Systematic study of liquidas phase relations in olivine melilitite +H2O +CO2 at high pressures and petrogenesis of an olivine melilitite magma

Near-liquidus phase relationships of a spinel lherzolite-bearing olivine melilitite from Tasmania were investigated over a P, T range with varying , , and . At 30 kb under MH-buffered conditions, systematic changes of liquidus phases occur with increasing ( = CO₂/CO₂ +H₂O+olivine melilitite). Olivine is the liquidus phase in the presence of H₂O alone and is joined by clinopyroxene at low . Increasing eliminates olivine and clinopyroxene becomes the only liquidus phase. Further addition of CO₂ brings garnet+orthopyroxene onto the liquidus together with clinopyroxene, which disappears with even higher CO₂. The same systematic changes appear to hold at higher and lower pressures also, only that the phase boundaries are shifted to different . The field with olivine- +clinopyroxene becomes stable to higher with lower pressure and approaches most closely the field with garnet+orthopyroxene+clinopyroxene at about 27 kb, 1160 °C, 0.08 and 0.2 (i.e., 6–7% CO₂+ 7–8% H₂O). Olivine does not coexist with garnet+orthopyroxene+clinopyroxene under these MH-buffered conditions. Lower oxygen fugacities do not increase the stability of olivine to higher and do not change the phase relationships and liquidus temperatures drastically. Thus, it is inferred that olivine melilitite 2927 originates as a 5% melt (inferred from K_{2 O} and P₂O₅ content) from a pyrolite source at about 27kb, 1160 dg with about 6–7% CO₂ and 7–8% H₂O dissolved in the melt. The highly undersaturated character of the melt and the inability to find olivine together with garnet and orthopyroxene on the liquidus (in spite of the close approach of the respective liquidus fields) can be explained by reaction relationships of olivine and clinopyroxene with orthopyroxene, garnet and melt in the presence of CO₂.     

Redox states of lithospheric and asthenospheric upper mantle

The oxidation state of lithospheric upper mantle is heterogeneous on a scale of at least four log units. Oxygen fugacities ( ) relative to the FMQ buffer using the olivine-orthopyroxene-spinel equilibrium range from about FMQ-3 to FMQ+1. Isolated samples from cratonic Archaean lithosphere may plot as low as FMQ-5. In shallow Proterozoic and Phanerozoic lithosphere, the relative is predominantly controlled by sliding Fe³⁺-Fe²⁺ equilibria. Spinel peridotite xenoliths in continental basalts follow a trend of increasing with increasing refractoriness, to a relative well above graphite stability. This suggests that any relative reduction in lithospheric upper mantle that may occur as a result of stripping lithosphere of its basaltic component is overprinted by later metasomatism and relative oxidation. With increasing pressure and depth in lithosphere, elemental carbon becomes progressively refractory and carbon-bearing equilibria more important for control. The solubility of carbon in H₂O-rich fluid (and presumably in H₂O-rich small-degree melts) under the P,T conditions of Archaean lithosphere is about an order of magnitude lower than in shallow modern lithosphere, indicating that high-pressure metasomatism may take place under carbon-saturated conditions. The maximum in deep Archaen lithosphere must be constrained by equilibria such as EMOG/D. If the marked chemical depletion and the orthopyroxene-rich nature of Archaean lithospheric xenoliths is caused by carbonatite (as opposed to komatiite) melt segregation, as suggested here, then a realistic lower limit may be given by the H₂O +C=CH₄+O₂ (C-H₂O) equilibrium. Below C –H₂O a fluid becomes CH₄ rather than CO₂-bearing and carbonatitic melt presumably unstable. The actual in deep Archaean lithosphere is then a function of the activities of CO₂ and MgCO₃. Basaltic melts are more oxidized than samples from lithospheric upper mantle. Mid-ocean ridge (MORB) and ocean-island basalts (OIB) range between FMQ-1 (N-MORB) and about FMQ +2 (OIB). The most oxidized basaltic melts are primitive island-arc basalts (IAB) that may fall above FMQ+3. If basalts are accurate probes of their mantle sources, then asthenospheric upper mantle is more oxidized than lithosphere. However, there is a wide range of processes that may alter melt relative to that of the mantle source. These include partial melting, melt segregation, shifts in Fe³⁺/Fe²⁺ melt ratios upon decompression, oxygen exchange with ambient mantle during ascent, and low-pressure volatile degassing. Degassing is not very effective in causing large-scale and uniform shifts, while the elimination of buffering equilibria during partial melting is. Upwelling graphite-bearing asthenosphere will decompress along -pressure paths approximately parallel to the graphite saturation surface, involving reduction relative to FMQ. The relative will be constrained to below the CCO equilibrium and will be a function of . Upwelling asthenosphere whose graphite content has been exhausted by partial melting, or melts that have segregated and chemically decoupled from a graphite-bearing residuum will decompress along -decompression paths controlled by continuous Fe³⁺-Fe²⁺ solid-melt equilibria. These equilibria will involve increases in relative to the graphite saturation surface and relative to FMQ. Melts that finally segregate from that source and erupt on the earth's surface may then be significantly more oxidized than their mantle sources at depth prior to partial melting. The extent of melt oxidation relative to the mantle source may be directly proportional to the depth of graphite exhaustion in the mantle source.     

