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P. B. Barton

Publications and source records attributed to P. B. Barton.

12 recordsLinked to original sources

Commentary on the sphalerite geobarometer

The FeS content of sphalerite in assemblages with pyrite and pyrrhotite has been widely used and widely criticized as a geobarometer. The commonly accepted form of the geobarometer is based on the composition of sphalerite being independent of temperature below about 550??C at all pressures up to at least 10 kbar, but strong thermodynamic arguments require a significant temperature dependence in this region. Most minor components have a negligible effect on the relevant equilibria, but the effect of CuS is somewhat more significant. Molar and partial molar volumes for binary (ZnS-FeS) and ternary (ZnS-FeS-CuS) sphalerite solutions are presented; the ternary data are consistent with charge transfer between Cu and Fe. -from Authors

American Mineralogist

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

Low-temperature heat capacity and entropy of chalcopyrite (CuFeS2): estimates of the standard molar enthalpy and Gibbs free energy of formation of chalcopyrite and bornite (Cu5FeS4)

The heat capacity of CuFeS2 (chalcopyrite) was measured between 6.3 and 303.5 K. At 298.15 K, Cp,mo and Smo(T) are (95.67??0.14) J??K-1??mol-1 and (124.9??0.2) J??K-1??mol-1, respectively. From a consideration of the results of two sets of equilibrium measurements we conclude that ??fHmo(CuFeS2, cr, 298.15 K) = -(193.6??1.6) kJ??mol-1 and that the recent bomb-calorimetric determination by Johnson and Steele (J. Chem. Thermodynamics 1981, 13, 991) is in error. The standard molar Gibbs free energy of formation of bornite (Cu5FeS4) is -(444.9??2.1) kJ??mol-1 at 748 K. ?? 1985.

Journal of Chemical Thermodynamics

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

Physical-chemical conditions of ore deposition

Ore deposits form under a wide range of physical and chemical conditions, but those precipitating from hot, aqueous fluids—i.e. the hydrothermal deposits—form generally below 700°C and at pressures of only 1 or 2 kbar or less. Natural aqueous fluids in rocks may extract metal and sulfur from a variety of rock types or may acquire them as a residual heritage from a crystallizing silicate magma. Ore-forming hydrothermal fluids never appear as hot springs (except in deep, submarine situations) because they boil, mix with surface waters, and cool, thereby losing their ore-bearing ability before reaching the surface. Mineral systems function as chemical buffers and indicators just as buffers and indicators function in a chemical laboratory. By reading the record written in the buffer/indicator assemblages of minerals one can reconstruct many aspects of the former chemical environment. By studying the record of changing conditions one may deduce information regarding the processes functioning to create the succession of chemical environments and the ore deposits they represent. The example of the OH vein at Creede, Colorado, shows a pH buffered by the K-feldspar + muscovite + quartz assemblage and the covariation of S 2 and O 2 buffered by the assemblage chlorite + pyrite + quartz. Boiling of the ore fluid led to its oxidation to hematite-bearing assemblages and simultaneously produced an intensely altered, sericitic capping over the vein in response to the condensation of vapors bearing acidic components. The solubility of metals as calculated from experimental and theoretical studies of mineral solubility appears too low by at least one or two powers of ten to explain the mineralization at Creede. In contrast to Creede where the mineral stabilities all point to a relatively consistent chemistry, the Mississippi Valley type deposits present a puzzle of conflicting chemical clues that are impossible to reconcile with any single equilibrium situation. Thus we must seriously consider metastable equilibria; those most likely involve redox disequilibrium among the sulfur species in solution and perhaps also involve organic compounds.

