Phosphorus distribution between potassic alkali feldspar and metaluminous haplogranitic liquid at 200 MPa (H<Subscript>2</Subscript>O): the effect of undercooling on crystal–liquid systematics

To evaluate the applicability of P₂O₅ concentration in potassic alkali feldspar as a monitor of P₂O₅ in melt for undercooled systems, crystal–melt partitioning for P was evaluated via feldspar growth experiments in P-bearing ((3 wt% P₂O₅), water-saturated haplogranitic liquids at 200 MPa, with liquidus undercoolings (ΔT) of 25, 50, 100, 200, and 300°C. Increasing undercooling in the range ΔT=25–200°C shows an evolution of crystal morphologies, from euhedral and well-filled individuals at ΔT=25–50°C to radial clusters with increasingly skeletal habit at greater undercooling. Experiments at ΔT=100–200°C also document the development of P- (up to (9 wt% P₂O₅) and Si-enriched, more alkaline boundary layers adjacent to crystals. Experiments at ΔT=300°C show an additional change in crystallization fabric in which spherulites of skeletal crystals form in open (vapor) space created by the dissolution of bulk silicate, and compositional boundary layers are not observed. We interpret the changes in reaction products at ΔT=300°C to indicate conditions below a glass transition; hence, partition coefficients were not determined for this undercooling. Values of K _d(P)^Kfs/melt from experiments at ΔT=25–200°C, calculated from pairs of crystal and immediately adjacent liquid compositions (including boundary layers at higher undercooling), are mostly in the range of 0.25–0.55 and show no effective change with increased undercooling. Essentially no change in K _d(P)^Kfs/melt with undercooling apparently stems from an interplay between boundary layer composition and a change in the substitution mechanism for P in feldspar from AlPSi₋₂, common in peraluminous to metaluminous liquids near equilibrium, to increasing proportions of ([ ],P)(M⁺,Si)₋₁ with increased undercooling. Bulk glass and liquid beyond boundary layers in experiments with significant percentages of crystallization are homogeneous, and show pronounced fractionation primarily due to the removal of an orthoclase component. Because crystallization was still in progress in experiments with ΔT≤200°C, compositional homogeneity in the bulk liquid requires extremely rapid diffusion of most haplogranite components (Na, K, and Al), apparently resulting from chemical potential gradients stemming from the removal of components from the liquid by crystal growth. Similar homogeneity and bulk fractionation in experiments with ΔT=300°C requires rapid diffusive equilibration for the alkalis even at temperatures below an apparent glass transition. Unlike the haplogranite components, P is only concentrated in liquid boundary layers (ΔT≤200°C) or low-density aqueous vapor (ΔT=300°C) adjacent to crystals. Hence, the P₂O₅ contents of melt inclusions likely are not representative of bulk melt concentrations in significantly undercooled systems (ΔT≤50–100°C).     

Geochemical syntheses among the cratonic,off-cratonic and orogenic garnet peridotites and their tectonic implications

Garnet-bearing mantle peridotites, occurring as either xenoliths in volcanic rocks or lenses/massifs in high-pressure and ultrahigh-pressure terrenes within orogens, preserve a record of deep lithospheric mantle processes. The garnet peridotite xenoliths record chemical equilibrium conditions of garnet-bearing mineral assemblage at temperatures (T) ranging from ~700 to 1,400°C and pressures (P) > 1.6–8.9 GPa, corresponding to depths of ~52–270 km. A characteristic mineral paragenesis includes Cr-bearing pyropic garnet (64–86 mol% pyrope; 0–10 wt% Cr₂O₃), Cr-rich diopside (0.5–3.5 wt% Cr₂O₃), Al-poor orthopyroxene (0–5 wt% Al₂O₃), high-Cr spinel (Cr/(Cr + Al) × 100 atomic ratio = 2–86) and olivine (88–94 mol% forsterite). In some cases, partial melting, re-equilibration involving garnet-breakdown, deformation, and mantle metasomatism by kimberlitic and/or carbonatitic melt percolations are documented. Isotope model ages of Archean and Proterozoic are ubiquitous, but Phanerozoic model ages are less common. In contrast, the orogenic peridotites were subjected to ultrahigh-pressure (UHP) metamorphism at temperature ranging from ~700 to 950°C and pressure >3.5–5.0 GPa, corresponding to depths of >110–150 km. The petrologic comparisons between 231 garnet peridotite xenoliths and 198 orogenic garnet peridotites revealed that (1) bulk-rock REE (rare earth element) concentrations in xenoliths are relatively high, (2) clinopyroxene and garnet in orogenic garnet peridotites show a highly fractionated REE pattern and Ce-negative anomaly, respectively, (3) Fo contents of olivines for off-cratonic xenolith are in turn lower than those of orogenic garnet and cratonic xenolith but mg-number of garnet for orogenic is less than that of off-cratonic and on-cratonic xenolith, (4) Al₂O₃, Cr₂O₃, CaO and Cr# of pyroxenes and chemical compositions of whole rocks are very different between these garnet peridotites, (5) orogenic garnet peridotites are characterized by low T and high P, off-cratonic by high T and low P, and cratonic by medium T and high P and (6) garnet peridotite xenoliths are of Archean or Proterozoic origin, whereas most of orogenic garnet peridotites are of Phanerozoic origin. Taking account of tectonic settings, a new orogenic garnet peridotite exhumation model, crust-mantle material mixing process, is proposed. The composition of lithospheric mantle is additionally constrained by comparisons and compiling of the off-cratonic, on-cratonic and orogenic garnet peridotite.     