Dry granulite mineral assemblages in the contact aureoles of the Nain complex,Labrador

Thermal aureoles surrounding intrusions of the Nain complex, Labrador, contain many unique or unusual mineral assemblages in aluminous gneisses and granulites, ironstones, and ultramafic rocks. Some of the limiting assemblages are (in addition to feldspars±pyrrhotite±ilmenite±graphite ±biotite±magnetite): Ga-Ol-Hy-Sp, Ga-Cd-Hy-Sp, Ga-Hy-Ol-Qz, Cd-Hy-Os-Qz, Ga-Cd-Sp-Si, Cd-Sp-Co-Si, Ga-Ol-Hy-Sp, Ga-Cd-Hy-Sp, Hy-Ol-Qz-Aug, and Ol-Hy-Sp(±Chl±Ca-amph±Aug). On the basis of some of these assemblages are (in addition to feldspars±pyrrhotite±ilmenite±graphite from 3.7–6.6 kbar and temperatures from 645–915 ° C. The paucity of hydrous phases, the preponderance of Ksp-Plag-Qz or even Cd-Ksp-Qz without evidence of a melt at these temperatures, the stable occurrence of osumilite, and the common presence of graphite suggest that was extremely low. The presence of graphite-pyrrhotite, the compositions of ilmenites, the compositions of coexisting Fe-Ti oxides, and other mineralogical data indicate the was relatively low and, despite the wide range in bulk compositions and rock types, may have followed an approximately buffered trend. It is possible that the magmas of the Nain complex may have acted as an external buffer for the aureole rocks. The unique nature of these mineral assemblages appears to be a function of the extremely low .     

Microphenocrystic pyrrhotite from dacite rocks of Satsuma-Iwojima,southwest Kyushu,Japan and the solubility of sulfur in dacite magma

Microphenocrystic pyrrhotites were observed in the glassy groundmass of two dacite rocks from Satsuma-Iwojima, southwest Kyushu, Japan. It suggests that the dacite magma was saturated with respect to pyrrhotite at the time of eruption, and thus the sulfur contents in the groundmass can be taken as the solubility of sulfur in the dacite magma. The solubility of sulfur in the dacite rocks thus calculated is 65 to 72 ppm sulfur at the estimated conditions of T=900±50°C, and atm.     

