ray study of well cuttings from the Tertiary limestone aquifer of central Florida indicates that it is composed primarily of calcite and dolomite with minor amounts of quartz and apatite. The magnesium content of the calcite is slightly lower (0-2 percent MgC03) in the recharge areas than in the deeper confined parts of the aquifer system (2-4 percent MgC03). Our data support other recent work and indicate an equilibrium constant for dolomite of 2 X 10-17. Inasmuch as this value is exactly the square of the calcite equilibrium constant (10~8-35), the Mg/Ca ratio must be unity for the three-phase equilibrium, calcite-dolomite-water. The Mg/Ca ratio in water from the aquifer is as low as 0.05 in the recharge area where the water is also undersaturated with respect to both calcite and dolomite. With time and length of travel path in the system, the water increases systematically in Mg/Ca ratio, which approaches unity; saturation with respect to the two carbonates also increases downgradient until the solution apparently becomes over-saturated with respect to both carbonates. In Tertiary limestones of the Yucatan Peninsula, the Mg/Ca range in water is similar to that for Florida. The small amount of magnesium available from the solution of magnesium calcites and dolomite in the potable zone of active circulation is insufficient to provide the amount required for extensive dolomitization unless enormous quantities of rock are available for dissolution. However, dolomite may be forming in the zones of brackish water that underlie the Florida and Yucatan Peninsulas. The required magnesium may be derived from the readily available ocean water or reflux brines as the hydrologic regimen is changed because of relative fluctuations of sea level.

Florida↗

An early middle ordovician age for collapse breccias in the east Tennessee zinc districts as indicated by compaction and porosity features

The carbonate strata of the Lower Ordovician formations in the southern Appalachian Valley were probably considerably thicker, less compacted, and more porous and permeable in early Middle Ordovician time than they are now. Analysis of selected compaction features of rocks associated with the breccias of the East Tennessee zinc districts permits quantitative estimation of the relative compaction (reduction in thickness) these sediments have undergone before and after brecciation. Total reduction in thickness of certain Lower Ordovician marker beds because of compaction during burial under younger Paleozoic sedimentary rocks and imbricate Appalachian thrust sheets appears to be at least some 40 to 50 percent. Furthermore, it is also estimated that about half of this compaction took place after brecciation in the solution-collapse structures of the zinc deposits. In comparison with laboratory compaction tests on carbonate muds it is apparent that the Lower Ordovician rocks had been buried to a depth of at least several thousand feet by the end of the Paleozoic Era. On the other hand the zones of collapse breccias probably formed at depths of generally less than a thousand feet, thus indicating an early Middle Ordovician age for their development. The general character of the rock during this time probably was similar to that of Tertiary limestone, which acts as the principal aquifer in the Coastal Plain region of southeastern United States.

Tennessee↗

A lower paleozoic paleoaquifer; the Kingsport Formation and Mascot dolomite of Tennessee and southwest Virginia

The Kingsport Formation (Lower Ordovician) in one section may be composed of two dominant rock types--limestone and medium to coarsely crystalline dolomite--whereas in an adjacent section, most of the formation may be largely composed of breccia. The breccia bodies, which are interpreted to be solution-collapse features, range in width from 30 feet to several hundred feet, in thickness from a few feet to more than 200 feet, and are hundreds of feet long. Many of the complexities of the Kingsport can be directly related to the development of an unconformity at the top of the overlying Mascot Dolomite. Erosion associated with the unconformity produced a widespread karst topography with an attendant paleoaquifer system. Ground water, apparently reacting to differences in solubility between limestone of the Kingsport and dense dolomite of the Mascot, is thought to be a major contributing factor in regional dolomitization and localization of solution-thinning and collapse features at the contact of the Kingsport and Mascot. Later mineralizing solutions invaded the paleoaquifer, locally depositing commercial quantities of zinc ore.

Virginia, Tennessee↗

Models of mineralized solution-collapse structures from drilling statistics: An aid to exploration

Variations in thickness and metal content of selected stratigraphic units cut by drill holes in the East Tennessee zinc districts have been analyzed by regression techniques. Such analysis demonstrated that as the thickness of an underlying limestone unit is decreased chiefly by solution thinning, overlying fine-grained dolomite units increase in thickness by collapse dilation. Variation in metal content is closely associated with this inverse thickness relationship because of the deposition of the ore minerals in the dilation openings. Most of the ore is found where the fine-grained dolomite units were so dilated by collapse as to form a series of rubble to crackle breccias. Hypothetical cross sections synthesized from widely spaced drill-hole data show mineralized structures of a size, shape, and distribution of metal comparable to those diagrammed in the literature from actual field relations. From these composite models of hypothetical structures the relative position of a particular hole can be approximated within its own structure. The exploration geologist thus has a numerical aid for estimating the amounts of offset needed to penetrate the most favorable part of the mineralized collapse structure with second-stage drill holes.

Economic Geology↗