The phase boundary between wadsleyite and ringwoodite in Mg2SiO4 determined by in situ X-ray diffraction

The phase boundary between wadsleyite and ringwoodite in Mg₂SiO₄ has been determined in situ using a multi-anvil apparatus and synchrotron X-rays radiation at SPring-8. In spite of the similar X-ray diffraction profiles of these high-pressure phases with closely related structures, we were able to identify the occurrence of the mutual phase transformations based on the change in the difference profile by utilizing a newly introduced press-oscillation system. The boundary was located at ~18.9 GPa and 1,400°C when we used Shim’s gold pressure scale (Shim et al. in Earth Planet Sci Lett 203:729–739, 2002), which was slightly (~0.8 GPa) lower than the pressure as determined from the quench experiments of Katsura and Ito (J Geophys Res 94:15663–15670, 1989). Although it was difficult to constrain the Clapeyron slope based solely on the present data due to the kinetic problem, the phase boundary [P (GPa)=13.1+4.11×10⁻³×T (K)] calculated by a combination of a P–T position well constrained by the present experiment and the calorimetric data of Akaogi et al. (J Geophys Res 94:15671–15685, 1989) reasonably explains all the present data within the experimental error. When we used Anderson’s gold pressure scale (Anderson et al. in J Appl Phys 65:1535–1543, 1989), our phase boundary was located in ~18.1 GPa and 1,400°C, and the extrapolation boundary was consistent with that of Kuroda et al. (Phys Chem Miner 27:523–532, 2000), which was determined at high temperature (1,800–2,000°C) using a calibration based on the same pressure scale. Our new phase boundary is marginally consistent with that of Suzuki et al. (Geophys Res Lett 27:803–806, 2000) based on in situ X-ray experiments at lower temperatures (<1,000°C) using Brown’s and Decker’s NaCl pressure scales.     

Rate and mechanism in prograde metamorphism

For a given rate of heat input into a prograde metamorphic sequence the extent of overstep of reaction temperature (disequilibrium) depends on the slowest of three sequential steps: (a) surface detachment of reactant minerals, (b) transport of material to the site of mineral growth, and (c) nucleation and growth of the product mineral. We have developed analytical expressions which enable determination of the rates of mineral dissolution and growth and of advective and diffusive mass transport during metamorphism. The dissolution and growth steps are linear functions of the driving force (– G) of the overall reaction while diffusion may take place either through a grain boundary fluid film or through the disorganized grain boundary itself.While little is known about heterogeneous nucleation, we argue from field observations that the rate of nucleation is not in general rate limiting. Additionally, if a fluid phase is present true grain boundary diffusion cannot be the mechanism which transports material over the mm to cm distances observed between reactant and product minerals.Simple models of contact (200° C temperature rise in 10,000 years) and regional (10° C per million years) metamorphic events lead to several conclusions concerning the rate determining step. Firstly, growth and dissolution are extremely rapid, dehydration reactions at 500° C going to completion in 2×10² years (contact) and 1×10⁴ years (regional), if all solutes are readily transported. Secondly, the effect of substantial fracture flow of fluid is to divert the transporting medium away from the grain boundary region and hence to retard the transport step. Under most such circumstances it appears that diffusive transport of aqueous SiO₂ or Mg species will be rate controlling. Despite this retardation of reaction rates, the extent of disequilibrium is rarely more than a few degrees C. Extensive disequilibrium (40° C) can only occur for reactions such as the andalusite sillimanite transformation which have very small entropy changes and which occur in rapid metamorphic events.     

