H2O in metamorphism and unexpected behaviour in the preservation of metamorphic mineral assemblages

The preservation of mineral assemblages that were fluid‐present during their prograde history is primarily related to the consumption of the fluid by growth of more hydrous minerals as the retrograde history begins. The range of behaviour relating to the preservation of mineral assemblages is examined using calculated phase diagrams for fluid‐saturated conditions, contoured for the H₂O content of the mineral assemblage. At equilibrium, as a mineral assemblage crosses contours of decreasing H₂O content along a pressure–temperature path, it dehydrates, the fluid being lost from the rock. If the assemblage crosses contours of increasing H₂O content, the mineral assemblage starts to rehydrate using any fluid on its grain boundaries. When the rock has consumed its fluid, the resulting mineral assemblage is that preserved in the rock. Conditions relating to the preservation of mineral assemblages are discussed, and examples of the consequences of different pressure–temperature paths on preservation in a metapelitic and a metabasic rock composition are considered on phase diagrams calculated with thermocalc .     

Synthetic Fluid Inclusions in the Systems NaCl-H2O and NaCl-CO2-H2O: Dissolution Temperatures of Halite

Abstract. This study examined the effect of CO₂ on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO₂ were synthesized, and their halite dissolution temperatures, T_m(halite), were measured. The solubilities of NaCl in CO₂-bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The T_m(halite) value in aqueous fluid with 5 mol % CO₂ obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO₂ reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits.     

Thermodynamic modelling of the reaction muscovite+cordierite→Al2SiO5+biotite+quartz+ H2O: constraints from natural assemblages and implications for the metapelitic petrogenetic grid

The reaction muscovite+cordierite→biotite+Al₂SiO₅ +quartz+H₂O is of considerable importance in the low pressure metamorphism of pelitic rocks: (1) its operation is implied in the widespread assemblage Ms + Crd +And± Sil + Bt + Qtz, a common mineral assemblage in contact aureoles and low pressure regional terranes; (2) it is potentially an important equilibrium for pressure estimation in low pressure assemblages lacking garnet; and (3) it has been used to distinguish between clockwise and anticlockwise P–T paths in low pressure metamorphic settings. Experiments and thermodynamic databases provide conflicting constraints on the slope and position of the reaction, with most thermodynamic databases predicting a positive slope for the reaction. Evidence from mineral assemblages and microtextures from a large number of natural prograde sequences, in particular contact aureoles, is most consistent with a negative slope (andalusite and/or sillimanite occurs upgrade of, and may show evidence for replacement of, cordierite). Mineral compositional trends as a function of grade are variable but taken as a whole are more consistent with a negative slope than a positive slope. Thermodynamic modelling of reaction 1 and associated equilibria results in a low pressure metapelitic petrogenetic grid in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (KFMASH) which satisfies most of the natural and experimental constraints. Contouring of the Fe–Mg divariant interval represented by reaction 1 allows for pressure estimation in garnet‐absent andalusite+cordierite‐bearing schists and hornfelses. The revised topology of reaction 1 allows for improved analysis of P–T paths from mineral assemblage sequences and microtextures in the same rocks.     

Evolution of H2O content in a polymetamorphic terrane: the Plattengneiss Shear Zone (Koralpe, Austria)

The Koralpe of the Eastern European Alps experienced high-temperature/low-pressure metamorphism (∼650 °C and 6.5 kbar) during the Permian and eclogite facies metamorphism (∼700 °C and 14 kbar) during the Eo-Alpine (Cretaceous) metamorphic event. In the metapelitic Plattengneiss shear zone that constitutes much of the Koralpe, the second metamorphism caused only partial re-equilibration of the assemblages formed during the first metamorphism. It is shown here that the Eo-Alpine mineral assemblage, garnet + biotite + muscovite + plagioclase + quartz (with or without kyanite), formed under low water activity conditions that are consistent with the level of dehydration that occurred during the Permian event. This implies that the rocks were essentially closed-system from the peak of the Permian metamorphism through the Eo-Alpine event. The evolution of water content of the rocks is traced through time: that prograde dewatering during the Permian metamorphic event terminated at the metamorphic peak with a water content around 3–4 mol.%. The water content remained then constant and led to water-undersaturation during the subsequent Eo-Alpine metamorphism. From the water content and activity evolution a post-peak isothermal decompression path close to the solidus is inferred for the Eo-Alpine event.     

