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Results for “Fluid Phase Equilibria”

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USGS1996

A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

A composite phase diagram is presented for Structure H (sH) clathrate hydrates, In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

Fluid Phase Equilibria↗

USGS2011

U-Pb dating of large zircons in low-temperature jadeitite from the Osayama serpentinite melange, southwest Japan: Insights into the timing of serpentinization

Crystals of zircon up to 3 mm in length occur in jadeitite veins in the Osayama serpentinite mélange, Southwest Japan. The zircon porphyroblasts show pronounced zoning, and are characterized by both low Th/U ratios (0.2-0.8) and low Th and U abundances (Th = 1-81 ppm; U = 6-149 ppm). They contain inclusions of high-pressure minerals, including jadeite and rutile; such an occurrence indicates that the zircon crystallized during subduction-zone metamorphism. Phase equilibria and the existing fluid-inclusion data constrain P-T conditions to P > 1.2 GPa at T > 350°C for formation of the jadeitite. Most U/Pb ages obtained by SHRIMP-RG are concordant, with a weighted mean 206 Pb/ 238 U age of 472 ± 8.5 Ma (MSWD = 2.7, n = 25). Because zircon porphyroblasts contain inclusions of high-pressure minerals, the SHRIMP U-Pb age represents the timing of jadeitite formation, i.e., the timing of interaction between alkaline fluid and ultramafic rocks in a subduction zone. Although this dating does not provide a direct time constraint for serpentinization, U-Pb ages of zircon in jadeitite associated with serpentinite result in new insights into the timing of fluid-rock interaction of ultramafic rocks at a subduction zone and the minimum age for serpentinization.

International Geology Review↗

USGS1984

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO2-H2O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks. Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed. Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ??18O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences. The range of Adirondack carbonate ??18O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor 18O and 13C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ??18O calcites (25.0 to 27.2), low ??18O wollastonites (-1.3 to 3.5), and sharp gradients in ??18O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn). Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts. ?? 1984 Springer-Verlag.

Contributions to Mineralogy and Petrology↗

USGS1987

Phase relations in the system NaCl-KCl-H 2 O. III: Solubilities of halite in vapor-saturated liquids above 445°C and redetermination of phase equilibrium properties in the system NaCl-H 2 O to 1000°C and 1500 bars

Halite solubilities along the three-phase curve in the binary system NaCl-H 2 O determined by DTA experiment can be represented by the equation Wt.% NaCl (±0.2) = 19.39 − 0.0364 t + 3.553 × 10 −4 T 2 − 2.298 × 10 −7 T 3 , where 447≦ T ≦ 800° C . Even though these halite solubilities are up to ~7 wt.% higher than those reported in literature, extrapolated values at temperatures below 447°C merge with the literature values. It is considered that the equation adequately describes halite solubilities between 382 and 800°C. The newly established solubility data are believed to be more reliable because they are compatible with data obtained by using synthetic fluid inclusions and with the observed DTA signals and also because they were measured in a relatively corrosion-free system. In an earlier publication (GUNTER et al ., 1983), we were puzzled greatly by multiple and rather unreproducible DTA peaks appearing during isobaric cooling (heating experiments were nondefinitive) at pressures below about 500 bars. These DTA signals apparently suggested that the “halite liquidus” swung sharply upward in temperature as pressure decreased from about 500 bars to that of the halite-saturated boiling curve. Further analysis of the data and helpful discussions with several individuals have revealed that the behavior is a consequence of the initial (precooling) separation of the fluid into NaCl-poor gas and NaCl-rich liquid that failed to homogenize in the short time encompassed by the DTA experiments. The present analysis is based on extrapolations of the slopes from pressures above 500 bars. Through use of these new halite solubility data and the data from synthetic fluid inclusions [formed by healing fractures in inclusion-free Brazilian quartz in the presence of two coexisting, immiscible NaCl-H 2 O fluids at various temperatures and pressures (Bodnar et al ., 1985)], phase equilibria in the system NaCl-H 2 O have been redetermined to 1000°C and 1500 bars.