Geochemical evidence for magmatic fluids in porphyry copper mineralization

The Koloula Igneous Complex comprises 26 different intrusive phases that have been divided into two major magmatic episodes — cycle 1 intrusions (4.5 Ma) and cycle 2 intrusions (2.4 to 1.5 Ma). The cycle 2 intrusions are further divided into the Inamumu Zoned Pluton (IZP) which is composed of 6 concentrically disposed quartz diorite and tonalite units; and several satellite intrusions. The IZP is host to porphyry-copper mineralization, whereas the cycle 1, and cycle 2 satellite intrusions are barren. Presently exposed mineralization in the IZP (A system) represents the deeply eroded core of a porphyry copper system, where widely-spaced veinlet alteration envelopes ( 1 mm thick) are separated by large volumes of unaltered rock.Compositional trends in biotites and amphiboles from both individual grains and throughout the differentiation series of the IZP, indicate fluctuating but generally increasing existed through the sequence from early magmatic late magmatic early hydrothermal conditions. In amphiboles, compositional domains (Mg-rich) that are indicative of high are correlated with episodes of fluid exsolution, independent evidence of which is provided by multiple generations of fluid inclusions in quartz phenocrysts. These high domains in amphiboles have higher Si, Mn, and Ca contents, but are depleted in Fe, Ti, Na, K, and Cl relative to the less oxidizing domains. The latter elements are those that are known from veinlet alteration assemblages and fluid-inclusion evidence to have been preferentially partitioned into the co-existing fluid phase (late magmatic hydrothermal solution).By contrast, amphiboles from barren rock types that are slightly older than, and of the same age as the IZP, exhibit restricted compositional ranges, and are more Fe-rich. Some individual grains and two cycle 2 satellite intrusions indicate Fe-enrichment during progressive crystallization. Siliceous deuteric amphiboles are commonly as Mg-rich as the high amphibole domains from the IZP, but are easily distinguished from them by their lack of smooth compositional trends versus Si, and by their highly variable Mg and Fe contents.Biotites from the IZP also indicate progressive oxidation, whereas biotites from the barren rock types show either little compositional variation or progressive Fe-enrichment. Biotites from the barren intrusions are richer in Cl, Li and Rb and poorer in Ba than those of the mineralizing intrusions. fHF was very low ( 0.003 bars) in both barren and mineralizing intrusions. During progressive differentiation, Rb content decreased and Ba content increased in IZP biotites, which is atypical, yet explicable owing to the former presence of a competing fluid phase during biotite crystallization.Because is a function of degree of fluid exsolution, then in igneous systems with sufficient Cu, Cl, and ultimately S, progressively higher should potentially lead to more mineralized intrusions. Higher is reflected by steeper Fe versus Si gradients in amphibole domains. Indeed, such a graph for amphiboles from 5 igneous complexes, indicates that two economically mineralized units produced steeper FeSi than those from weakly mineralized intrusions. Steep FeSi trends that do not continue to amphibole domains more siliceous than Si=7.3 (atoms per 23 oxygens) are unlikely to have resulted from subsolidus crystallization and these intrusions are unlikely to be strongly mineralized.     

A regional gradient in the composition of metamorphic fluids in pelitic schist,Pecos Baldy,New Mexico

Two metamorphic isograds cut across graphitic schist near Pecos Baldy, New Mexico. The southern isograd marks the first coexistence of staurolite with biotite, whereas the northern isograd marks the first coexistence of andalusite with biotite. The isograds do not record changes in temperature or pressure. Instead, they record a regional gradient in the composition of the metamorphic fluid phase. Ortega Quartzite, which contains primary hematite, lies immediately north of the graphitic schist. Mineral compositions within the schist change gradually toward the quartzite, reflecting gradients in and . The chemical potential gradients, locally as high as 72 cal/m in and 9 cal/m in , controlled the positions of the two mapped isograds. The staurolite-biotite isograd records where fell below 0.80, at near 10^–23 bars; the andalusite-biotite isograd records where fell below 0.25, at near 10^–22 bars. Dehydration and oxidation were coupled by graphite-fluid equilibrium.The chemical potential gradients apparently formed during metamorphism, as graphite in schist reacted with hematite in quartzite. Local oxidation of graphite formed CO₂ which triggered dehydration reactions along the schistquartzite contact. This process created a C-O-H fluid which infiltrated into overlying rocks. Upward infiltration, local fluid-rock equilibration and additional infiltration proceeded until the composition of the infiltrating fluid evolved to that in equilibrium with the infiltrated rock. This point occurs very close to the staurolite-biotite isograd. Pelitic rocks structurally above this isograd show no petrographic evidence of infiltration, even though calculations indicate that volumetric fluid/rock ratios may have exceeded 15 and thin, rare calc-silicate beds show extensive K-metasomatism and quartz veining.     