Calculated mineral equilibria for eclogites in CaO–Na2O–FeO–MgO–Al2O3–SiO2–H2O: application to the Pouébo Terrane, Pam Peninsula, New Caledonia

The high- P , medium- T  Pouébo terrane of the Pam Peninsula, northern New Caledonia includes barroisite- and glaucophane-bearing eclogite and variably rehydrated equivalents. The metamorphic evolution of the Pouébo terrane is inferred from calculated P–T  and P–T  – X H2O pseudosections for bulk compositions appropriate to these rocks in the model system CaO–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O. The eclogites experienced a clockwise P–T  path that reached P ≈19  kbar and T  ≈600  °C. The eclogitic mineral assemblages are preserved because reaction consequent upon decompression consumed the rocks' fluid. Extensive reaction occurred only in rocks with fluid influx during decompression of the Pouébo terrane.     

Reactive flow of mixed CO2–H2O fluid and progress of calc-silicate reactions in contact metamorphic aureoles: insights from two-dimensional numerical modelling

Previous models of hydrodynamics in contact metamorphic aureoles assumed flow of aqueous fluids, whereas CO₂ and other species are also common fluid components in contact metamorphic aureoles. We investigated flow of mixed CO₂–H₂O fluid and kinetically controlled progress of calc‐silicate reactions using a two‐dimensional, finite‐element model constrained by the geological relations in the Notch Peak aureole, Utah. Results show that CO₂ strongly affects fluid‐flow patterns in contact aureoles. Infiltration of magmatic water into a homogeneous aureole containing CO₂–H₂O sedimentary fluid facilitates upward, thermally driven flow in the inner aureole and causes downward flow of the relatively dense CO₂‐poor fluid in the outer aureole. Metamorphic CO₂‐rich fluid tends to promote upward flow in the inner aureole and the progress of devolatilization reactions causes local fluid expulsion at reacting fronts. We also tracked the temporal evolution of P‐T‐X_CO2conditions of calc‐silicate reactions. The progress of low‐ to medium‐grade (phlogopite‐ to diopside‐forming) reactions is mainly driven by heat as the CO₂ concentration and fluid pressure and temperature increase simultaneously. In contrast, the progress of the high‐grade wollastonite‐forming reaction is mainly driven by infiltration of chemically out‐of‐equilibrium, CO₂‐poor fluid during late‐stage heating and early cooling of the inner aureole and thus it is significantly enhanced when magmatic water is involved. CO₂‐rich fluid dominates in the inner aureole during early heating, whereas CO₂‐poor fluid prevails at or after peak temperature is reached. Low‐grade metamorphic rocks are predicted to record the presence of CO₂‐rich fluid, and high‐grade rocks reflect the presence of CO₂‐poor fluid, consistent with geological observations in many calc‐silicate aureoles. The distribution of mineral assemblages predicted by our model matches those observed in the Notch Peak aureole.     

The formation of eclogite facies metatroctolites and a general petrogenetic grid in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O (NCFMASH)

