The pressure dependence of the zirconium-in-rutile thermometer

The solubility of ZrO₂ in rutile is strongly temperature-dependent and has been identified as a potentially powerful thermometer when the rutile coexists with an appropriate buffer assemblage, e.g. zircon + quartz. In combination with experimental data at 10 kbar, previous consideration of data on natural rutile has not identified a pressure dependence for the thermometer. However, the expected volume change as a result of substitution of the larger Zr⁴⁺ cation for Ti⁴⁺ suggests that the Zr content of rutile should decrease with increasing pressure. To investigate the pressure dependence of the thermometer, piston cylinder (at 10, 20 & 30 kbar) and 1 atm furnace experiments were performed in the system ZrO₂-TiO₂-SiO₂. The solubility of ZrO₂ in rutile, in the presence of zircon and quartz was reversed at each pressure value. From these experiments, the thermodynamics of the end-member reaction ZrSiO₄ = SiO₂ + ZrO₂ (in rutile) have been determined. There is a secondary pressure effect accompanying the primary temperature dependence of the Zr content of rutile. New thermometer equations are, in the α -quartz field: in the β -quartz field and in the coesite field in which φ is ppm Zr, P is in kbar and R is the gas constant, 0.0083144 kJ K⁻¹. Thermometric results using these equations are shown for a range of geological settings.     

A thermodynamic model for Ca–Na clinoamphiboles in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O for petrological calculations

A calibration is presented for an activity–composition model for amphiboles in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–O (NCFMASHO), formulated in terms of an independent set of six end‐members: tremolite, tschermakite, pargasite, glaucophane, ferroactinolite and ferritschermakite. The model uses mixing‐on‐sites for the ideal‐mixing activities, and for the activity coefficients, a macroscopic multicomponent van Laar model. This formulation involves 15 pairwise interaction energies and six asymmetry parameters. Calibration of the model is based on the geometrical constraints imposed by the size and shape of amphibole solvi inherent in a data set of 71 coexisting amphibole pairs from rocks, formed over 400–600 °C and 2–18 kbar. The model parameters are calibrated by combining these geometric constraints with qualitative consideration of parameter relationships, given that the data are insufficient to allow all the model parameters to be determined from a regression of the data. Use of coexisting amphiboles means that amphibole activity–composition relationships are calibrated independently of the thermodynamic properties of the end‐members. For practical applications, in geothermobarometry and the calculation of phase diagrams, the amphibole activity–composition relationships are placed in the context of the stability of other minerals by evaluating the properties of the end‐members in the independent set that are in internally consistent data sets. This has been performed using an extended natural data set for hornblende–garnet–plagioclase–quartz, giving the small adjustments necessary to the enthalpies of formation of tschermakite, pargasite and glaucophane for working with the Holland and Powell data set.     

Hydration of orthopyroxene–cordierite-bearing assemblages at Laouni, Central Hoggar, Algeria

In the Laouni region (Central Hoggar, Algeria), retrogression of high-grade orthopyroxene–cordierite-bearing rocks led to the crystallization of orthoamphibole and garnet, and at a later stage of chlorite, from the original paragenesis. Calculated phase diagrams show that this retrogression occurred at about 3  kbar with the simplest model involving hydration at 650–700°  C and at around 500°  C, with the rocks experiencing a H₂O less than 1, except possibly in the last stages of chlorite crystallization. As the other rock types occurring in the same area as the orthopyroxene–cordierite rocks display similar features, it is concluded that regional hydration occurred, presumably related to the release of fluids during the crystallization of the Pan-African granitic and mafic magmas that are widespread in the Laouni area.     

