A molal-based model for strong acid chemistry at low temperatures (<200 to 298 K)

Geochemical processes occurring in cold environments on Earth, Mars, and Europa have elicited considerable interest in the application of geochemical models to subzero temperatures. Few existing geochemical models explicitly include acid chemistry and those that do are largely restricted to temperatures ≥0°C or rely on the mole-fraction scale rather than the more common molal scale. This paper describes (1) use of the Clegg mole-fraction acid models to develop a molal-based model for hydrochloric, nitric, and sulfuric acids at low temperatures; (2) incorporation of acid chemistry and nitrate minerals into the FREZCHEM model; (3) validation and limitations of the derived acid model; and (4) simulation of hypothetical acidic brines for Europa.The Clegg mole-fraction acid models were used to estimate activities of water and mean ionic activity coefficients that serve as the database for estimating molal Pitzer-equation parameters for HCl (188 to 298 K), HNO₃ (228 to 298 K), and H₂SO₄ (208 to 298 K). Model eutectics for HNO₃ and H₂SO₄ agree with experimental measurements to within ± 0.2°C. In agreement with previous work, the experimental freezing point depression (fpd) data for pure HCl at subzero temperatures were judged to be flawed and unreliable. Three alternatives are discussed for handling HCl chemistry at subzero temperatures. In addition to defining the solubility of solid-phase acids, this work also adds three new nitrate minerals and six new acid salts to the FREZCHEM model and refines equilibria among water ice, liquid water, and water vapor over the temperature range from 180 to 298 K. The final system is parameterized for Na-K-Mg-Ca-H-Cl-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-H₂O.Simulations of hypothetical MgSO₄-H₂SO₄-H₂O and Na₂SO₄-MgSO₄-H₂SO₄-H₂O brines for Europa demonstrate how freezing can convert a predominantly salt solution into a predominantly acid solution at subzero temperatures. This result has consequences for the effects of salinity, acidity, and temperature as limiting factors for potential life on Europa. Strong acidity would limit life-forms to highly acidophilic organisms.     

Diagenetic history and porosity evolution of Upper Carboniferous sandstones from the Spring Valley #1 well, Maritimes Basin, Canada–implications for reservoir development

Eighty-two core samples were collected from the Spring Valley #1 well which penetrates the Upper Carboniferous strata in the Late Devonian–Early Permian Maritimes Basin. The strata consist of alternating sandstones and mudstones deposited in a continental environment. The objective of this study is to characterize the relationship of sandstone porosity with depth, and to investigate the diagenetic processes related to the porosity evolution. Porosity values estimated from point counting range from 0% to 27.8%, but are mostly between 5% and 20%. Except samples that are significantly cemented by calcite, porosity values clearly decrease with depth. Two phases of calcite cement were distinguished based on Cathodoluminescence, with the early phase being largely dissolved and preserved as minor relicts in the later phase. Feldspar dissolution was extensive and contributed significantly to the development of secondary porosity. Quartz cementation was widespread and increased with depth. Fluid inclusions recorded in calcite and quartz cements indicate that interstitial fluids in the upper part of the stratigraphic column were dominated by waters with salinity lower than that of seawater, the middle part was first dominated by low-salinity waters, then invaded by brines, and the lower part was dominated by brines. Homogenization temperatures of fluid inclusions generally increase with depth and suggest a paleogeothermal gradient of 25 °C/km, which is broadly consistent with that indicated by vitrinite reflectance data. An erosion of 1.1–2.4 (mean 1.75) km of strata is inferred to have taken place above the stratigraphic column. δ¹⁸O values of calcite cements (mainly from the late phase) decrease with depth, implying increasing temperatures of formation, as also suggested by fluid-inclusion data. δ¹³C values of calcite cements range from −13.4‰ to −5.7‰, suggesting that organic matter was an important carbon source for calcite cements. A comparison of the porosity data with a theoretical compaction curve indicates that the upper and middle parts of the stratigraphic column show higher-than-normal porosity values, which are related to significant calcite and feldspar dissolution. Meteoric incursion and carboxylic acids generated from organic maturation were probably responsible for the abundant dissolution events.     