Melting and phase relations in the plane tholeiite-lherzolite-nepheline basanite to 40 kilobars with geological implications

Six crystalline mixtures, picrite, olivine-rich tholeiite, nepheline basanite, alkali picrite, olivine-rich basanite, and olivine-rich alkali basalt were recrystallized at pressures to 40 kb, and the phase equilibria and sequences of phases in natural basaltic and peridotitic rocks were investigated.The picrite was recrystallized along the solidus to the assemblages (1) olivine+orthopyroxene+ clinopyroxene +plagioclase+spinel below 13 kb, (2) olivine+orthopyroxene+clinopyroxene+spinel between 13 kb and 18 kb, (3) olivine+orthopyroxene+clinopyroxene+ garnet+spinel between 18 kb and 26 kb, and (4) olivine+clinopyroxene+garnet above 26 kb. The solidus temperature at 1 atm is slightly below 1,100° and rises to 1,320° at 20 kb and 1,570° at 40 kb. Olivine is the primary phase crystallizing from the melt at all pressures to 40 kb.The olivine-rich tholeiite was recrystallized along the solidus into the assemblages (1) olivine+ clinopyroxene+plagioclase+spinel below 13 kb, (2) clinopyroxene+orthopyroxene+ spinel between 13 kb and 18 kb, (3) clinopyroxene+garnet+spinel above 18 kb. The solidus temperature is slightly below 1,100° at 1 atm, 1,370° at 20 kb, and 1,590° at 40 kb. The primary phase is olivine below 20 kb but is orthopyroxene at 40 kb.In the nepheline basanite, olivine is the primary phase below 14 kb, but clinopyroxene is the first phase to appear above 14 kb. In the alkali-picrite the primary phase is olivine to 40 kb. In the olivine-rich basanite, olivine is the primary phase below 35 kb and garnet is the primary phase above 35 kb. In the olivine-rich alkali basalt the primary phase is olivine below 20 kb and is garnet at 40 kb.Mineral assemblages in a granite-basalt-peridotite join are summarized according to reported experimental data on natural rocks. The solidus of mafic rock is approximately given by T=12.5 P _Kb+1,050°. With increasing pressure along the solidus, olivine disappears by reaction with plagioclase at 9 kb in mafic rocks and plagioclase disappears by reaction with olivine at 13 kb in ultramafic rocks. Plagioclase disappears at around 22 kb in mafic rocks, but it persists to higher pressure in acidic rocks. Garnet appears at somewhat above 18 kb in acidic rocks, at 17 kb in mafic rocks, and at 22 kb in ultramafic rocks.The subsolidus equilibrium curves of the reactions are extrapolated according to equilibrium curves of related reactions in simple systems. The pyroxene-hornfels and sanidinite facies is the lowest pressure mineral facies. The pyroxene-granulite facies is an intermediate low pressure mineral facies in which olivine and plagioclase are incompatible and garnet is absent in mafic rocks. The low pressure boundary is at 7.5 kb at 750° C and at 9.5 kb at 1,150° C. The high pressure boundary is 8.0 kb at 750° C and 15.0 kb at 1,150° C. The garnet-granulite facies is an intermediate high pressure facies and is characterized by coexisting garnet and plagioclase in mafic rocks. The upper boundary is at 10.3 kb at 750° C and 18.0 kb at 1,150° C. The eclogite facies is the highest pressure mineral facies, in which jadeite-rich clinopyroxene is stable.Compositions of minerals in natural rocks of the granulite facies and the eclogite facies are considered. Clinopyroxenes in the granulite-facies rocks have smaller jadeite-Tschermak's molecule ratios and higher amounts of Tschermak's molecule than clinopyroxenes in the eclogite-facies rocks. The distribution coefficients of Mg between orthopyroxene and clinopyroxene are normally in the range of 0.5–0.6 in metamorphic rocks in the granulite facies. The distribution coefficients of Mg between garnet and clinopyroxene suggest increasing crystallization temperature of the rocks in the following order: eclogite in glaucophane schist, eclogite and granulite in gneissic terrain, garnet peridotite, and peridotite nodules in kimberlite.Temperatures near the bottom of the crust in orogenic zones characterized by kyanitesillimanite metamorpbism are estimated from the mineral assemblages of metamorphic rocks in Precambrian shields to be about 700° C at 7 kb and 800° C at 9 kb, although heat-flow data suggest that the bottom of Precambrian shield areas is about 400° C and the eclogite facies is stable.The composition of liquid which is in equilibrium with peridotite is estimated to be close to tholeiite basalt at the surface pressure and to be picrite at around 30 kb. The liquid composition becomes poorer in normative olivine with decreasing pressure and temperature.During crystallization at high pressure, olivine and orthopyroxene react with liquid to form clinopyroxene, and a discontinuous reaction series, olivine orthopyroxene clinopyroxene is suggested. By fractional crystallization of pyroxenes the liquid will become poorer in SiO₂. Therefore, if liquid formed by partial melting of peridotite in the mantle slowly rises maintaining equilibrium with the surrounding peridotite, the liquid will become poorer in MgO by crystallization of olivine, and tholeiite basalt magma will arrive at the surface. On the other hand, if the liquid undergoes fractional crystallization in the mantle, the liquid may change in composition to alkali-basalt magma and alkali-basalt volcanism may be seen at a late stage of volcanic activity.Publication No. 681, Institute of Geophysics and Planetary Physics, University of California, Los Angeles.     