An almandine garnet isograd in the Rogers Pass area,British Columbia: The nature of the reaction and an estimation of the physical conditions during its formation

In the Rogers Pass area of British Columbia the almandine garnet isograd results from a reaction of the form: 5.31 ferroan-dolomite+8.75 paragonite+4.80 pyrrhotite+3.57 albite+16.83 quartz+1.97 O₂=1.00 garnet+16.44 andesine+1.53 chlorite+2.40 S₂+1.90 H₂O+10.62 CO₂. The coefficients of this reaction are quite sensitive to the Mn content of ferroan-dolomite.Experimental data applied to mineral compositions present at the isograd, permits calculation of two intersecting P, T equilibrium curves. P=29088–39.583 T is obtained for the sub-system paragonite-margarite (solid-solution), plagioclase, quartz, ferroan-dolomite, and P=28.247 T–14126 is obtained for the sub-system epidote, quartz, garnet, plagioclase. These equations yield P=3898 bars and T=638° K (365° C). These values are consistent with the FeS content of sphalerite in the assemblage pyrite, pyrrhotite, sphalerite and with other estimates for the area.At these values of P and T the composition of the fluid phase in equilibrium with graphite in the system C-O-H-S during the formation of garnet is estimated as: bars, bars, bars, bars, bars, bars, bars, bars, , bars, bars.     

The Shaw bomb,an ideal hydrogen sensor

A simple modification was made to the reaction vessel designed by Shaw (1963) in order to use it as a hydrogen sensor instead of a hydrogen source, thereby allowing a continuous record of to be made during an experiment. The advantage of this arrangement is that (reversed) curves for minerals can be generated from a single experimental run. Other applications are possible.This method was successfully used in the determination of the Ni-NiO-H₂O equilibrium between 580 ° and 830 °C at 2 kbar fluid pressure. The corrected 1 atm values are in agreement with electrochemical measurements. An Ag₇₀Pd₃₀ hydrogen permeable membrane was used for the experiment and flow rates of hydrogen through the membrane were calculated by monitoring the rate of increase or decrease in pressure with an induction pressure transducer. These flow rates range up to two times greater than those calculated for a pure platinum membrane.     

The stability and phase relations of iron chlorite below 8.5 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Iron chlorites with compositions intermediate between the two end-members daphnite (Fe₅Al₂Si₃O₁₀(OH)₈) and pseudothuringite (Fe₄Al₄Si₂O₁₀(OH)₈) were synthesized from mixtures of reagent chemicals. The polymorph with a 7 Å basal spacing initially crystallized from these mixtures at 300 °C and 2 kb after two weeks. Conversion to a 14 Å chlorite required a further 6 weeks at 550 °C. Shorter conversion times were required at higher water pressures. The products contained up to 20% impurities.The maximum equilibrium decomposition temperature for iron chlorite, approximately 550 °C at 2kb, is at an between assemblages (1) and (2) listed below. Synthetic iron chlorite will break down by various reactions with variable P, T, and fugacity of oxygen. For the composition FeAlSi = 523, the sequence of high temperature breakdown products with increasing traversing the magnetite field for P _total = =2kb is: (1) corierite+ fayalite+hercynite; (2) cordierite+fay alite+magnetite; (3) cordierite+magnetite+quartz; (4) magnetite+mullite+quartz. Almandine should replace cordierite in assemblages (1) and (2) but it did not nucleate. The significance of the relationship between iron cordierite and almandine in this system is discussed.At water pressures from 4 to 8.5 kb and at the nickel-bunsite buffer, iron chlorite+quartz break down to iron gedrite+magnetite with temperature 550 to 640 °C along the curve. At temperatures 50 °C greater and along a parallel curve, almandine replaces iron gedrite. For on this buffer curve, almandine is unstable below approximately 4 kb for temperatures to approximately 750 °C.     