Physics and Chemistry of the Earth

Thermochemical study of the system Fe-As-S

The results of Toulmin and Barton (1964) for the Fe-S system have been combined with a series of new measurements on As-bearing assemblages in the 500°–850°C temperature range to derive data on the free energies, enthalpies, and entropies of formation for arsenopyrite, loellingite, orpiment, realgar, FeAs, and Fe 2 As. The enthalpies and free energies of formation of orpiment and realgar are only approximately one-half as large as indicated in recent compilations of thermochemical data ( Wagman et al ., 1965). Data are also presented for the covariation of activity of S 2 (g) with temperature and composition of the sulfur-arsenic liquid.

Geochimica et Cosmochimica Acta

Phase relations involving sphalerite in the Fe-Zn-S system

The equilibrium diagram for the Fe - Zn - S System has been worked out in détail from 580° to 850° C. Previous work on this System is proven to be seriously in error and températures heretofore estimated from the " sphalerite geothermometer" are without a sound quantitative foundation. Sphalerite solid solutions lie essentially along the FeS-ZnS join. Neither pyrite nor pyrrhotite takes up appréciable amounts of zinc. The FeS-ZnS binary solvus (équivalent to the assemblage sphalerite + stoichi-ometric FeS) is very steep, passing through 56 mole percent FeS at 850° C and 52 mole percent FeS at 580° C. It is not useful geologically because of the rarity of stoichiometric FeS as a primary minerai in sphalerite -bearing assemblages; however, the relatively large rôle played by total pressure on the binary solvus might permit the iron content of sphalerite to be useful in determining the pressure of équilibration of some météorites. Of greater géologie interest is the sphalerite + pyrite + pyrrhotite assemblage in which the composition of sphalerite changes from 13 mole percent FeS at 742° C to 19 percent at 580° C. Unfortunately, this equilibrium cannot be quantitatively extrapolated to lower températures from the presently available data and therefore quantitative geothermom-etry of pyrite + pyrrhotite + sphalerite assemblages is not feasible at présent. Thermochemical calculations prove that the iron content of sphalerite in pyrite + sphalerite assemblages is very sensitive to variations in température and fugacity of S 2; this relationship provides an explanation of growth-zoned sphalerite as the resuit of fluctuations of sul-fur fugacity, and, in combination with other sulfide assemblages that define isobarically univariant relations between température and sulfur fugacity, forms a potential basis for quantitative geothermometry.

Economic Geology

Experimental determination of the reaction chalcopyrite + sulfur = pyrite + bornite from 350 to 500° C

The fugacity of sulfur along the curve representing the univariant equilibrium assemblage, chalcopyrite + bornite + pyrite + vapor, has been determined by the electrum tarnish method (1). The conditions of the equilibrium may be expressed by the equation (TP) - /°s 2 (T, 1 atm) = -50,730 + 56.95T (cal.) ( 350 - 500° C ) (T in °K). With gentle curvature, the line may be extended upward to the invariant point at 568° C , which represents the assemblage chalcopyrite + bornite -j- pyrite + liquid + vapor (8).

Economic Geology

The electrum-tarnish method for the determination of the fugacity of sulfur in laboratory sulfide systems

A new method for the determination of the fugacity of sulfur in laboratory systems consists of visual observation of the development and decomposition of a sulfide tarnish phase on silver-gold alloy (electrum) of precisely known composition. The alloy system is calibrated against pure sulfur. The method has the following advantages: simple apparatus; ability to cover a large range of fugacity of S 2 ; ability to cover a large temperature range by permitting runs of long duration; ability to tolerate other components in the gas phase; and ease of recovery of the quenched charges for determinations of phases and compositions. Results obtained by the electrum-tarnish method are in satisfactory agreement with those obtained by other workers for the f s2 vs. T curves for the assemblage Ni (1– x ) S + NiS 2 . The electrum-tarnish method shows promise for investigating many other reactions. Univariant reactions studied by this method can be represented as lines forming a genetic grid in terms of the environmental parameters f s2 and T , The slopes of such lines can yield valuable thermodynamic data for the phases involved, but activity coefficients must be known for phases of variable composition.