Chloride and Boron behavior in fluids of Los Humeros geothermal field (Mexico): A model based on the existence of deep acid brine

Geothermal field Los Humeros, Mexico, is characterized by a high steam fraction in the well fluids, by extremely high B concentrations in separated water (grams per liter, with a magmatic B signature, δ¹¹B ± 2σ = −0.8 ± 1.6‰), by the absence of correlation between B and Cl concentrations and by positive correlation between B content in separated water and fluid enthalpy. Such behavior is consistent with the existence of moderately acid brine (pH 3–5) at depth with a high B concentration (500–600 mg/kg). In this case a 3-level model can be suggested for Los Humeros: (1) immature, moderately acid brine at depth which is boiling at a temperature ∼350 °C producing the HCl-bearing vapor with a high B content; (2) partial condensation of this vapor at the upper level accompanying water–rock interaction and neutralization; (3) formation of a shallow water-dominated aquifer above a lithologic low-permeability boundary as has been proposed by other authors. A thermochemical computer code has been used to model boiling of an aqueous fluid at 350 °C with 0.1 M of NaCl, 0.05 M of H₃BO₃ and variable amount of HCl (0.001–0.1 M), then a partial condensation of the produced vapor at 250 °C and then separation of the steam–water mixture at 150 °C. Results of simulation are in a qualitative agreement with the observed data.     

A lateglacial climatic reversion in hokkaido, Northeast Asia, inferred from the Larix pollen record

At present, Larix gmelini is a main component of taiga developed in north Sakhalin, northeast China and east Siberia. During the interval from ∼11.8 to 12.4 ka BP, pollen assemblages from north Hokkaido, Japan, are dominated by Larix. Pollen assemblages of this Lateglacial climatic reversal, known as the “Kenbuchi Stadial”, are similar to pollen assemblages from the Last Glacial Maximum in north Hokkaido. Vegetation of Hokkaido inferred from these pollen assemblages — open taiga composed of Larix gmelini, Pinus pumila and Picea jezoensis and/or Picea glehnii — may have been like that of north Sakhalin today. Comparison of these fossil pollen assemblages from Hokkaido with pollen assemblages from modern surface samples in Sakhalin suggests that ∼ 11.8 to 12.4 ka BP, temperatures relative to today were at least 9°C lower in January and 7°C lower in August, and that annual precipitation was at least 735 mm lower than present.     

The upper thermal stability of clinochlore,Mg5Al[AlSi3O10](OH)8, at 10–35 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Clinochlore, which is, within the limits of error, the thermally most stable member of the Mg-chlorites, breaks down at = P _tot to the assemblage enstatite+forsterite+spinel+H₂O along a univariant curve located at 11 kb, 838 ° C; 15kb, 862 ° C; and 18 kb, 880 ° C (±1 kb ±10 ° C). At water pressures above that of an invariant point at 20.3 kb and 894 ° C involving the phases clinochlore, enstatite, forsterite, spinel, pyrope, and hydrous vapor, clinochlore disintegrates to pyrope+forsterite+spinel+H₂O. The resulting univariant curve has a steep, negative dP/dT slope of –930 bar/ °C at least up to 35 kb.Thus, given the proper chemical environment, Mg-chlorites have the potential of appearing as stable phases within the earth's upper mantle to maximum depths between about 60 and 100 km depending on the prevailing undisturbed geotherm, and to still greater depths in subduction zones. However, unequivocal criteria for mantle derived Mg-chlorites are difficult to find in ultrabasic rocks.     

