Water in microcrystalline quartz of volcanic origin: Agates

Agates of volcanic origin, containing the different quartz species, fibrous, length-fast chalcedony (CH), granular fine quartz (FQ), and fibrous, length-slow, to lepidospheric quartzine (QN), have been investigated to evaluate possible relations between microstructure, i.e. crystallite size and texture, refractive indices, densities, contents of trace elements and of water, as well as dehydration behaviour. By means of near infrared spectroscopy, total water contents , could be differentiated quantitatively into contents of molecular water, , and silanole-group water, . Despite the low total water contents of the agates studied ( between 1 and 2 wt.%), near infrared spectroscopy results in reliable data on and .Wall-layering CH consists of fibrous quartz crystals and exhibits higher C-ratios, , than horizontally layered FQ which consists predominantly of granular quartz crystals (C _CH=0.45±0.11 (N=6), C _FQ=0.36±0.10 (N=4). This result is interpreted to be due to analogy with the behaviour of C-ratios in fluid phase-deposited opals-AN (hyalithe) and liquid phase-deposited opals-AG (non-crystalline opal) or -CT (common opal) (Langer and Flörke 1974).Translucent layers of CH show mostly lower refractive indices, when measured parallel than when measured perpendicular to the axes of the quartz fibers. The same is true for milky layers of CH. Crystallite sizes are smaller in the latter than in the former.For all samples studied, exists a positive correlation between at% (1/2Ca+1/2Mg+Na+K+Li) and at% (Al³⁺+Fe³⁺). This indicates that at least parts of (A1³⁺+ Fe³⁺) substitute for Si in the quartz structure. The charge is balanced by incorporation of di- and mono-valent cations in structural interstices. When the quantity at % H⁺, as obtained from , is included into the sum at% (1/2 Me²⁺+Me⁺), the above correlation is destroyed. This result could be indicative for a strong concentration of the Si-OH groups in the surface of the quartz microcrystallites.     

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.     

An experimental study of the diffusion of oxygen in quartz and albite using an overgrowth technique

Diffusion rates of¹⁸O tracer in quartz ( c, 1 Kb H₂O) and Amelia albite ( 001, 2 Kb H₂O) have been measured, using Secondary Ion Mass Spectrometry (SIMS). A new technique involving hydrothermal deposition of labelled materials has removed the possibility of pressure solution-reprecipitation processes adversely affecting the experiments. Reported diffusion constants are:-quartz ( c), ,Q=98±7 KJ mol^–1 (600–825° C, 1 Kb); Amelia albite ( 001), ,Q=85±7 KJ mol^–1, (400–600° C, 2 Kb). Measured quartz¹⁸O diffusivities decrease discontinuously at the- transition, reflecting strong structural influences. The reported albite data agree with previously recorded studies, but-quartz data indicate significantly lower activation energies. Possible causes of this discrepancy, and some geological consequences, are noted.     

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.     

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 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.     

New thermodynamic models and revised calibrations for the Ti-in-zircon and Zr-in-rutile thermometers

The models recognize that ZrSiO₄, ZrTiO₄, and TiSiO₄, but not ZrO₂ or TiO₂, are independently variable phase components in zircon. Accordingly, the equilibrium controlling the Zr content of rutile coexisting with zircon is ZrSiO₄ = ZrO₂ (in rutile) + SiO₂. The equilibrium controlling the Ti content of zircon is either ZrSiO₄ + TiO₂ = ZrTiO₄ + SiO₂ or TiO₂ + SiO₂ = TiSiO₄, depending whether Ti substitutes for Si or Zr. The Zr content of rutile thus depends on the activity of SiO₂ as well as T, and the Ti content of zircon depends on and as well as T. New and published experimental data confirm the predicted increase in the Zr content of rutile with decreasing and unequivocally demonstrate that the Ti content of zircon increases with decreasing . The substitution of Ti in zircon therefore is primarily for Si. Assuming a constant effect of P, unit and that and are proportional to ppm Zr in rutile and ppm Ti in zircon, [log(ppm Zr-in-rutile) + log] = A₁ + B₁/T(K) and [log(ppm Ti-in-zircon) + log − log] = A₂ + B₂/T, where the A and B are constants. The constants were derived from published and new data from experiments with buffered by either quartz or zircon + zirconia, from experiments with defined by the Zr content of rutile, and from well-characterized natural samples. Results are A₁ = 7.420 ± 0.105; B₁ = −4,530 ± 111; A₂ = 5.711 ± 0.072; B₂ = −4,800 ± 86 with activity referenced to α-quartz and rutile at P and T of interest. The zircon thermometer may now be applied to rocks without quartz and/or rutile, and the rutile thermometer applied to rocks without quartz, provided that and are estimated. Maximum uncertainties introduced to zircon and rutile thermometry by unconstrained and can be quantitatively assessed and are ≈60 to 70°C at 750°C. A preliminary assessment of the dependence of the two thermometers on P predicts that an uncertainty of ±1 GPa introduces an additional uncertainty at 750°C of ≈50°C for the Ti-in-zircon thermometer and of ≈70 to 80°C for the Zr-in-rutile thermometer.     