Geochimica et Cosmochimica Acta↗

USGS1991

Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria

The thermodynamic properties of minerals retrieved from consideration of solid-solid and dehydration equilibria with calorimetric reference values, and those of aqueous species derived from studies of electrolytes, are not consistent with experimentally measured high-temperature solubilities in the systems K 2 O- and Na 2 O-Al 2 O 3 -SiO 2 -H 2 O-HCl (e.g., K-fs — Ms — Qtz — K + — H + ). This introduces major inaccuracies into the computation of ionic activity ratios and the acidities of diagenetic, metamorphic, and magmatic hydrothermal fluids buffered by alkali silicate-bearing assemblages. We report a thermodynamic analysis of revised solubility equilibria in these systems that integrates the thermodynamic properties of minerals obtained from phase equilibria studies ( Berman , 1988) with the properties of aqueous species calculated from a calibrated equation of state ( Shock and Helgeson , 1988). This was achieved in two separate steps. First, new values of the free energies and enthalpies of formation at 25°C and 1 bar for the alkali silicates muscovite and albite were retrieved from the experimental solubility equilibria at 300°C and P sat . Because the latter have stoichiometric reaction coefficients different from those for solid-solid and dehydration equilibria, our procedure preserves exactly the relative thermodynamic properties of the alkali-bearing silicates ( Berman , 1988). Only simple arithmetic adjustments of −1,600 and −1,626 ( ±500 "> ±500 ) cal/mol to all the K- and Na-bearing silicates, respectively, in Berman (1988) are required. In all cases, the revised values are within ±0.2% "> ±0.2% of calorimetric values. Similar adjustments were derived for the properties of minerals from Helgeson et al. (1978). Second, new values of the dissociation constant of HCl were retrieved from the solubility equilibria at temperatures and pressures from 300–600°C and 0.5–2.0 kbars using a simple model for aqueous speciation. The results agree well with the conductance-derived dissociation constants from Franck (1956a,b) for temperatures from 300–550°C. Compared to the conductance-derived results of Frantz and Marshall (1984), our dissociation constants agree well at the highest densities, but are greater at lower densities. At the lowest density, at 600°C and 1 kbar, the discrepancy of 0.9 log units is within the overall uncertainties associated with our experimental results and those associated with deriving dissociation constants from conductance measurements in highly associated solutions ( Oelkers and Helgeson , 1988). Finally, we also report an equation of state fit to the standard thermodynamic properties of the aqueous HCl molecule that is consistent with a wide array of independently determined dissociation constants of HCl and permits interpolation and extrapolation of the dissociation constant of HCl to 1000°C and 5.0 kbars.