Eclogite facies metatroctolites from a variety of Western Alps localities (Voltri, Monviso, Lanzo, Allalin, Zermat–Saas, etc.) that preserve textural evidence of their original form as bimineralic olivine‐plagioclase rocks are considered in terms of calculated mineral equilibria in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (NCFMASH). Pseudosections, based on a new petrogenetic grid for NCFMASH presented here, are used to unravel the metamorphic history of the metatroctolites, considering the rocks to consist of different composition microdomains corresponding to the original olivine and plagioclase grains. On the basis that the preservation of the mineral assemblage in each microdomain will tend to be from where on a rock's P–T path the metamorphic fluid phase is used up via rehydration reactions, P–T pseudosections contoured for water content, and P–T path‐M_H2O (amount of water) pseudosections, are used to examine fluid behaviour in each microdomain. We show that the different microdomains are likely to preserve their mineral assemblages from different places on the P–T path. For the olivine microdomain, the diagnostic mineral assemblage is chloritoid + talc (+ garnet + omphacite). The preservation of this assemblage, in the light of the closed system P–T path‐M_H2O relationships, implies that the microdomain loses its metamorphic fluid as it starts to decompress, and, in the absence of subsequent hydration, the high pressure mineral assemblage is then preserved. In the plagioclase microdomain, the diagnostic assemblage is epidote (or zoisite) + kyanite + quartz suggesting a lower pressure (of about 2 GPa) than for the olivine microdomain. In the light of P–T path‐M_H2O relationships, development of this assemblage implies breakdown of lawsonite across the lawsonite breakdown reaction, regardless of the maximum pressure reached. It is likely that the plagioclase microdomain was mainly fluid‐absent prior to lawsonite breakdown, only becoming fluid‐present across the reaction, then immediately becoming fluid‐absent again.     

Experimental study of the stability of sudoite and magnesiocarpholite and calculation of a new petrogenetic grid for the system FeO–MgO–Al2O3–SiO2–H2O

The solid-solid reaction magnesiocarpholite = sudoite + quartz has been bracketed between 350 and 500°C, 6.3 and 7.8 kbar. Because it is impossible to synthesize end-member sudoite, all experiments were carried out using natural minerals as starting materials. Although mineral compositions were very close to those of the end-members, the effect of the fluorine content in carpholite was significant. Particularly in those experiments where sudoite grows at the expense of carpholite, electron microprobe analysis of the run products shows that a more stable F-rich carpholite crystallizes too, and consumes the fluorine released in solution by the breakdown of the original carpholite.
Our experimental results are combined, through a thermodynamic analysis, with a previous data set and with previous experimental data concerning the relative stability of chlorite, talc and magnesiocarpholite with excess of quartz and water as a function of P–T and AlAl(SiMg)_-1 substitutions in phyllosilicates. This allows us to constrain the feasible thermodynamic parameters (H°_f, sud; S ° sud) and (H°_f,car; S °_car) for the Mg end-members. Using the partition coefficients calculated from natural parageneses, we have computed a petrogenetic grid for the system FeO–MgO–Al₂O₃–SiO₂–H₂O. It demonstrates that parageneses involving sudoite and carpholite can be used as indicators of P–T conditions, up to 600° C, 8 kbar for sudoite, and at higher pressure for carpholite.     

Eclogites from the south Tianshan, NW China: petrological characteristic and calculated mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O system

Eclogites from the south Tianshan, NW China are grouped into two types: glaucophane and hornblende eclogites, composed, respectively, of garnet + omphacite + glaucophane + paragonite + epidote + quartz and garnet + omphacite + hornblende (sensu lato) + paragonite + epidote + quartz, plus accessory rutile and ilmenite. These eclogites are diverse both in mineral composition and texture not only between the two types but also among the different selected samples within the glaucophane eclogite. Using thermocalc 3.1 and recent models of activity–composition relation for minerals, a P–T projection and a series of P–T pseudosections for specific samples of eclogite have been calculated in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) with quartz and water taken to be in excess. On the basis of these phase diagrams, the phase relations and P–T conditions are well delineated. The three selected samples of glaucophane eclogite AK05, AK11 and AK17 are estimated to have peak P–T conditions, respectively, of 540–550 °C at c. 16 kbar, c. 560 °C at 15–17 kbar and c. 580 °C at 15–19 kbar, and two samples of hornblende eclogite AK10 and AK30 of 610–630 °C and 17–18 kbar. Together with H₂O‐content contours in the related P–T pseudosections and textural relations, both types of eclogite are inferred to show clockwise P–T paths, with the hornblende eclogite being transformed from the glaucophane eclogite assemblage dominantly through increasing temperature.     