Solubility of CO2 in olivine melilitite at high pressures and role of CO2 in the earth's upper mantle

The positions of the liquidi and the near-liquidus phases of olivine-melilitite+CO₂ have been determined under MH-buffered and furnace-buffered conditions up to 40 kb. It is found that CO₂ alone lowers the liquidus compared to dry conditions, yet its influence is minor compared to H₂O. The major role of CO₂ is to favour the growth of orthopyroxene and garnet over that of olivine at least at high pressures. CO₂-contents of glasses from experiments just above the liquidus (MH-buffered) were determined as 5.1 % at 10kb; 7.5 % at 20kb, 9.3 % at 30kb and 10–11 % (estimated) at 40 kb. Experiments on (pyrolite –40 % olivine)+H₂O+CO₂ show that CO₂ occurs under mantle conditions as carbonate under subsolidus conditions and dissolved in a melt above the solidus. At 30kb, the solidus lies between 1,000 ° C and 1,050 ° C for vapour-saturated conditions, at and at .     

Aluminum partitioning between olivine and ultrabasic silicate liquid to 6 GPa

Trace element analyses of 1-atm and high-pressure experiments show that in komatiite and peridotite, the olivine (OL)/liquid (L) distribution coefficient for Al₂O₃ ( ) increases with pressure and temperature. Olivine in equilibrium with liquid accepts as much as 0.2 wt% Al₂O₃ in solution at 6 GPa. Convergence to equilibrium compositions at this high level is shown by cation diffusion of Al into synthetic forsterite crystals of low-Al contents in the presence of melt. Convergence to low-Al equilibrium compositions at lower P and T is shown by diffusion of Al out of synthetic forsterite with high initial Al content. Isobaric and isothermal experimental data subsets reveal that temperature and pressure variations both have real effects on . Variation in silicate melt composition has no detectable effect on within the limited range of experimentally investigated mixtures. Least-squares regression for 24 experiments, using komatiite and peridotite, performed at 1 atm to 6 GPa and 1300 to 1960°C, gives the best fit equation: Increase in with increasingly higher-pressure melting is consistent with incorporation of a spinel-like component of low molar volume into olivine, although other substitutions possibly involving more complex coupling cannot be ruled out. High P-T ultrabasic melting residues, if pristine, may be recognized by the high calculated from microprobe analyses of Al₂O₃ concentrations in residual olivines and estimated Al₂O₃ concentration in the last liquid removed. In general the low levels of Al in natural olivine from mantle xenoliths suggest that pristine residues are rarely recovered.     

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.     

Fe2+-Mg2+ partition between coexisting cordierite and garnet — a discussion of the experimental data

The partition of iron and magnesium between cordierite and garnet depends on as well as temperature. The apparently conflicting experimental data on the values of K _D may be reconciled by considering the pertaining during the different experiments.     

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.     

High-temperature creep and kinetic decomposition of Ni2SiO4

To investigate high-temperature creep and kinetic decomposition of nickel orthosilicate (Ni₂SiO₄), aggregates containing 3 vol% amorphous SiO₂ have been deformed in uniaxial compression at a total pressure of one atomsphere. Twenty-three samples with grain sizes (d) from 9 to 30 m were deformed at temperatures (T) from 1573 to 1813 K, differential stresses () from 3 to 20 MPa, and oxygen fugacities (f o ₂) from 10^-1 to 10⁵ Pa. At temperatures up to 1773 K, the steady-state creep rate () can be described by the flow law

APL computer programs for thermodynamic calculations of equilibria in P-T-X CO 2 space