Geochimica et Cosmochimica Acta

A thermodynamic study of pyrite and pyrrhotite

Through the use of the electrum-tarnish method the following equation has been found to interrelate the composition of pyrrhotite, fugacity of sulfur, and temperature: In this equation f s2 is the fugacity of sulfur relative to the ideal diatomic gas at 1 atm, N is the mol fraction of FeS in pyrrhotite (in the system FeS-S 2 ), and T the absolute temperature. The experimental uncertainty in the equation is 0–003 in N . The activity of FeS ( a FeS ) in pyrrhotite relative to the pure substance at the temperature of consideration follows from the above equation by virtue of the Gibbs-Duhem relation; it is given by: The electrum-tarnish method has permitted us to determine the f s2 vs. T curve for the univariant assemblage pyrrhotite-pyrite-vapor from 743 to 325°C. Our determinations of the composition of pyrrhotite are in excellent agreement with the results of Arnold. The activity of FeS in pyrite-saturated pyrrhotite is very different from unity, a fact that greatly influences the interpretation of some other phase equilibrium studies involving pyrrhotite and their application to sulfide mineral assemblages, but has little effect on the more general calculations of composition of hydrothermal or magmatic fluids. Pressure effects calculated from available volumetric data on the phases are small.

Geochimica et Cosmochimica Acta

Some aspects of the geochemistry of sphalerite, Central City District, Colorado

Detailed studies of sphalerite , as a part of a larger study of the Central City district , Colorado , have been undertaken to learn something of the physico-chemical environment of ore deposition. More than 90 samples have been analyzed by chemical and spectrochemical methods and these data are interpreted in the light of experimental information. Sphalerite is a widespread and moderately abundant constituent of the gold- and silver-rich veins of the district . It was deposited during one stage of mineralization, in all environments of the concentrically zoned district except in the core. On a district -wide basis it occurs in three mineral assemblages: sphalerite -pyrite- chalcopyrite-tennantite-galena, sphalerite -pyrite-tennantite-galena, and sphalerite -pyrite-enargite-tennan-tite-galena. Quartz and, locally, other gangues are present.The sphalerite samples contain from 12 to 0.05 weight percent iron and detectable amounts of a restricted suite of minor elements, principally manganese, cadmium, copper, and lead. Manganese correlates directly with iron content, but the other minor elements have random correlations.The iron content of Central City sphalerite is interpreted to be mainly a function of activity of sulfur and temperature. Total pressure and minor elements that may enter the structure of either sphalerite or coexisting pyrite are thought to have negligible effects on the amount of iron in the sphalerite .The iron content of the sphalerite and fluid inclusion studies indicate that mineralization occurred over a temperature range from at least 620° C to about 150° C. In general, the temperatures tended to decrease from the vicinity of the central zone outward toward the peripheral zone. The thermal pattern, however, was complex, and marked by local irregularities.The activity of sulfur decreased with temperature, but to an extent such that more sulfur-rich mineral assemblages could form toward the margins of the district .The minor-element content of the sphalerite is governed by the activities of the various components and by the ability of the host mineral to accomodate it. Manganese varies widely because (1) it is geochemically much more abundant than is zinc and (2) it can also enter other minerals on a large scale. Conversely, because the amount of cadmium is small relative to that of zinc and because it enters only sphalerite in quantitatively significant amounts in hydrothermal environments, the cadmium content of sphalerite is constant. The copper content of the sphalerites is low and in good agreement with recent experimental data of Priestley Toulmin 3d.

Colorado

Effect of FeS on the unit cell edge of sphalerite, a revision

Redeterminations of the relation between the composition and unit-cell size of Fe-bearing sphalerites, necessitated because of partial oxidation of the FeS sample used in earlier measurements, are presented. It is noted that the Fe-ZnS solvus curve may also require revision and should be used with caution, particularly for temperature determinations in the higher ranges.

Economic Geology