Experimental study of phase relations involving osumilite in the system K2O-FeO-MgO-Al2O3-SiO2-H2O at high pressure and temperature

Abstract Phase relations and mineral chemistry for garnet (Grt), orthopyroxene (Opx), sapphirine (Spr), water-undersaturated cordierite (Crd), osumilite (Osu), sillimanite (Sil), K-feldspar (Kfs), quartz (Qtz) and a water-undersaturated liquid (Liq) have been determined experimentally in the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O) under low P_H2O and f_O2 conditions. Four compositions have been studied with 100 [Mg/(Mg + Fe)] ranging from 65.6 to 89.7. Based on our experimental data, a P-T grid is derived for the KFMASH system in the presence of quartz, orthopyroxene and liquid. Osumilite has been found in various mineral assemblages from 950 to 1100°C and 7.5 to 11 kbar. In the temperature range 1000-1100°C, the pair Os-Grt is stable over a pressure range of about 3kbar. The divariant reaction Os + Opx = Grt + Kfs + Qtz runs to the right with increasing pressure. Because osumilite is the most magnesian phase it is restricted to Mg-rich compositions at high pressure. The reaction defining the upper pressure stability limit of Os-Grt is located around 11 kbar with a nearly flat dP/dT slope over the temperature range 950–100°C. Over the entire temperature range investigated osumilite is not stable beyond 12 kbar. The data imply a restricted pressure range between 11 and 12 kbar for the stability of the assemblage Os-Opx-Sil-Kfs-Qtz. At 1050°C and above, osumilite occurs in various mineral assemblages together with the high-T pair Spr-Qtz. When coexisting with garnet, orthopyroxene or sapphirine, osumilite is always the most magnesian phase. At 1050 and 1100°C, liquid is invariably the most Fe-rich phase in the run product. Our data support a theoretical P-T grid for the KFMAS system in which osumilite is stable outside the field of the high-T assemblage Spr-Qtz. Moreover, our grid indicates that Os-Opx-Sil-Kfs-Qtz has a more restricted pressure and compositional stability domain than Os-Grt, in agreement with natural occurrences. Osumilite is stable over a large pressure range, such that in Mg-rich rocks, and at high temperature, it can occur at any depth in normal thickness continental crust.     

Hydrogen isotope exchange kinetics between H2O and H4SiO4 from ab initio calculations

Hydrogen isotope exchange between water and orthosilicic acid (H₄SiO₄) was modeled using B3LYP calculations and classical transition-state theory. Configurations of 1, 2, 3 and 7 water molecules and H₄SiO₄ were used to investigate energetically viable reaction pathways. An upper-bound of 71 kJ/mol was assumed for the zero-point energy corrected barrier (ZPECB) because this is the experimentally determined activation energy for Si-O bond breaking (Rimstidt and Barnes, 1980) and ZPECB is expected to be close to this value. Long range solvation forces were accounted for using the integral equation formalism polarized continuum model (IEFPCM; Cancès et al., 1997). Primary and secondary isotope effects were computed by exchanging hydrogen atoms with deuterium. Results show that reaction mechanisms involving 3 and 7 water molecules have ZPECB of 34 to 38 kJ/mol, whereas those involving 1 and 2 water molecules have ZPECB in excess of the set upper-bound. The lower range of ZPECB with 3 or 7 water molecules is reasonable to explain rapid hydrogen isotope exchange with silicates. Rate constant calculations accounting for tunneling, anharmonicity and scaling factors indicate that the reaction is fast and equilibrium can be assumed under most geologic conditions.     