Genetic significance of fluid inclusions in the CSA Cu–Pb–Zn deposit, Cobar, Australia

CSA mine exploits a ‘Cobar-type’ Cu–Pb–Zn±Au±Ag deposit within a cleaved and metamorphosed portion of the Cobar Supergroup, central New South Wales. The deposit comprises systems of ‘lenses’ that encompass veins, disseminations and semi-massive to massive Cu–Pb–Zn ores. The systems and contained lenses truncate bedding, are approximately coplanar with regional cleavage and similarly oriented shear zones and plunge parallel to the elongation lineation. Systems have extreme vertical continuity (>1000 m), short strike length (400 m) and narrow width (100 m), exhibit vertical and lateral ore-type variation and have alteration haloes. Models of ore formation include classical hydrothermalism, structurally controlled remobilisation and polymodal concepts; syntectonic emplacement now holds sway.Fluid inclusions were examined from quartz±sulphide veins adjacent to now-extracted ore, from coexisting quartz–sulphide within ore, and from vughs in barren quartz veins. Lack of early primary inclusions precluded direct determination of fluids associated with D₂–D₃ ore and vein emplacement. Similarly, decrepitation (by near-isobaric heating) of the two oldest secondary populations precluded direct determination of fluid phases immediately following D₂–D₃ ore and vein emplacement. Post-decrepitation outflow (late D₃ to early post-D₃) is recorded by monophase CH₄ inclusions. Entrained outflow of deeply circulated meteoric fluid modified the CH₄ system; modification is recorded by H₂O+CH₄ and H₂O+(trace CH₄) secondary populations and by an H₂O+(trace CH₄) primary population. The contractional tectonics (D₂–D₃) of ore emplacement was superseded by relaxational tectonics (D_4P) that facilitated meteoric water penetration and return flow.Under D₂ prograde metamorphism, entrapment temperatures (Tt) and pressures (Pt) for pre-decrepitation secondary inclusions are estimated as Tt300–330 °C and Pt1.5–2 kbar≈Plith (the lithostatic pressure). Decrepitation accompanied peak metamorphism (T350–380 °C) in mid- to late-D₃, while in late-D₃ to early post-D₃, essentially monophase CH₄ secondary inclusions were entrapped at Tt350 °C and Pt=1.5–2 kbar≈Plith. Subsequently, abundant CH₄ and entrained meteoric water were entrapped as H₂O+CH₄ secondaries under slowly decreasing temperature (Tt330–350 °C) and constant pressure (Pt1.5–2 kbar). Finally, with increasingly dominant meteoric outflow, H₂O+(trace CH₄) populations record decreasing temperatures (Tt>300 to <350 down to 275–300 °C) at pressures of Phydrostatic<Pt (1 kbar) <Plith (1.5 kbar).The populations of inclusions provide insight into fluid types, flow regimes and P–T conditions during parts of the deposit's evolution. They indirectly support the role of basin-derived CH₄ fluids in ore formation, but provide no insight into a basement-sourced ore-forming fluid. They fully support post-ore involvement of meteoric water. The poorly constrained entrapment history is believed to span 10 Ma from 395 to 385 Ma.     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Syn‐metamorphic folding in the Tauern Window,Austria dated by Th–Pb ages from individual allanite porphyroblasts

High‐precision ²³²Th–²⁰⁸Pb dates have been obtained from allanite porphyroblasts that show unambiguous microstructural relationships to fabrics in a major syn‐metamorphic fold in the SE Tauern Window, Austria. Three porphyroblasts were analysed from a single garnet mica schist from the Peripheral Schieferhülle in the core of the Ankogel Synform, one of a series of folds which developed shortly before the thermal peak of Alpine epidote–amphibolite facies metamorphism: allanite grain 1 provided two analyses with a combined age of 27.7 ± 0.7 Ma; grain 2, which was slightly bent and fractured during crenulation, provided two analyses with a combined age of 27.7 ± 0.4 Ma; a single analysis from grain 3, which overgrew an already crenulated fabric, gave an age of 28.0 ± 1.4 Ma. The five ²³²Th–²⁰⁸Pb ages agree within error and define an isochron with an age of 27.71 ± 0.36 Ma (95% confidence level; MSWD = 0.46). The results imply that the crenulation event was in progress in a short interval (<1 Ma) c. 28 Ma, and that the Ankogel Synform was forming at this time. The thermal peak of regional metamorphism in the SE Tauern Window was probably attained shortly after 28 Ma, only c. 5 Ma after eclogite facies metamorphism in the central Tauern Window. Metasediment may contain allanite porphyroblasts with clear‐cut microstructural relationships to fabric development and metamorphic crystallization; for such rocks, ²³²Th–²⁰⁸Pb dating on microsamples offers a powerful geochronological tool.     