Hydrothermal studies on fluorine metamorphic reactions in siliceous dolomite

Metamorphic fluorine reactions in silica deficient dolomite have been investigated between 300 and 560° C in the pressure range from 700 to 2000 bars.The equilibrium temperature for the reaction: 1 talc + 7 dolomite + 2 fluorite 2 chondrodite + 9 calcite + 5 CO₂ + 1 H₂O was experimentally determined as a function of the CO₂-content of the CO₂-H₂O gas phase for the total pressure of 2000 bars. The results are given as an isobaric equilibrium curve in the -diagram of Fig. 2. The equilibrium data were checked and confirmed by reversed reactions.Under the specified pressure conditions the equilibrium temperatures for the above reaction changes from 380° C for very low -values to approximately 500° C for -values around 0.5, and then remains slightly above 500° C in the -interval between 0.5 and 1.0. The temperature conditions for the formation of chrondrodite from tremolite, dolomite, and fluorite are similar to those for the reaction including talc.     

The volatile component of quaternary ignimbrite magmas from the North Island,New Zealand

Ignimbrites from the central North Island consist mainly of glass or its devitrified product (70–95%); their phenocryst mineralogy is varied and includes plag., hyp., ti-mag., ilm., aug., hblende, biot., san., qtz, ol., with accessory apatite, zircon and pyrrhotite. The Fe-Mg minerals can be used to divide the ignimbrites into four groups with hyp.+aug. reflecting high quench temperatures and biot.+hblende +hyp.+aug., low quench temperatures. Oxygen fugacities lie above the QMF buffer curve and even in ignimbrites with low crystal contents the solid phases apparently buffered fO₂. Some ignimbrites contain the assemblage actinolite, gedrite, magnetite and hematite, reflecting post-eruption oxidation. The mineralogy also allows estimation of using pyrrhotite and thence , . The assemblage biotite-sanidine can be used to estimate and thence . Water fugacity is calculated in a variety of ways using both biotite and hornblende as well as the combining reaction . It is high and approaches P _total in most ignimbrites (~4kb) but is lower in unwelded pumice breccias. Comparison of temperature estimates using mineral geothermometers for the various phenocryst phases suggests that the ignimbrite magmas showed temperature differences of 60–100 °C and pressure differences of several kilobars. Individual magma chambers therefore, would have extended over several kilometres vertically. The chemical potential of water may have been constant through the magma.     

The graphite-COH fluid equilibrium in P,T, f_{O_2 } space

The oxygen fugacity ( ) of a C-O-H fluid in equilibrium with graphite has been determined in the range 10–30 kbar by equilibrating solid -buffer assemblages in graphite capsules containing C-O-H fluid. By using different buffers (Fe_xO-Fe₃O₄, Ni-NiO, Co-CoO, Mo-MoO₂), the of the graphite-saturated fluid is bracketed within a narrow range. This technique produces a calibration for the imposed on a sample contained within a graphite capsule. To achieve a thermodynamically-invariant system at fixed P and T, the was imposed on the system with an external buffer and the double-capsule technique. The experiments were performed in solid-media, high pressure apparatus with 19 mm tale-pyrex assemblies. A series of experiments at 10, 15, 20, 25, and 30 kbar, 800–1600° C, with imposed by the Fe₂O₃-Fe₃O₄-H₂O equilibrium were conducted. The experimental results have been fitted to the following equation:

Manganese olivine I: Electrical conductivity

To investigate the point defect chemistry and the kinetic properties of manganese olivine Mn₂SiO₄, electrical conductivity () of single crystals was measured along either the [100] or the [010] direction. The experiments were carried out at temperatures T=850–1200 °C and oxygen fugacities atm under both Mn oxide (MO) buffered and MnSiO₃ (MS) buffered conditions. Under the same thermodynamic conditions, charge transport along [100] is 2.5–3.0 times faster than along [010]. At high oxygen fugacities, the electrical conductivity of samples buffered against MS is 1.6 times larger than that of samples buffered against MO; while at low oxygen fugacities, the electrical conductivity is nearly identical for the two buffer cases. The dependencies of electrical conductivity on oxygen fugacity and temperature are essentially the same for conduction along the [100] and [010] directions, as well as for samples coexisting with a solid-state buffer of either MO or MS. Hence, it is proposed that the same conduction mechanisms operate for samples of either orientation in contact with either solid-state buffer.The electrical conductivity data lie on concave upward curves on a log-log plot of vs , giving rise to two regimes with different oxygen fugacity exponents. In the low- regime , the exponent, m, is 0, the MnSiO₃-activity exponent, q, is 0, and the activation energy, Q, is 45 kJ/mol. In the high regime 10^{ - 7} {\text{atm}}} \right)$$ " align="middle" border="0"> , m=1/6, q=1/4–1/3, and Q=45 and 200 kJ/mol for T<1100 °c=" and=">T>1100 °C, respectively.     

Antigorite-ophicarbonates: Phase relations in a portion of the system CaO-MgO-SiO2-H2O-CO2

The occurrence of critical assemblages among antigorite, diopside, tremolite, forsterite, talc, calcite, dolomite and magnesite in progressively metamorphosed ophicarbonate rocks, together with experimental data, permits the construction of phase diagrams in terms of the variables P, T, and composition of a binary CO₂-H₂O fluid. Equilibrium constants are given for the 30 equilibria that describe all relations among the above phases. Ophicalcite, ophidolomite, and ophimagnesite assemblages occupy partially overlapping fields in the diagram. The upper temperature limit of ophicalcite rocks lies below that of ophidolomite and ophimagnesite. The fluid phase in ophicarbonate rocks has 0.8$$ " align="middle" border="0"> , and there are indications that during their progressive metamorphism is approximately equal to P _total.     

Zur Bestimmung einer definierten mittleren Lichtbrechung optisch einachsiger Minerale im Dünnschliff

Zusammenfassung Durch Gangunterschiedsbestimmungen in der auf dem Drehtisch eingemessenen Kreisschnittebene optisch einachsiger Kristalle läßt rich eine mittlere Lichtbrechung theoretisch ableiten and experimentell direkt bestimmen. Ein graphisches and ein rechnerisches Verfahren zur Gewinnung der aus den Ganguntersehieden wird entwickelt and an Quarz, Korund, Zirkon, Turmalin und Eisenorthoklas ausprobiert. Man erhält für die mittlere Lichtbrechung Werte, die günstigenfalls mit der Immersionsmethode an Genauigkeit vergleichbar sind.     

Pyroclastic flows and lavas of the Mogan and Fataga formations,Tejeda Volcano,Gran Canaria,Canary Islands: mineral chemistry,intensive parameters,and magma chamber evolution