The H2O+ Contents of Some Geochemical Standards Predicted by a Calibration Line

The combined water (H₂O⁺) in 30 geochemical standards having known and unknown water contents was determined by an elemental analyzer on 1 day during each of 6 weeks over a period of several months. The analysis of variance of the data measured in the form of a Youden square shows an extremely significant variation due to some unknown cause during the weeks in which the data were obtained. The higher water contents of the first two sets were obtained in the fall season when this area (Reston, Va.) has high and variable humidity, whereas the last four sets were measured during winter months. Humidity, however, was not included as a variable in the design and was not measured. The first two of three average blanks for H₂O⁺, measured after determining H₂O⁺ contents of about 11 percent for two samples, are noticeably higher than the third average blank. Similarly, the first of two average blanks for H₂O⁺, measured after determining the H₂O⁺ content (4.70 percent) of PCC-1, is higher than the second. Data for the last 4 weeks were used to calculate the line of regression and the extremely significant correlation coefficient. The line is used to predict suggested revisions of the “best” H₂O⁺ contents of the standards. Coefficients of variation calculated from the data for the last 4 weeks indicate that there is no severe sampling problem due to the small sample size (20 mg) taken for the determinations. The coefficients follow the general trend of large coefficients for samples containing the least amount of the constituent (BHVO-1: x?= 11.76% H₂O⁺; C.V. = 7.3%) and of small coefficients for samples containing the greatest amount (BX-N: x?= 11.76% H₂O⁺; C.V. = 0.4%).     

Desilication veins in the Cadillac Mountain granite (Maine, USA): a record of reversals in the SiO2 solubility of H2O-rich vapour released during subsolidus cooling

Late-stage hydrous fluids, which evolved during the cooling of the Cadillac Mountain granite, Maine, USA, produced narrow veins that transect the pluton. The vein margins contain microstructures transitional between granite and the vein centre. They preserve the vestige shapes of original Na-rich alkali feldspar crystals that have been pseudomorphed by cordierite+quartz+K-rich alkali feldspar. Closer to the centres of the veins, the minerals change from an outer zone with cordierite, hercynitic–galaxite spinel, minor corundum, K-feldspar and plagioclase to an inner zone with remnant cordierite, hercynitic gahnite, strongly zoned almandine–spessartine garnet, chlorite and quartz. Three allochemical reactions are inferred to have occurred with the influx of hydrous fluids during the replacement process. Reaction (1) is Na-rich alkali feldspar+iron ions in solution=Fe-cordierite+quartz+K-feldspar+sodium ions in solution. Reactions (2) and (3) occurred during desilication. Reaction (2) is Fe-cordierite=hercynite+silica in solution, and reaction (3) is Fe-cordierite+water=corundum+iron hydroxide in solution+silicic acid in solution. Two independent techniques, experimental silica-solubility data and spinel–cordierite thermobarometry, constrain the conditions of vein formation to c.   1.0  kbar and both methods indicate that the progressive mineral reactions occurred during cooling of the hydrous fluids from c. 775° to 400–340  °C. This cooling trend is consistent with the petrographic evidence, which demonstrates that reactions occurred before desilication, during desilication, and then diminished with a final phase of resilication. Although the veins are minor features of the Cadillac Mountain granite, they provide insight into the conditions that prevailed during cooling of the pluton, and similar features may be important for constraining the cooling history of shallow-level plutonic complexes elsewhere.     

Precipitation of pyroxenes and Mg2SiO4 from majoritic garnet: simulation of peridotite exhumation from great depth

Our experimental simulations of the exhumation path of mantle peridotites show that high‐temperature (1400 °C) decompression of lherzolite from 14 to 13 and 12 GPa results in exsolution of interstitial blebs of diopside and Mg₂SiO₄ (wadsleyite) lamellae from majoritic garnet. At lower pressures (from 8 to 5 GPa, at T = 1400 °C) only enstatite exsolves as blebs at garnet boundaries. Continuous high‐temperature decompression from 14 to 7 GPa produces zoned majoritic garnet containing blebs of exsolved pyroxenes inside garnet rims. No intracrystalline precipitation of pyroxene was observed in garnet, although such lamellae are found in some natural garnet peridotites. The explanation appears to be the three orders of magnitude difference in grain size between experimental and natural specimens. Our data suggest that Mg₂SiO₄ and diopside exsolutions reflect the deepest point of the exhumation path of garnet peridotites, whereas enstatite precipitation may be restricted to garnets with less majoritic component at shallower depths.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