APL computer programs for the thermodynamic calculation of devolatilization and solid-solid equilibria operate using stored values for the molar volume and entropy of solids, the free energies of H₂O and CO₂, and the free energies of formation for 110 geologically-important phases. P-T-X _{CO 2} calculations of devolatilization equilibria can be made at pressures from 0.2 through 10 kb, and temperatures from 200 through 1,000° C. P-T-X calculations of solid-solid equilibria may be accomplished at pressures to 30 kb and temperatures to 1,000° C. Calculations can be extrapolations from experimental points, or direct calculations from thermochemical data alone. Options are available in these programs to consider effects of: real vs. ideal gas mixing, thermal expansion and compressibility, solid solution, fluid pressure differing from solid pressure, and uncertainties in high-temperature entropies.A collection of thermodynamic data programs accompanies the programs for calculating P-T-X _{CO 2} equilibria. Over a wide range of physical conditions, the data functions report free energies, entropies, fugacities of H₂O and CO₂, high temperature entropies of solids, and activities of components in H₂O-CO₂ mixtures.List of Symbols Activity of H₂O and CO₂ - G_f Free energy of formation of a phase from elements - G_r Free energy change of reaction - G _r ^o Standard state free energy change of a reaction - Free energies of pure H₂O and CO₂ - H _r ^o Standard state enthalpy change for a reaction - K Equilibrium constant - R Gas constant - S _r ^o Standard state entropy change of reaction - S _s ^o Standard state entropy change of solids in a reaction - V_s ^o Standard state volume change of a reaction - V_s ^o Standard state volume change of solids in a reaction - Mole fraction of H₂O and CO₂ - Activity coefficient of H₂O and CO₂     

Stability of the assemblage cordierite +K feldspar+quartz

Under hydrous conditions the stability field of the assemblage Mg-cordierite+K feldspar+quartz is limited on its low-temperature side by the breakdown of cordierite+K feldspar into muscovite, phlogopite and quartz, whereas the high-temperature limit is given by eutectic melting. The compatibility field of the assemblage ranges from 530° C to 745° C at 1 kbar , from 635 to 725° C at 3 kbars , from 695 to 725° C at 5 kbars and terminates at 5.5 kbars . Most components not considered in the model system will tend to restrict this field even more. However, the condition < P _total will increase the range of stable coexistence drastically, making the assemblage common at elevated temperatures from contact metamorphic rocks up to intermediate pressure granulites of appropriate bulk composition.     

Impact of land use change on groundwater quality in a typical karst watershed of southwest China: a case study of the Xiaojiang watershed,Yunnan Province

The impact of land-use change on the quality of groundwater in the Xiaotjiang watershed, China was assessed for the period 1982–2004. Groundwater samples were collected from 30 monitoring points across the watershed, and were representative of the various changes, determined by remote sensing and geographical information systems. The results indicate that 610 km² (60% of the total watershed area) were subject to land-use change during the period. The most important changes were the conversion of 135 km² of forested land to cultivated land, and 211 km² of unused land to cultivated land. The main impact was ascribed to diffuse pollution from fertilizers applied to newly cultivated land, and from building development. Overall the groundwater pH value was significantly increased, as were the concentrations of ions , , , , and Cl⁻ in groundwater whilst the concentrations of Ca²⁺ and declined. More precisely, in the regions where forested land and unused land were converted into cultivated land, the pH value and the concentrations of Mg²⁺, , , , , Cl⁻ increased whilst the concentrations of Ca²⁺ and declined. However in the region where cultivated land was converted into construction land, the pH value and the concentrations of Ca²⁺, Mg²⁺, , , , , , Cl⁻ increased.

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Résumé  L’impact des changements de l’utilisation du territoire sur la qualité de l’eau souterraine dans le bassin versant de Xiaojiang, en Chine, a été évalué de 1982 à 2004. Des échantillons d’eau souterraine ont été récoltés à partir de 30 points d’observation éparpillés sur le bassin, représentant les divers changements déterminés par télédétection et système d’information géographique. Les résultats indiquent que 610 km² (soit 60% de la surface du bassin) ont été sujets à des modifications de l’utilisation du territoire sur cette période. Les changements les plus importants furent la conversion de 135 km² de forêt et 211 km² de terres inutilisées en terres cultivées. Le principal impact est attribué à la pollution diffuse des engrais utilisés en agriculture et pour les batiments. De manière générale le pH de l’eau souterraine a augmenté significativement, ainsi que les concentrations des ions , , , , et Cl⁻, tandis que les concentration en Ca²⁺ et ont diminué. Plus précisément dans les régions transformées en terres cultivées, la valeur du pH et les concentrations en Mg²⁺, , , , , Cl⁻ ont augmenté tandis que les concentrations en Ca²⁺ et ont diminué. Toutefois dans les régions cultivées converties en zones de construction, le pH et les concentrations en Ca²⁺, Mg²⁺, , , , , , Cl⁻ ont augmenté.