Effects of diffusional modification of garnet growth zoning on P-T path calculations

The effect of intragranular diffusion on chemical zoning in garnet and on P-T paths calculated from that zoning was evaluated using a numerical model of multicomponent diffusion in combination with simulations of garnet growth. Syn-and post-growth diffusion of Mg–Fe–Mn–Ca species in garnet was calculated for a model pelitic assemblage over a range of temperatures from 485 to 635°C. Compositions from zoned garnet, as modified by diffusion, hypothetical inclusions of plagioclase within garnet and matrix phases were used to reconstruct pressure-temperature (P-T) paths from isobaric and polybaric model histories. P-T path calculations, based on numerical simulations conducted over an input isobaric heating path that reached peak temperatures between 585 and 635°C, show that relaxation of garnet compositional gradients by diffusion can induce modest to appreciable curvature in the inferred paths. Retrieved paths also indicated somewhat smaller overall temperature changes relative to the actual temperature difference of the input path. The magnitude of these distortions is shown to depend upon the heating and cooling rate and garnet crystal size as well as the actual peak temperature condition. The effect of diffusion on path trajectories in simulations with thermal histories that also included cooling were comparable to heating-only models that reached peak temperatures approximately 15–30°C higher. Compositions of garnets with radii less than 1 mm, that reached actual peak temperatures of 605°C along temperature-time histories characteristic of regional metamorphism, experienced sufficient diffusional relaxation to introduce errors of hundreds of bars to in excess of one kilobar in path trajectories. Path distortions were significant at heating/cooling rates less than 10°C/Ma, but rapidly diminished for rates faster than this. In polybaric simulations diffusion effects were least noticeable when the actual pressure-temperature conditions changed in a clockwise sense (i.e., convex to higher P and higher T), but apprecciable modification was seen in path models that underwent counterclockwise changes in P and T. Reequilibration of garnet rim compositions occurred during cooling on all paths, and temperature maxima obtained from garnet-biotite geothermometry underestimated actual peak conditions by 40 to 70°C. Calculations suggest that P-T path trajectories calculated from garnets of at least 1 mm size, and that experienced actual thermal maxima below 585°C, are not likely to be distorted by diffusional effects during regional metamorphism. However, P-T path reconstructions based on garnet zonation with smaller grains or higher temperatures may lead to misinterpretation of crystallization history. The partitioning record of peak metamorphic temperatures may be destroyed by diffusional reequilibration of garnet rim compositions during cooling, seriously complicating the task of quantitatively estimating diffusion effects on path calculations.     

Mg-cordierite: Si/Al ordering,optical properties,and distortion

Flux-grown crystals of Mg-cordierite, Mg_1.93 Al_3.95 Si_5.07 O₁₈ synthesized by Lee and Pentecost (1976) appear biaxial (2V _x=10°–25°) under the polarizing microscope whereas their distortion index =0°. Between crossed polars, (001) sections display lamellar and cyclic twinning on {110} and, less frequently, {310}. As duration of annealing at 1,300° C, increased, 2V _x increased. Simultaneously, undulatory extinction and intragrain variations in 2V _x increased slightly up to 4 h annealing, then steadily decreased. For this Mg-cordierite, which lacks significant channel H₂O or CO₂, 2V _x and reach maxima of 88° (=589 nm) and 0.25° after 42 h of annealing but other sectors still display lesser values for 2V _x. Presumably, to the extent 2V _x is less than 88°, these sectors represent intergrown submicros copically twinned orthorhombic domains and thus possess shortrange but not long-range order. Annealing at 1,300° C likely increased long-range order by promoting growth of larger domains at the expense of smaller ones. Ultimately, two differently oriented domains, growing toward each other by annexation (and re-orientation) of smaller domains, meet in a twin boundary that, with time, tends to become straight.The cause of intermediate values for , whether compositional or from submicroscopic {110} or {310} twinning, may be revealed by single crystal X-ray photographs. Streaking of diffraction spots along a^* or b^* (but not c^*) will indicate such twinning as the sole or major cause.     

Mineralogy and chemistry of Cu-Fe-Ni sulfides in orogenic-type spinel peridotite bodies from Ariege (Northeastern Pyrenees,France)