Granulite facies metamorphism and subsolidus fluid-absent reworking, Strangways Range, Arunta Block, central Australia

Orthopyroxene‐rich quartz‐saturated granulites of the Strangways Range, Arunta Block, central Australia, record evidence of two high‐grade metamorphic events. Initial granulite facies metamorphism (M₁, at c. 1.7 Ga) involved partial melting and migmatization culminating in conditions of 8.5 kbar and 850 °C. Preservation of the peak M₁ mineral assemblages from these conditions indicates that most of the generated melt was lost from these rocks at or near peak metamorphic conditions. Subsequent reworking (M₂, at c. 1.65 Ga) is characterized by intense deformation, the absence of partial melting and the development of orthopyroxene–sillimanite ± gedrite‐bearing mineral assemblages. Gedrite is only present in cordierite‐rich lithologies where it preferentially replaces M₁ cordierite porphyroblasts. Pseudosection calculations indicate that M₂ occurred at subsolidus fluid‐absent conditions (a_H2o ～ 0.2) at 6–7.5 kbar and 670–720 °C. The mineral assemblages in the reworked rocks are consistent with closed system behaviour with respect to H₂O subsequent to M₁ melt loss. M₂ reworking was primarily driven by increased temperature from the stable geotherm reached after cooling from M₁ and deformation‐induced recrystallization and re‐equilibration, rather than rehydration from an externally derived fluid. The development of the M₂ assemblages is strongly dependent on the intensity of deformation, not only for promoting equilibration, but also for equalizing the volume changes that result from metamorphic reactions. Calculations suggest that the protoliths of the orthopyroxene‐rich granulites were cordierite–orthoamphibole gneisses, rather than pelites, and that the unusual bulk compositions of these rocks were inherited from the protoliths. Melt loss is insufficient to account for the genesis of these rocks from more typical pelitic compositions. In quartz‐rich gneisses, however, melt loss along the M₁ prograde path was able to modify the bulk rock composition sufficiently to stabilize peak metamorphic assemblages different from those that would have otherwise developed.     

Identification and micro‐stratigraphy of hyperpycnites and turbidites in Cretaceous Lewis Shale,Wyoming

Sandy hyperpycnal flows and their deposits, hyperpycnites, have been documented in modern environments and, more recently, in Cretaceous and Tertiary strata; they may be more common in the rock record, and within petroleum reservoirs, than has been previously thought. Muddy hyperpycnites also occur within the rock record, but these are more difficult to document because of their finer‐grained nature and lack of common sedimentary structures. This paper documents the presence of submarine slope mudstone and siltstone hyperpycnites (and muddy turbidites) in the delta‐fed, Upper Cretaceous Lewis Shale of Wyoming; based on field measurements, analyses of rock slabs and thin sections, and laser grain‐size distributions. Four lithofacies comprise laminated and thin‐bedded mudstones that are associated with levéed channel sandstones: (L1) grey, laminated, graded mudstone with thin siltstone and sandstone interbeds; (L2) dark grey to tan, laminated mudstone with very thin siltstone and sandstone stringers; (L3) light grey, laminated siltstones; and (L4) laminated mudstones and siltstones with thin sandstone interbeds. Two styles of mudstone grain‐size grading have been documented. The first type is an upward‐fining interval that typically ranges in thickness from 2·5 to 5 cm. The second type is a couplet of a lower, upward‐coarsening interval and an upper, upward‐fining interval (sometimes separated by a micro‐erosion surface) which, combined, are about 3·8 cm thick. Both individual laminae and groups of laminae spaced millimetres apart exhibit these two grain‐size trends. Although sedimentary structures indicative of traction‐plus‐fallout sedimentary processes associated with sandier hyperpycnites are generally absent in these muddy sediments, the size grading patterns are similar to those postulated in the literature for sandy hyperpycnites. Thus, the combined upward‐coarsening, then upward‐fining couplets are interpreted to be the result of a progressive increase in river discharge during waxing and peak flood stage (upward increase in grain‐size), followed by waning flow after the flood begins to abate (upward decrease in grain‐size). The micro‐erosion surface that sometimes divides the two parts of the size‐graded couplet resulted from waxing flows of sufficiently high velocity to erode the sediment previously deposited by the same flow. Individual laminae sets which only exhibit upward‐fining trends could be either the result of waning flow deposition from either dilute turbidity currents or from hyperpycnal flows. The occurrence of these sets with the size‐graded couplets suggests that they are associated with hyperpycnal processes.     