Geochimica et Cosmochimica Acta↗

USGS2012

Origin of Hawaiian tholeiite: A metasomatic model

Two voluminous magma types generated in the mantle underlying the Pacific plate are mid‐ocean ridge tholeiite (MORB) erupted at the East Pacific Rise spreading center and Hawaiian tholeiite (HT) erupted above the Hawaiian hot spot or melting anomaly. MORB has low initial 87 Sr/ 86 Sr ratios and low amounts of all incompatible trace elements including rare earths; chondrite‐normalized patterns are depleted in light rare earths. HT, by contrast, has higher initial 87 Sr/ 86 Sr and higher amounts of incompatible trace elements; chondrite‐nor‐malized patterns are enriched in the middle and light rare earths. HT is generally poorer in CaO and Al 2 O 3 and much richer in total iron and TiO 2 compared with MORB having the same MgO content. Primary magma compositions for the two volcanic systems are calculated in Fe‐Mg equilibrium with residual olivine (Fo 92 ). MORB is generated by partial melting of a trace element depleted Iherzolite source leaving a residual assemblage dominated by olivine and orthopyroxene. The percentage of partial melting for a primary magma containing 15% MgO is calculated to be 35–42% in a source mantle having a heavy rare earth content of 3×chondrite and 33–35% MgO. HT, represented by Kilauea tholeiite, is generated by partial melting of a mixture of unmelted and residual mantle for MORB which has been modified by metasomatic addition of a nephelinitic fluid, amphibole, and minor amounts of apatite and Fe‐bearing phases such as sulfide and magnetite/ilmenite. This model yields a picritic magma in equilbrium with magnesian dunite at high (>40%) degrees of partial melting. The source also has 35% MgO before partial melting. Melting in both systems in polyvariant and not controlled by lower‐temperature invariant equilibria. The low‐velocity zone is considered to be the source of metasomatic fluids that are driven upward into the lowermost lithosphere in response to a thermal plume. Picritic primary magmas are produced by shear melting, localized in the zone of thinned and metasomatized lithosphere beneath Hawaii. Melt extraction is rapid and episodic at intervals of months to decades; magma is not stored in the mantle but passes upward to a plexus of storage reservoirs located 2–6 km beneath the surface of Kilauea. Kilauea primary magmas fractionate olivine during upward transport to reach bulk compositions of 13–14% MgO in storage. Different magma batches erupted to the surface, distinguished by different major and minor element compositons compared at similar MgO content, represent combinations of differing degrees of metasomatic enrichment, differing degrees of partial melting, and some effects of premelting mantle heterogeneity.

Hawaii↗

USGS2021

Eocene magma plumbing system beneath Cortez Hills Carlin-type gold deposit, Nevada: Is there a deep-seated pluton?

The magmatic-hydrothermal conceptual model for Carlin-type gold deposit genesis calls upon deep-seated Eocene plutons as the primary source of gold-bearing fluids. However, geophysical surveys, geologic mapping, drilling, geochronology, isotopic tracers, and fluid inclusion chemistry have returned ambiguous evidence for the existence of such plutons. The high-grade Cortez Hills gold deposit in northern Nevada hosts shallow, Eocene syn- and postmineralization intrusions, offering an ideal site to investigate the existence of a deep-seated pluton beneath the district. Here, major and trace element analyses of quartz-hosted melt inclusions from four Eocene rhyolite dikes cropping out within the Cortez Hills pit and results from independent thermobarometers provide a window into the subsurface Eocene magmatic plumbing system to test the existence of a deep-seated source pluton. Dissolved volatile contents, melt inclusion entrapment pressures, and thermodynamic phase equilibria indicate that dike magmas were sourced from ~4- to ≥9-km depth from a polybaric magma reservoir residing as a physically and geochemically interconnected crystal mush with extractable or eruptible magma pockets. Magmas ascended adiabatically (nearly isothermally), exsolving fluids, evolving modestly by fractional crystallization, while trapping quartz-hosted melt inclusions steadily from depth to subvolcanic levels where they were emplaced. These data represent the first unequivocal evidence for a deep-seated magma reservoir from which fluid-saturated magma emanated and released magmatic fluids beneath the Cortez district during gold mineralization. However, further investigation into the specific metallogenic potential and metal budget of parental magmas and the partitioning of gold between silicate melt and aqueous fluids will be necessary to provide evidence that exsolved magmatic fluids may have been gold bearing.

Nevada↗

USGS2006

Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent volumetric rate of evolved magma production. ?? Copyright 2007 Oxford University Press.

Journal of Petrology↗

USGS2024

Paleoproterozoic reworking of Archean crust and extreme back-arc metamorphism in the enigmatic southern Trans-Hudson orogen

The crustal evolution of the southernmost ∼2000–1800 Ma Trans-Hudson orogen (THO) is enigmatic due to burial by Phanerozoic sediments. We provide new insights through petrochronologic analysis of a paragneiss drill core sample. Detrital zircon age peaks at 2625, 2340, and 1880 Ma and Hf isotopes suggest Paleoproterozoic arc development proximal to Archean source(s). Phase equilibria modeling and ternary feldspar thermometry suggest peak conditions of ≥1 GPa, ≥900°C, the first recognition of extreme, ultra-high temperature metamorphism in the THO. The largely isobaric P-T path, rapid heating rate, and ∼20 Myr duration (1872–1850 Ma) of peak conditions suggest that this metamorphism occurred in a back-arc tectonic setting. The sample records post-peak (1850–1815 Ma) mid-crustal residence, slow cooling, and exhumation. Further retrogression occurred during Proterozoic regional exhumation (1630–1470 Ma) and Phanerozoic (360–220 Ma) reheating and/or fluid influx. Evidence for Paleoproterozoic arc(s) supports geophysical data for Archean cratonic and Paleoproterozoic arc crust in this region.

