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.     

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.     

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.     

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.     

Estimation of the depth of origin of basic magmas: A modified thermodynamic approach and a comparison with experimental melting studies

Thermodynamic calculations, modified after Nicholls et al. (1971), which relate the activity of silica in a lava to the temperature and pressure conditions at which the lava could be in equilibrium with a mantle mineral assemblage, have been extended to H₂O-bearing magmas by using published experimental data to derive the dependence of on the weight fraction of H₂O dissolved in a magma. A petrogenetic grid has been calculated which gives the P-T conditions under which a magma with a given at its liquidus at 1 atm could equilibrate with a mantle mineral assemblage containing olivine (ol) and orthopyroxene (opx) for different amounts of H₂O in the magma at its source. This grid is in good agreement with the results of experimental studies as summarized by Green (1971) and Brey and Green (1975). The results show that the pressure at which a given magma composition can equilibrate with ol + opx increases for increasing amounts of H₂O dissolved in the magma at depth.In addition, experimental data have been used to calculate the effect of olivine crystallization and removal on the in the residual liquid to assess the effect of low-pressure differentiation on . The results show that if 20 % olivine is added to a basalt magma, its calculated pressure of equilibration with ol+opx increases by 4–5 kbar for a given temperature. The calculated effects of olivine removal and H₂O addition on are reasonably consistent with the silicate mixing model of Burnham (1975).Thermodynamic calculations of this type may be useful for assessing the internal consistency of certain experimental data, and in extrapolating the results to other magma compositions. The application of these calculations to determining the possible depth of origin of natural lavas appears to be limited primarily by the difficulty in determining in a lava at its liquidus temperature.     

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.     

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.     

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.     

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.     

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.     

Aenigmatite stability in silica-undersaturated rocks

Aenigmatite is common in many trachytes, phonolites and agpaitic nepheline syenites. Petrographic evidence suggests that the aenigmatite in these rocks arises by the reaction of Ti-magnetite with a peralkaline silica-undersaturated liquid, and it is postulated that a no-oxide field, where aenigmatite is stable, exists in alkaline undersaturated magmas. This field is similar to that found in silicic liquids but lies below the FMQ buffer curve in space and is probably confined within narrow limits of temperature and oxygen fugacity. The hydrated equivalent of aenigmatite is possibly astrophyllite and the latter mineral is frequently associated with Na-amphiboles in natural rocks. This suggests that the stability field of astrophyllite is similar to that of Na-amphiboles with respect to temperature and .     

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.     

Genesis of the calc-alkaline igneous rock suite

A high pressure experimental study of the partial melting fields of synthetic high-alumina olivine tholeiite, high-alumina quartz tholeiite, basaltic andesite, andesite, dacite and rhyodacite under dry and wet conditions has been conducted in order to investigate possible origins of the calc-alkaline series from the upper mantle. Detailed analyses of crystallizing phases using the electron microprobe has enabled calculation of the liquid line of descent in these compositions at various pressures.At 27–36 kb garnet and clinopyroxene are the liquidus or near-liquidus phases in dry tholeiite, basaltic andesite and andesite, while quartz is the liquidus phases in dry dacite and rhyodacite. Under wet conditions at 27 kb garnet, not quartz, is the liquidus phase in the dacite. Qualitatively these results show that the low melting fraction of a quartz eclogite at 27–36 kb under dry conditions is of andesitic composition whereas under wet conditions it is rhyodacitic or granodioritic. At these pressures under dry conditions the andesite liquidus lies in a marked low temperature trough between the more basic and more acid compositions. Quantitatively, the calculated compositions of liquid fractionates for varying degrees of melting of the quartz eclogite bulk composition broadly follow the calc-alkaline trend.At 9–10 kb under wet conditions sub-silicic amphibole and pyroxenes are the near-liquidus phases in tholeiite and basaltic andesite compositions. Calcic plagioclase and garnet occur nearer the solidus. The calculated liquid fractionates follow the calc-alkaline trend and demonstrate that the calc-alkaline series may be derived by the partial melting of amphibolite at lower crustal depths under wet conditions , Or by the fractional crystallization of a hydrous basalt magma at similar depths.These experimental results support two complementary hypotheses for the derivation of the calc-alkaline igneous rock suite from the mantle by a two stage igneous process. In the first stage of both hypotheses large piles of basalt are extruded on the earth's surface. Subsequently this pile of basalt may, under dry conditions, transform to quartz eclogite, sink into the mantle and finally undergo partial melting at 100–150 kms depth. This partial melting gives rise to the calc-alkaline magma series leaving a residuum of clinopyroxene and garnet. Alternatively, if wet conditions prevail in the basalt pile and the geotherms remain high, partial melting of the basalt may take place near the base of the pile, at about 10 kb pressure . The liquids so formed constitute the calc-alkaline suite and the residuum consists of amphibole, pyroxenes and possibly minor garnet and calcic plagioclase. Both models may be directly linked to the hypothesis of sea-floor spreading.     

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 .     

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.     

Geothermometry and geobarometry of a cummingtonite-bearing dacite from Martinique,Lesser Antilles

A dacite sample from a nuée ardente deposit at Pitons du Carbet, Martinique, contained cummingtonite, orthopyroxene, quartz, magnetite, and ilmenite as phenocrysts, and thus was suitable for evaluation of the conditions of crystallization of nuée ardente materials according to the method of Ewart et al. (1971). The estimations were obtained with the aid of a Fortran IV program, which permitted the operation of all the arrangements between the available microprobe analyses. The results indicated that the phenocrystic association crystallized at moderate temperatures (ca. 750° C), under high oxygen fugacities (> NNO) and total pressures (2.3–4.5 Kb, with a maximal density of points at about 3.5 Kb), and water pressures approximating total pressures. The groundmass Fe-Ti oxides equilibrated at lower temperatures and under relatively increasing oxygen fugacities, the variation of which is tentatively ascribed to the aerial emplacement of the nuée ardente materials. The phenocryst data imply that in the case studied the high fluid pressures characterizing the nuée ardente eruptions were not acquired at a shallow level because of the deep intratelluric stage of crystallization of these differentiated calcalkalic magmas.     

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.     

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.     

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.