Mantle-derived peridotite bodies of Ariège are composed of spinel lherzolites and harzburgites ranging from remarkably fresh (less than 5% serpentinized) samples with protogranular texture to secondary foliated samples, which are generally 10%–20% serpentinized. The foliated samples have passed through two cycles of deformation and re-crystallization, the earlier ones occurring at temperatures above 950° C for 15 kbar pressure, the later ones at temperatures between 950° and 750° C for 8–15 kbar. Microscopic investigation of 140 samples reveals an accessoy sulfide component which is more abundant in lherzolie than in harzburgite. This component occurs in two differet textural locations, either as inclusions trapped within silicates during the first stage of re-crystallization or as interstitial grains among silicates. Mineralogy and chemistry of both sulfide occurrences are quite similar, at least in samples less than 5% serpentinized. In these fresh samples, sulfides are composed of complex intergrowths between nickel-rich pentlandite and pyrite, coexisting with minor primary pyrrhotite (Fe₇S₈) and chalcopyrite. Pentlandite and pyrite are interpreted as low-temperature breakdown products of upper mantle monosulfide solid solutions. The mineralogy and chemistry of interstitial sulfides in serpentinized rocks vary in parallel with the degree of serpentinization. In samples less than 10% serpentinized, primary pyrrhotite grades into FeS. In samples more than 10% serpentinized, pyrite is replaced by secondary pyrrhotite, and then disappears totally, whereas the coexisting pentlandite is Fe-enriched and replaced by mackinawite. This sequence of alteration indicates a decrease of sulfur fugacity, resulting from serpentinization of olivine at temperatures below 300° C. This is also the case for the inclusions which have been fractured during the tectonic emplacement of the host peridotites within the crust. The presence of non-equilibrium sulfide assemblages in both cases reflects the sluggishness of solid state reactions at near-surface temperatures. It is inferred from these results that sulfides disseminated within orogenic peridotite massifs are so sensitive to serpentinization that most sulfur fugacity estimates based on fractured inclusions and intergranular sulfides are unreliable.     

Retrograde deformation within the Carthage-Colton Zone as recorded by fluid inclusions and feldspar compositions: tectonic implications for the southern Grenville Province

The Carthage-Colton Zone (CCZ), located in the northwestern portion of the Proterozoic Adirondack terrane, forms the boundary between the Adirondack lowlands and highlands and is characterized by textures indicative of ductile deformation. Samples from three rock types have been collected from this zone: (1) pyroxene bearing syenite gneisses of the Diana igneous complex; (2) paragneiss samples from near the northwestern boundary of the Diana complex; (3) a quartz-rich metasediment. Feldspar geothermometry performed on the Diana metasyenites shows that porphyroclasts are relict igneous grains that formed atT900° C, while dynamic recrystallization occurred at temperatures as low as 470 to 550° C as shown by the compositions of feldspar neoblasts. All samples examined in this study from the CCZ contain a suite of CO₂-rich fluid inclusions that are distinctive both texturally and in their microthermometric behavior (Th=-27.7 to-7.1° C) as compared to CO₂-rich Adirondack fluid inclusions that do not lie within this zone (Th=-45.9 to +31.0° C). The results from fluid inclusion microthermometry and feldspar geothermometry restrict the conditions of dynamic recrystallization to temperatures and pressures of 400 to 550° C and 3 to 5 kbar. The retrograde pressure-temperature path must pass through these conditions. Similar fluid inclusion results have been obtained from the Parry Sound Shear Zone (PSSZ) which is a Grenvillian shear zone that is located in Southern Ontario (Lamb and Moecher 1992). However, the inferred retrogradeP-T paths for these two areas, the CCZ and the PSSZ, are different and this difference may be a result of late deformation along shear zones that are located between the two areas.     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.     

The miscibility gap between rhodonite and bustamite along the join MnSiO3-Ca0.60Mn0.40SiO3

The miscibility gap between rhodonite and bustamite has been experimentally determined at temperatures between 600° and 1,100° C. For temperatures below 700° C the resulting limbs have been extrapolated on T-X-diagram as at such low temperatures equilibrium could not be attained. According to microprobe analyses for the natural assemblages of Ravinella di Sotto (Ivrea zone, Italy) and Broken Hill (N.S.W., Australia) equilibrium temperatures are estimated to be at 500° to 550° C. However these assemblages are thought to have re-equilibrated during cooling and the compositions of equilibrium assemblages are also pressure dependent. According to experiments and to molar volume data the rhodonite structure is stabilized by high pressures whereas bustamite by high temperatures. Based on available experimental results and natural data an isobaric T-X _Ca diagram and two isotherm -X _Ca diagrams (for T=400° C and T=600° C) are given.     