Evolution of the Australian lithosphere

The evolution of the Australian plate can be interpreted in a plate‐tectonic paradigm in which lithospheric growth occurred via vertical and horizontal accretion. The lithospheric roots of Archaean lithosphere developed contemporaneously with the overlying crust. Vertical accretion of the Archaean lithosphere is probably related to the arrival of large plumes, although horizontal lithospheric accretion was also important to crustal growth. The Proterozoic was an era of major crustal growth in which the components of the North Australian, West Australian and South Australian cratons were formed and amalgamated during a series of accretionary events and continent‐continent collisions, interspersed with periods of lithospheric extension. During Phanerozoic accretionary tectonism, approximately 30% of the Australian crust was added to the eastern margin of the continent in a predominantly supra‐subduction environment. Widespread plume‐driven rifting during the breakup of Gondwana may have contributed to the destruction of Archaean lithospheric roots (as a result of lithospheric stretching). However, lithospheric growth occurred at the same time due to mafic underplating along the eastern margin of the plate. Northward drift of Australia during the Tertiary led to the development of a complex accretionary margin at the leading edge of the plate (Papua New Guinea).     

Thematic mapping from remotely sensed data with neural networks: MLP, RBF and PNN based approaches

 Neural networks are attractive tools for the derivation of thematic maps from remotely sensed data. Most attention has focused on the multilayer perceptron (MLP) network but other network types are available and have different properties that may sometimes be more appropriate for some applications. Here a MLP, radial basis function (RBF) and probabilistic neural network (PNN) were used to classify remotely sensed data of an agricultural site. The accuracy of these classifications ranged from 86.25–91.25%. The accuracy of the PNN classification could be increased through the incorporation of prior probabilities of class membership but the accuracy of each classification could also be degraded by the presence of an untrained class. Post-classification analyses, however, could be used to identify potentially misclassified cases, including those belonging to an untrained class, to increase accuracy. The effect of the post-classification analysis on the accuracy of the classification derived from each of the three network types investigated differed and it is suggested that network type be selected carefully to meet the requirements of the application in-hand. Received: 23 March 2000 / Accepted: 9 July 2000     

Partial melting in the Inzie Head gneisses: the role of water and a petrogenetic grid in KFMASH applicable to anatectic pelitic migmatites

A sequence of prograde isograds is recognized within the Dalradian Inzie Head gneisses where pelitic compositions have undergone variable degrees of partial melting via incongruent melting reactions consuming biotite. Three leucosome types are identified. At the lowest grades, granitic leucosomes containing porphyroblasts of cordierite (CRD‐melt) are abundant. At intermediate grades, CRD‐melt mingles with garnetiferous leucosomes (GT‐melt). At the highest grades, CRD‐melt coexists with orthopyroxene‐bearing leucosomes (OPX‐melt), while garnet is conspicuously absent. The prograde metamorphic field gradient is constrained to pressures of 2–3 kbar below the CRD‐melt isograd, and no greater than 4.5 kbar at the highest grade around Inzie Head. A petrogenetic grid, calculated using thermocalc , is presented for the K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH) system for the phases orthopyroxene, garnet, cordierite, biotite, sillimanite, H₂O and melt with quartz and K‐feldspar in excess. For the implied field gradient, the reaction sequence predicted by the grid is consistent with the successive prograde development of each leucosome type. Compatibility diagrams suggest that, as anatexis proceeded, bulk compositions may have been displaced towards higher MgO content by the removal of (relatively) ferroan granitic leucosome. An isobaric (P = 4 kbar) T–a_H2O diagram shows that premigmatization fluids must have been water‐rich (a_H2O > 0.85) and suggests that, following the formation of small volumes of CRD‐melt, the system became fluid‐absent and melting reactions buffered a_H2O to lower values as temperatures rose. GT‐ and OPX‐melt formed by fluid‐absent melting reactions, but a maximum of 7–11% CRD‐melt fraction can be generated under fluid‐absent conditions, much less than the large volumes observed in the field. There is strong evidence that the CRD‐melt leucosomes could not have been derived by buoyantly aided upwards migration from levels beneath the migmatites. Their formation therefore required a significant influx of H₂O‐rich fluid, but in a quantity insufficient to have exhausted the buffering capacity of the solid assemblage plus melt. Fluid : rock ratios cannot have exceeded 1 : 30. The fluid was channelled through a regionally extensive shear zone network following melt‐induced failure. Such an influx of fluid at such depths has obvious consequences for localized crustal magma production and possibly for cordierite‐bearing granitoids in general.