La sénégalite,Al2 (PO4) (OH)3 · H2O,un nouveau minéral

Senegalite is orthorhombic, mm2, a:b:c:=1.296:1:1.007; $\text{a}{}_0\text{=9.673,}\text{b}{}_0\text{=7.596,}\text{c}{}_0\text{=7.668}\text{A}\text{?}$, Z=4, G_calc=2551; space group Pna2. The strongest lines in the powder pattern are: 5.41(7); 4.089(9); 3.834(10); 3.610(8); 2.990(9); 2.348(8); 2.070(7) 1.929(7); 1.505(7) Å. The chemical analysis: Al₂O₃ ? 46.23; Fe₂O₃ ? 0.28; P₂O₅ ? 31.85 H₂O ? 21.00; sum 99.34, gives a formula Al₂(PO₄)(OH)₃ · H₂O. Colourless optically biaxial positive, n_S: α=1.562, β=1.566, γ=1.587, plane of optical axies (001), Z=a, Y=c; 2V=53°, weak dispersion r > v. Measured density 2.552. The DTA curve shows endothermic reactions at 250, 370 and 440°C corresponding to the dehydration of mineral. Infrared spectrum indicates the presence of OH and H₂O groups. Found in oxidation zone of Kouroudiako iron deposit, Senegal, associated with turquoise, augelite, wavellite and crandallite.     

Concentrations,sources, and losses of H2O,CO2, and S in Kilauean basalt

Basaltic glasses included in olivine phenocrysts from Kilauea volcano contain concentrations of H₂O, CO₂, and S similar to glassy Kilauean basalt dredged from the deep sea floor and greater than vesicular, subaerial Kilauean basalt. Our result contrasts with earlier reports that inclusions of basaltic glass in phenocrysts have little or no H₂O and large ratios of $\text{CO}{}_2\text{H}{}_2\text{O}$. Our analysed inclusions of glass are larger than 100 micrometers thick and similar in chemical composition to the host glass surrounding the olivine crystals indicating that the trapped melts are representative of the bulk liquid from which the crystals grew. Crystallization of about 2–8% of olivine from the melts after they were trapped is indicated by slight departures from the experimentally established equilibrium distribution of Mg and Fe between olivine and liquid. The measured concentrations of CO₂ correspond to phenocryst crystallization pressures of about 1.3 kbar for a subaerial basalt and about 5 kbar for a submarine basalt, consistent with geophysical models of Kilauea volcano. The compositions of volcanic gas predicted from our analyses are consistent with restored compositions of actual Kilauean gases. The rate of sulfur emission predicted from our analyses is greater than the sulfur dioxide emission rate observed during repose, but probably consistent with total degassing including eruptive episodes. The concentrations of H₂O, K₂O, Cl, and P in parental Kilauean basalt can be derived from upper mantle phlogopitic mica, pargasitic amphibole and apatite with compositions close to those of natural primary minerals in ultramafic xenoliths from continental kimberlites, or solely from apatite and phlogopitic mica with $\text{H}{}_2\text{O}\text{K}{}_2\text{O}$ near 0.47 ± 0.03, slightly higher than the range of values reported. The amounts of phlogopitic mica and pargasitic amphibole contributing volatiles to Kilauean tholeiite is about 10 percent by mass of the parental liquid, or about 5% if the source does not include amphibole. In view of an estimated 20% of partial melting of mantle source rock to produce Kilauean tholeiites, there may be about 2 weight percent of mica plus amphibole in part of the mantle beneath Kilauea, or about 1 weight percent of phlogopitic mica if amphibole is absent.