The Mogan and Fataga formations on the island of Gran Canaria, Canary Islands, represent a sequence of approximately 30 intercalated pyroclastic and lava flows (total volume about 500 km³ dense-rock equivalent) including subalkaline rhyolitic, peralkaline rhyolitic and trachytic pyroclastic flows, nepheline trachyte lavas and a small volume of alkali basaltic lavas and tephra deposits. The eruption of the intermediate to silicic rocks of the Mogan and Fataga formations follows the roughly 4 Ma duration of basaltic shield volcanism. The most common assemblage in the evolved (Mogan and Fataga) rocks is anorthoclase+ edenitic amphibole+ilmenite+magnetite±augite±hypersthene +apatite+pyrrhotite. A few flows also contain plagioclase, biotite, or sphene. Coexisting Fe-Ti oxides yield equilibrium temperatures between 835 and 930° C and log between –11.2 and –12.6. The lowermost pyroclastic flow of the Mogan formation is zoned from a rhyolitic base (848° C) to a basaltic top (931° C). Unit P1 has an oxygen isotope feldspar-magnetite temperature (850° C) very close to its Fe-Ti oxide temperature. One of the youngest Mogan flows is zoned from a comendite (836° C) at the base to a comenditic trachyte (899° C) at the top. The Fataga formation pyroclastic flows show only slight compositional zonation, and one flow has the same Fe-Ti oxide compositions at top and base.Calculations using the reaction 1/3 magnetite+SiO₂ (melt)=ferrosilite+1/6 O₂ indicate total pressures of 1–4 (±3) kb for six of the Mogan flows and one of the Fataga flows. For four of the pyroclastic flows, equilibria involving tremolite-SiO₂-diopside-enstatite-H₂O and phlogopite-SiO₂-sanidine-enstatite-H₂O imply water contents of 0.9 to 2.6 (±0.5) wt% and between 80 and 610 bars, which indicates that magma within the Tejeda reservoir was H₂O-undersaturated throughout the entire history of Mogan to Fataga volcanism. The fluorine contents of amphibole, biotite, and apatite, and chlorine contents of apatite reveal thatf _HF/ andf _HCl/ high compared to most igneous rocks and are consistent with the peralkaline nature of most of the volcanics. Thef _HCl estimate for one flow is 10^–2 to 10^–1 bars andf _HF for six of the flows ranges from about 10^–1 to 6 bars. Pyrrhotite compositions yield estimates for log between –1 and –3, log between –2 and 1.5, and log between 0.5 and 3, which fall in the range of most intermediate to silicic systems. The lack of a systematic trend with time for magma composition, Fe-Ti oxide temperatures, water contents, phenocryst abundances, and ferromagnesian phase composition indicate that the Tejeda magmatic system was open and kept at nearly the same conditions by the periodic addition of more primitive melts.The intensive thermodynamic parameters estimated from coexisting phenocryst equilibria are used to constrain the eruption dynamics based on solution of the conservation equations for a vapor plus pyroclast mixture. The estimates of magma reservoir temperature, pressure, and water concentration, when combined with a one-dimensional fluid dynamical model of a pyroclastic eruption, imply that the velocities of the ash flows at the vent exit were on the order of 100 to 200 m s^–1, and the mass flow rates were about 10⁷ kg s^–1 for an assumed vent radius of 10 m.     

Devolatilization equilibria in graphite-pyrite-pyrrhotite bearing pelites with application to magma-pelite interaction

The proportions of species in a C-O-H-S fluid in equilibrium with graphite, pyrite and pyrrhotite were calculated for a range of pressure, temperature and conditions, using the equilibrium constants and mass balance method, for ideal and non-ideal mixing in the fluid. Under typical metamorphic conditions, H₂O, CO₂, CH₄ and H₂S are the principal fluid species with H₂S favored by higher temperatures, lower pressures and lower conditions. The dominance of H₂S in the fluid at high temperatures leads to values of becoming significantly less than 1, and causes hydrous minerals to dehydrate at lower temperatures than the case when . The production of H₂S-bearing fluids provides a mechanism for the selective transfer of sulfur from a graphite-pyrite-pyrrhotite bearing pelite into a pluton via a fluid phase, without requiring wholesale melting and assimilation of rocks. Such a process is feasible if a magma is intruded by stoping, which allows a significant volume of pelite country rock to be raised rapidly to temperatures approaching that of the magma. H₂S-bearing fluids produced from graphite-pyrite-pyrrhotite pelites (due either to magmatic intrusion or regional metamorphism) may also mobilize ore-forming metals as sulfide complexes.     

Manganese pyroxenoids and carbonates: Critical phase relations in metamorphic assemblages from the Alps

The compositions of coexisting pyroxmangites, rhodonites, rhodochrosites and manganese calcites in regional metamorphosed manganese cale-silicate marbles from Val Scerscen and Alagna were analysed by microprobe and permit definition of critical tie lines at metamorphic grades appropriate to temperatures between 400 and 450 °C.Variations in composition of coexisting mineral pairs in one and the same locality are attributed to variations in and not to metamorphic temperatures. From the analysed assemblages isothermal plots (with SiO₂ as excess component) were constructed for the system CaO-MnO-SiO₂-CO₂.     