Lithofacies and sequence development on an Upper Devonian mixed carbonate-siliciclastic fore-reef slope, Canning Basin, Western Australia

Detailed sedimentological and stratigraphical analysis coupled with conodont biostratigraphy of a fore-reef slope succession in the Napier Range (Napier Formation) is used to develop a depositional model and relative sea-level history for late Frasnian to late Famennian reef evolution in the Canning Basin of north-western Australia. Changes in sedimentary style on the slope, reflecting differing rates of carbonate production on the platform, are linked to third- and higher order relative sea-level fluctuations. Overlapping slope aprons accumulated along the base of a steep-walled platform margin. Coarse carbonate debris was deposited adjacent to the margin as talus breccias (via rockfall) and debris-flow breccias. Depositional slopes up to 45°, and locally steeper, are demonstrated using rotated geopetal cavity fills. The predominance of channel-filling lithofacies throughout the slope succession indicates the highly channelized nature of the aprons. The middle slope is dominated by sandy oolitic-peloidal turbiditic grainstones interpreted as sediment exported from an active platform. The turbidites and associated debris-flow breccias contrast with condensed carbonate intervals and deep-water, non-fenestral stromatolites that record times of very low platform production. Lower slope turbidites and associated intraclastic breccias indicate widespread redeposition of sediment eroded from lithified and semi-lithified limestones higher up the slope. Several third-order sequences are recognized in the fore-reef succession and these are composed primarily of transgressive and highstand deposits. Carbonate production was severely restricted in the early Famennian coinciding with development of onlapping siliciclastic aprons during a relative sea-level lowstand. Evidence for a subaerial exposure event is also preserved within the siliciclastic strata. Controls on sequence development are difficult to constrain. Although two sequence boundaries can be correlated with falls on the global sea-level curve, the reef complexes evolved in an active extensional regime and it is highly likely that tectonism, in conjunction with eustasy, controlled accommodation on the platform and therefore carbonate productivity.     

Evaporitic sediments of Early Archaean age from the Warrawoona Group, North Pole, Western Australia

Chemical sediments are common and diverse in the c. 3500 Myr old North Pole chert-barite unit in the Warrawoona Group, Western Australia. Although almost all original minerals were replaced during hydrothermal alteration, metamorphism and deformation, pseudomorphic relics of sedimentary and diagenetic textures and structures show that at least six lithofacies were partly or wholly chemical in origin. These contained five main chemical sedimentary components: primary carbonate mud, diagenetic carbonate crystals, primary sulphate crystals, diagenetic sulphate crystals and diagenetic sulphate nodules. All show a wide range of characteristics consistent only with a marine evaporative origin. Diagenetic carbonate and sulphate crystals, once ferroan dolomite and gypsum, were precipitated within volcanogenic lutites high on littoral mudflats. The other evaporative phases were apparently deposited behind a barrier bar composed of stranded pumice rafts. Primary sulphate crystals, once gypsum and now barite, were precipitated in semi-permanent pools immediately behind the bar. Primary carbonate mud, originally calcitic or aragonitic but now silicified, was deposited in nearby channels and on surrounding mudflats. Within these sediments, diagenetic carbonate crystals (formerly ferroan dolomite) and diagenetic sulphate nodules and crystals (once gypsum) grew during later desiccation. The existence of these evaporites, and more like them in the sediments of other Early Archaean cratons, suggests that shallow marine and terrestrial conditions prevailed over a small but significant portion of the early Earth, contrary to some models of global tectonic evolution. Their overall similarity with more recent evaporitic deposits indicates that there was greater conformity between conditions in modern and primeval sea-shore environments than might be expected, given the great age difference. The attitude implicit in many accounts of Earth's early history, that evaporites were either not deposited or not preserved in Archaean sediments, thus seems to be incorrect.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.