Hydrogen isotopic fractionation factor between brucite and water in the temperature range from 100° to 510° C

The hydrogen isotopic fractionation factor between brucite and water has been determined in the temperature range of 100°–510° C. Brucite is always depleted in deuterium relative to the coexisting water, and the degree of depletion becomes larger with decreasing temperature. The fractionation factor changes smoothly in the temperature range of 144°–510° C and its temperature dependence was obtained by the method of least square fit in the following form: 10³In=8.72×10⁶ T ^–2–3.86×10⁴ T ^–1+14.5However, a marked decrease of about 5 was observed at 100°–144° C. The D/H fractionation factor for the brucite-water system is not similar to that for serpentine-water system presented by Sakai and Tsutsumi (1978), though all the hydroxyl ions coordinate to magnesium ion in both minerals. This discrepancy cannot be attributed to hydrogen bonding but to distortion of Mg-octahedron of serpentine, in which the Mg-OH bonding length is shorter than the sum of ionic radius of Mg²⁺ and O^2– and there is no distortion in brucite. It is indicated that aside from hydrogen bonding, the structure effect also controls the D/H fractionation between hydrous mineral and water.     

Evidence of Dry and Cold Climatic Conditions at Glacial Times in Tropical Southeastern Brazil

Last-glacial paleoenvironments have been reconstructed from a pollen and charcoal record analyzed in organic sediments and dated between ca. 18,000 and >48,000¹⁴C yr B.P. The site is located near the village Catas Altas in the lower highland region of southeastern Brazil. The last-glacial landscape was covered by extensive areas of subtropical grasslands and small areas of gallery forests along the rivers, where tropical semideciduous forests and cerrado ecosystems exist today. The subtropical gallery forests were composed ofAraucariaforest trees such asAraucaria angustifolia, Podocarpus, Drimys, Ilex,andSymplocos.Paleofires were frequent. The record indicates that subtropical grassland vegetation, which today is found in patches on the highlands in southern Brazil (especially in the state of Santa Catarina), expanded from southern Brazil to southeastern Brazil, over a distance of more than 750 km, from latitudes of about 28° S to at least 20° S. The completely different last-glacial environment, in comparison to the present-day environment, reflects a dry and cold climate with strong frosts during the winter months. Temperatures of 5°–7°C below those of the present are inferred for the last glaciation.     

Hydrothermal recrystallization and transformation of tridymite

Well ordered tridymites containing atmost 0.016% Na (0.004% Na) were prepared at 1400° C from Na₂WO₄-(K₂WO₄-) fluxes using high purity amorphous silica as starting material. No further reduction of these Na-contents was attainable by soxhlet extraction. These tridymites were treated hydrothermally at temperatures between 815 and 950° C and 200 bars H₂O. The products obtained were investigated optically as well as by powder X-ray methods and were analyzed for Na-contents: the hydrothermal treatment resulted either in recrystallization of tridymite or transformation into quartz mostly depending on Na-contents. Na-contents below about 0.015% tend to favour recrystallization of tridymite within the quartz field (<870° C), Na-contents above about 0.03% tend to favour formation of quartz within the tridymite field (>870° C). This may be due to influences of Na-traces either on the kinetics or on the equilibrium temperature of tridymite-quartz transformation.     

Hydration and phase relations of grossular-spessartine garnets at P H 2O=2 Kb

The phase relations in the system grossular-spessartine-H₂O were investigated at 2.0 Kb aqueous fluid pressure and at subsolidus temperatures down to 420 ° C. Despite metastable persistence of a compositional gap found in some intermediate members, a complete solid solution between grossular and spessartine exists.Linear relations between the unit cell edge, a ₀, and composition were readily observed down to 620 ° C with a ₀=11.849(2) Å and 11.613(2) Å for grossular and spessartine, respectively. Hydrated garnets began to appear at higher temperature for the Ca-rich members. Grossular and spessartine formed at 420 ° C have a ₀=11.901(2) Å and 11.632(2) Å, indicating the presence of 0.6 and 0.2 mol H₂O, respectively. Intermediate members show varying degrees of hydration. Infrared spectra of the more hydrated members show a major and minor absorption bands at 3,620 cm^–1 and 3,660 cm^–1, respectively, in addition to a broad band around 3,430 cm^–1. All the hydrogarnets formed at 420 ° C were proven to be metastable.The rare occurrence of the intermediate grossular-spessartine garnets may be attributed to the lack of appropriate bulk chemistry of the rock rather than to the P-T conditions to which the rock is subjected. There may be a stability field for hydrogrossular below 420 ° C at 2 Kb, but not for hydrospessartine. Any occurrence of hydrogarnet may be used as a temperature indicator setting the maximum of formation for the hydrogarnet-bearing assemblage below 420 ° C at 2 Kb.     