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Resumen  El impacto del cambio en uso de la tierra en la calidad del agua en la cuenca Xiaojiang, China fue evaluado para el periodo 1982–2004. Muestras de agua subterránea fueron tomadas de 30 puntos de monitoreo a través de la cuenca, y fueron representativas de los múltiples cambios, determinados por sensores remotos y sistemas de información geográfica. Los resultados indican que 610 km² (60% del área total de la cuenca) estaban sujetos a cambios de uso de la tierra durante el periodo estudiado. Los cambios más importantes fueron la conversión de 135 km² de bosques a tierra cultivada, y 211 km² de tierra sin uso (ociosa) a tierra cultivada. El impacto principal fue causado por contaminación difusa de fertilizantes aplicados a la tierra recientemente cultivada, y a desarrollo de construcciones. En general el pH en agua subterránea creció significantemente, al igual que las concentraciones de los iones , , , , y Cl⁻ en agua subterránea mientras que las concentraciones de Ca²⁺ y decrecieron. Mas precisamente, en las regiones donde bosque y tierra ociosa fueron convertidas en tierra cultivada, el valor de pH y las concentraciones de Mg²⁺, , , , , Cl⁻ crecieron mientras las concentraciones de Ca²⁺ y decrecieron. Sin embargo en la región donde tierra cultivada fue convertida en construcciones, el valor de pH y las concentraciones de Ca²⁺, Mg²⁺, , , , , , Cl⁻ crecieron.

     

The origin of the high-K latites from Camp Creek,Arizona: constraints from experiments with variable fO2 and a_{{\text{H}}_{\text{2}} {\text{O}}}

Near-liquidus melting experiments were performed on a high-K latite at fO₂'s ranging from iron-wustite-graphite (IWG) to nickel-nickel oxide (NNO) in the presence of a C-O-H fluid phase. Clinopyroxene is a liquidus phase under all conditions. At IWG , the liquidus at 10 kb is about 1,150° C but is depressed to 1,025° C at NNO and . Phlogopite and apatite are near-liquidus phases, with apatite crystallizing first at pressures below 10 kb. Phlogopite is a liquidus phase only at NNO and high . Under all conditions the high-K latites show a large crystallization interval with phlogopite becoming the dominant crystalline phase with decreasing temperature. Increasing fO₂ affects phlogopite crystallization but the liquidus temperature is essentially a function of . The chemical compositions of the near-liquidus phases support formation of the high-K latites under oxidizing conditions (NNO or higher) and high . It is concluded from the temperature of the H₂O-saturated liquidus at 10 kb, the groundmass: crystal ratio and presence of chilled latite margins around some xenoliths that the Camp Creek high-K latite magma passed thru the lower crust at temperatures of 1,000° C or more.     

H<Subscript>2</Subscript>O diffusion in peralkaline to peraluminous rhyolitic melts

The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing about 2 wt% H₂O _t in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H₂O _t ) and water-rich (~2 wt% H₂O _t ) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles of hydrous species (OH groups and H₂O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity () was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess of Al₂O₃ with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:

Sillimanite-potash feldspar assemblages in graphitic pelites,Strontian area,Scotland

Graphitic pelites of the western Moinian were metamorphosed at the time of emplacement of the Strontian Granodiorite intrusion, at a late stage of the Caledonian Orogeny, producing a metamorphic zonation. The Sillimanite Zone (in which K feldspar does not occur with sillimanite) is succeeded by the Muscovite-Sillimanite-K feldspar Zone, Sillimanite-K feldspar Zone (without primary muscovite) and Cordierite-K feldspar Zone. Secondary muscovite from retrograde hydration of sillimanite+K feldspar is distinguished texturally from primary muscovite, but is compositionally similar. Primary porphyroblastic muscovite, inherited from the regional metamorphic textural evolution of the rocks, disappears abruptly at the muscovite-out isograd. Migmatites of earlier regional origin, with recrystallized textures, are distinguished from those associated with the late Caledonian metamorphism, which are confined to the Sillimanite-K feldspar and Cordierite-K feldspar Zones. Muscovite compositions are inferred to be very low in Fe³⁺. There are no marked changes in muscovite composition at the entry of sillimanite+K feldspar. Higher Na contents than in some other muscovites coexisting with sillimanite+K feldspar are interpreted in terms of relatively low P in the Strontian area. Andalusite is found at two localities. From cordierite-garnet-sillimanite-biotite-K feldspar-quartz assemblages, a P estimate of 4.1±0.4 kbar is obtained, with the aqueous fluid having , and the T at the cordierite-K feldspar isograd is estimated as 690° C. T at the muscovite-out isograd is inferred to the maximum for muscovite-quartz-sillimanite-K feldspar equilibrium with graphite at P4.1 kbar: T 645° C, with . The well-defined lower boundary of the Muscovite-Sillimanite-K feldspar Zone is attributed to regionally rather homogeneous fluid composition at . The low P prevented melting in the Muscovite-Sillimanite-K feldspar Zone. Migmatites in the higher zones are attributed to partial melting, which accounts for the low necessary to produce the cordierite assemblages. Obscurity of these migmatites is attributed to deformation during and after the migmatization. A breccia structure in and near the Cordierite-K feldspar Zone, where pelites have flowed around disrupted pieces of psammite and amphibolite, can be explained by presence of grain-boundary melts in the pelites.