The volcanoes and caldera of Talasea,New Britain: Mineralogy

The Talasea Peninsula is composed of a chain of Quaternary volcanoes whose lavas range from basalt to rhyolite. The peninsula is situated in an orogenic environment and the lavas, while essentially calc-alkaline, show some differences from other orogenic suites on the Pacific rim. The most distinctive feature of the Talasea series is absolute iron enrichment in some lavas. Mineralogically, the andesites are characterized by phenocrysts of plagioclase, orthopyroxene, clinopyroxene and titanomagnetite, while the basalts lack titanomagnetite phenocrysts but contain olivine. The acid rocks have a mineralogy similar to that of the andesites, but also contain quartz, amphibole, biotite and ilmenite. The compositions of coexisting titanomagnetite and ilmenite in the acid lavas indicate equilibration temperatures in the range 920° to 860° C and oxygen fugacities ( ) above those of the fayalitemagnetite-quartz buffer assemblage. The mineralogical evidence supports the hypothesis of a crystal fractionation origin for this series and there is a possibility that the was more or less constant during the early stages of its evolution. The iron enriched lavas may be an offshoot from the main line of descent, resulting from near-surface fractionation, with the dominance of plagioclase in the crystal residuum producing an iron-rich liquid.     

Aenigmatite,sodic pyroxene,arfvedsonite and associated minerals in syenites from Morotu,Sakhalin

Aenigmatite, sodic pyroxene and arfvedsonite occur as interstitial minerals in metaluminous to weakly peralkaline syenite patches in alkali dolerite, Morotu, Sakhalin. Aenigmatite is zoned from Ca, Al, Fe³⁺-rich cores to Ti, Na, Mn, Si-rich rims reflecting the main substitutions Fe²⁺Ti⁴⁺Fe³⁺, NaSiCaAl and Mn²⁺Fe²⁺. Aenigmatite replaces aegirine and ilmenite supporting the existence of a no-oxide field in — T space. In one case aenigmatite has apparently formed by reaction between ilmenite and arfvedsonite. Titanian aegirine (up to 3.0 wt% TiO₂) and Fe-chlorite may replace aenigmatite. Sodic pyroxene occurs as zoned crystals with cores of aegirine-augite rimmed by aegirine and in turn by pale green aegirine containing 93 mol% NaFe³⁺Si₂O₆. Additional substitution of the type NaAlCaFe²⁺ is indicated by significant amounts (up to 6 mol%) of NaAlSi₂O₆. Arfvedsonite is zoned with rims enriched in Na, Fe and depleted in Ca which parallels the variation of these elements in the sodic pyroxenes.The high peralkalinity of the residual liquid from which the mafic phases formed resulted from the early crystallization of microperthite (which makes up the bulk of the syenites) leading to an increase in the Na₂O/(Na₂O+K₂O) and (Na₂O+K₂O)/Al₂O₃ ratios of the remaining interstitial liquid which is also enriched in Ti, Fe, and Mn. Bulk composition of the melt, , temperature and volatile content were all important variables in determining the composition and stability of the peralkaline silicates. in the residual liquid appears to have been buffered by arfvedsonite-aegirine and later by the arfvedsonite-aenigmatite and aenigmatite-aegirine equilibria under conditions of a no-oxide field. An increase in , above that of the alkali buffer reactions, is inferred by an increase of Ti and Mn in aenigmatite rims. The latest postmagmatic vapour crystallization stage of the syenites is marked by extremely low which may have been facilitated by exsolution of a gas phase. Low is supported by the replacement of aenigmatite by titanian aegirine, and the formation of rare Ti-rich garnet with a very low (Ti⁴⁺+Fe³⁺)/(Ti+Fe) ratio of 0.51, associated with leucoxene alteration of ilmenite.