Titanium solubility in olivine in the system TiO<Subscript>2</Subscript>–MgO–SiO<Subscript>2</Subscript>: no evidence for an ultra-deep origin of Ti-bearing olivine

The finding of ilmenite rods in olivine from orogenic peridotites has sparked a discussion about the processes of incorporation and exsolution of titanium in olivine. We have experimentally investigated the solubility of Ti in olivine as a function of composition, temperature and pressure in the synthetic TiO₂–MgO–SiO₂ system. Experiments at atmospheric pressure in the temperature range 1,200–1,500°C showed that the highest concentration of TiO₂ is obtained when olivine coexists with spinel (Mg₂TiO₄). The amount of TiO₂ in olivine in the assemblages olivine + spinel + periclase and olivine + spinel + ilmenite at 1,500°C was 1.25 wt.%. Changes in the coexisting phases and decreasing temperature result in a significant reduction of the Ti solubility. Olivine coexisting with pseudobrookite (MgTi₂O₅) and a Ti–Si-rich melt at 1,500°C displays a fourfold lower TiO₂ content than when buffered with spinel. A similar decrease in solubility is obtained by a decrease in temperature to 1,200°C. There is a negative correlation between Ti and Si and no correlation between Ti and Mg in Ti-bearing olivine. Together with the established phase relations this suggests that there is a direct substitution of Ti for Si at these temperatures, such that the substituting component has the stoichiometry Mg₂TiO₄. The unit cell volume of olivine increases systematically with increasing TiO₂ content demonstrating that the measured TiO₂ contents in olivine are not caused by micro-inclusions but by incorporation of Ti in the olivine structure. Least squares fitting of 20 olivine unit cell volumes against the Ti content yield the relation: V (ų)=290.12(1) + 23.67(85) N_Ti. The partial molar volume of end-member Mg₂TiO₄ olivine (N_Ti=1) is thus 47.24±0.13 cm³. The change of the Ti solubilty in olivine coexistent with rutile and orthopyroxene with pressure was investigated by piston cylinder experiments at 1,400°C from 15 to 55 kbar. There is no increase in TiO₂ contents with pressure and in all the experiments olivine contains ~0.2 wt.% TiO₂. Moreover, a thermodynamic analysis indicates that Ti contents of olivine coexisting with rutile and orthopyroxene should decrease rather than increase with increasing pressure. These data indicate that the ilmenite exsolution observed in some natural olivine does not signify an ultra-deep origin of peridotite massifs.     

An experimental study of Fe-Mg partitioning between garnet and olivine and its calibration as a geothermometer

The partitioning of Fe and Mg between coexisting garnet and olivine has been studied at 30 kb pressure and temperatures of 900 ° to 1,400 °C. The results of both synthesis and reversal experiments demonstrate that K _D (= (Fe/Mg)_gt/(Fe/Mg)_OI) is strongly dependent on Fe/Mg ratio and on the calcium content of the garnet. For example, at 1,000 °C/30 kb, K _D varies from about 1.2 in very iron-rich compositions to 1.9 at the magnesium end of the series. Increasing the mole fraction of calcium in the garnet from 0 to 0.3 at 1,000 ° C increases K _D in magnesian compositions from 1.9 to about 2.5.The observed temperature and composition dependence of K _D has been formulated into an equation suitable for geothermometry by considering the solid solution properties of the olivine and garnet phases. It was found that, within experimental error, the simplest kind of nonideal solution model (Regular Solution) fits the experimental data adequately. The use of more complex models did not markedly improve the fit to the data, so the model with the least number of variables was adopted.Multiple linear regression of the experimental data (72 points) yielded, for the exchange reaction: 3Fe₂SiO₄+2Mg₃Al₂Si₃O₁₂ olivine garnet 2Fe₂Al₂Si₃O₁₂+3Mg₂SiO₄ garnet olivine H ° (30kb) of –10,750 cal and S ° of –4.26 cal deg^–1 mol^–1. Absolute magnitudes of interaction parameters (W _ij ) derived from the regression are subject to considerable uncertainty. The partition coefficient is, however, strongly dependent on the following differences between solution parameters and these differences are fairly well constrained: W _FeMg ^ol -W _FeMg ^gt 800 cal W _CaMg ^gt -W _CaFe ^gt 2,670 cal.The geothermometer is most sensitive in the temperature and composition regions where K _D is substantially greater than 1. Thus, for example, peridotitic compositions at temperatures less than about 1,300 ° C should yield calculated temperatures within 60 °C of the true value. Iron rich compositions (at any temperature) and magnesian compositions at temperatures well above 1,300 °C could not be expected to yield accurate calculated temperatures.For a fixed K _D the influence of pressure is to raise the calculated temperature by between 3 and 6 °C per kbar.