Geophysical Research Letters↗

USGS1985

Some mineral stability relations in the system CaO MgO SiO2 H2O HCl

Mineral-aqueous solution equilibria for the assemblages talc-quartz, tremolite-talc-quartz, diopside-tremolite-quartz, wollastonite-diopside-quartz and wollastonite-quartz have been studied at 2 kb total pressure, 500° to 700°C and chloride concentrations from 0.03 to 6.0 molal. Most work was at 1 m chloride. Both buffered and unbuffered data were obtained and a recalibration of the Ag-AgCl buffer is presented. Log equilibrium quotients at 500°, 600° and 700°C are respectively: Ta-Qz ( m MgCl 2 m HCl 2 "> mMgCl2mHCl2 ) 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz ( m CaCl 2 m MgCl 2 m HCl 2 "> mCaCl2mMgCl2mHCl2 ) 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz ( m CaCl 2 m MgCl 2 "> mCaCl2mMgCl2 ) 3.30, 3.00, 2.79: Wo-Qz ( m CaCl 2 m HCl 2 "> mCaCl2mHCl2 ) 5.15, 3.95, 2.68. Mineral stability fields plotted in terms of these concentration data more tangibly represent the compositional character of real systems and the mass transfer capabilities of their fluids than do the analogous theoretical activity diagrams. Overall dissociation constants of MgCl 2 and CaCl 2 were calculated from the experimental data using the calculated ionic activity constants for the reactions and the established dissociation constants of HCl. The negative log values are respectively: 3.88. 6.63, 9.20 for CaCl 2 and 4.60, 7.54, 10.37 for MgCl 2 at 500°, 600° and 700°C, 2 kb. The Ca values are about an order of magnitude more positive than the conductance-derived values by Frantz and Marshall (1982). The phase relations developed in this study have application to the genesis of talc, tremolite, and diopside-bearing assemblages in some regional metamorphic rocks, but more specifically to the calcsilicate skarn assemblages of many metasomatic aureoles. The equilibrium fluids are characterized by high concentrations of Ca relative to Mg and increasing Ca Mg "> CaMg ratios with decreasing temperatures. The stability fields of talc, tremolite, and quartz expand relative to those of diopside and wollastonite with decreasing temperature, hence their more common appearance as retrograde products in skarn systems.

Geochimica et Cosmochimica Acta↗

USGS1969

Geology and regional metamorphism of some high-grade cordierite gneisses, Front Range, Colorado

Cordierite is common in regional metamorphic gneisses of Precambrian age in the central part of the Front Range. It occurs in discontinuous stratigraphic units that are structurally a minor component, except locally, of the thick succession of biotite gneisses that comprise the widespread Idaho Springs Formation. The rocks have mineral assemblages, that are characteristic of the sillimanite grade of metamorphism. The cordierite occurs in three principal rock types: (1) potassic feldspar-bearing cordierite-garnet-sillimanite-biotite gneiss, (2) cordierite-biotite gneiss, and (3) cordierite-gedrite-biotite gneiss; each type contains several characteristic mineral assemblages. The rock types are gradational and overlap in areal distribution, and mainly owe their diversity in mineralogy to differences in bulk chemical composition. The field relations are consistent with an interpretation that the diverse cordierite rocks were derived from original sedimentary rocks, largely pelitic sediments. The potassic feldspar-bearing cordierite-garnet gneisses were formed from shales that contained more MgO and FeO than the more abundant sedimentary facies that yielded sillimanitic biotite gneisses. Cordierite-gedrite-biotite gneisses contain much aluminum, iron, and magnesium and little sodium and potassium as compared to the other biotite gneisses; they have an extremely low content of minor elements. Although their chemical compositions are unlike those of known modern sediments, the cordierite-gedrite gneisses are considered also to have been derived from sedimentary rocks. The physical properties and chemical compositions of the mineral phases vary somewhat from one rock type to another. Biotite varies systematically in composition, and the changes are closely related to rock type and thus to bulk composition; the MgO/FeO ratios range from 1.7 in the more mafic cordierite-gedrite rocks to 0.49 in potassic feldspar-bearing cordierite-garnet gneisses. Cordierite is magnesium-rich and intermediate in the range of composition of all analyzed cordierites (Leake, 1960); its MgO/FeO ratio is higher in the gedrite-bearing gneisses than in the potassic feldspar-bearing gneisses. The garnets consist dominantly of the almandine and pyrope molecules, and range from 64 to 75 percent almandine and from 14 to 27 pyrope. These crystals are zoned; their rims are slightly more ferrous and less magnesian than their cores. Both monoclinic and triclinic alkali feldspars coexist in the potassic feldspar-bearing cordierite-garnet gneisses. The potassic feldspars contain from 18 to 27 weight percent NaAlSi 3 O 8 . Plagioclase (oligoclase-andesine) is uncommon in the rocks. Gedrite has an MgO/FeO ratio ranging from 1 to 1.2. Associated minor minerals include iron oxides, andalusite, spinel and its alteration product högbomite, and corundum. The mineral assemblages can be correlated imperfectly with episodes of deformation and metamorphism. Relict staurolite and associated garnet occur locally as remnants of an assemblage formed early in regional metamorphism, presumably early in the first period of deformation. The dominant assemblage biotite-cordierite-garnet-magnetite-plagioclase-potassic feldspar-quartz-sillimanite and associated assemblages having fewer phases, were formed during period one and period two deformations, the principal episodes of regional dynamothermal metamorphism in the central part of the Front Range. A minor assemblage andalusite-biotite-magnetite-plagioclase-quartz was formed later, possibly coincident with a third period of deformation, largely cataclastic in effects, which was more local than the earlier deformations and metamorphism. Phase equilibria studies of the assemblage biotite-cordierite-garnet-magnetite-plagioclase-potassic feldspar-quartz-sillimanite and associated assemblages are interpreted to indicate that the cordierite assemblages approach a state of chemical equilibrium. The scatter of points in a distribution diagram can be interpreted in terms of at least two sets of equilibrium conditions that prevailed during the major plastic deformations. Other discrepancies indicating departure from a homogeneous equilibrium can be explained as a result of mosaic equilibrium involving limited diffusion of iron and magnesium for short distances. The mineral assemblages and the compositions of the ferromagnesian minerals in the cordierite rocks of this region are dependent primarily on the bulk composition of the rocks and variations in the mineral species that comprise the rocks and, to a lesser degree, on the grade of metamorphism. Biotite and cordierite are markedly more magnesian in the more mafic cordierite-gedrite-biotite gneiss than in the potassic feldspar-bearing cordierite-garnet-sillimanite-biotite gneiss. Associated microcline gneiss and biotite-sillimanite gneiss that contains muscovite as a primary stable mineral provides a means to define the metamorphic grade in the area of study. It is concluded from analyses of the assemblages with respect to theoretical phase relations in the system SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-H 2 O that at least some of the rocks in the Central City-Nederland area are above the sillimanite-potassic feldspar isograd as defined by Evans and Guidotti (1966). In rocks of appropriate composition, muscovite is a stable phase in assemblages containing potassic feldspar and sillimanite. The cordierite assemblages and associated rocks are inferred to have formed in an environment having a load pressure of 3–5 kilobars (fluid pressure equaled load pressure) and a temperature somewhat in excess of 620° C.

Colorado↗