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The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H 2 O-bearing (0–6 wt% H 2 O) and CO 2 -bearing (0.5 wt% CO 2 ) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO 2 hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w 0.5 )/( T  − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H 2 O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.

The water-saturated phase relations have been determined for a primitive magnesian andesite (57 wt% SiO 2 , 9 wt% MgO) from the Mt. Shasta, CA region over the pressure range 200–800 MPa, temperature range of 915–1,070 °C, and oxygen fugacities varying from the nickel–nickel oxide (NNO) buffer to three log units above NNO (NNO+3). The phase diagram of a primitive basaltic andesite (52 wt% SiO 2 , 10.5 wt% MgO) also from the Mt. Shasta region (Grove et al. in Contrib Miner Petrol 145:515–533; 2003 ) has been supplemented with additional experimental data at 500 MPa. Hydrous phase relations for these compositions allow a comparison of the dramatic effects of dissolved H 2 O on the crystallization sequence. Liquidus mineral phase stability and appearance temperatures vary sensitively in response to variation in pressure and H 2 O content, and this information is used to calibrate magmatic barometers-hygrometers for primitive arc magmas. H 2 O-saturated experiments on both compositions reveal the strong dependence of amphibole stability on the partial pressure of H 2 O. A narrow stability field is identified where olivine and amphibole are coexisting phases in the primitive andesite composition above 500 MPa and at least until 800 MPa, between 975–1,025 °C. With increasing H 2 O pressure ( ), the temperature difference between the liquidus and amphibole appearance decreases, causing a change in chemical composition of the first amphibole to crystallize. An empirical calibration is proposed for an amphibole first appearance barometer-hygrometer that uses Mg# of the amphibole and : This barometer gives a minimum recorded by the first appearance of amphibole in primitive arc basaltic andesite and andesite. We apply this barometer to amphibole antecrysts erupted in mixed andesite and dacite lavas from the Mt. Shasta, CA stratocone. Both high H 2 O pressures (500–900 MPa) and high pre-eruptive magmatic H 2 O contents (10–14 wt% H 2 O) are indicated for the primitive end members of magma mixing that are preserved in the Shasta lavas. We also use these new experimental data to explore and evaluate the empirical hornblende barometer of Larocque and Canil ( 2010 ).

Basaltic crystal cargoes often preserve records of mantle-derived chemical variability that have been erased from their carrier liquids by magma mixing. However, the consequences of mixing between similarly primitive but otherwise chemically variable magmas remain poorly understood despite ubiquitous evidence of chemical variability in primary melt compositions and mixing-induced disequilibrium within erupted crystal cargoes. Here we report observations from magma–magma reaction experiments performed on analogues of primitive Icelandic lavas derived from distinct mantle sources to determine how their crystal cargoes respond to mixing-induced chemical disequilibrium. Chemical variability in our experimental products is controlled dominantly by major element diffusion in the melt that alters phase equilibria and triggers plagioclase resorption within regions that were initially plagioclase saturated. Isothermal mixing between chemically variable basaltic magmas may therefore play important but previously underappreciated roles in creating and modifying crystal cargoes by unlocking plagioclase-rich mushes and driving resorption, (re-)crystallisation and solid-state diffusion. Chemically variable primitive basalts undergo mixing during ascent from the mantle. Here the authors show observations from magma–magma reaction experiments which demonstrate how isothermal mixing between chemically variable basalts creates and modifies crystal cargoes erupted in oceanic settings.

Granulite facies migmatitic gneisses from the Seiland Igneous Province (northern Norway) were deformed during deep crustal shearing in the presence of melt, which formed by dehydration melting of biotite. Partial melting and deformation occurred during the intrusion of large gabbroic plutons at the base of the lower crust at 570 to 520 Ma in an intracontinental rift setting. The migmatitic gneisses consist of high‐aspect‐ratio leucosome‐rich domains and a leucosome‐poor, restitic domain of quartzitic composition. According to thermodynamic modeling using synkinematic mineral assemblages, deformation occurred at T = 760°C–820°C, P = 0.75–0.95 GPa and in the presence of ≤5 vol % of residual melt. There is direct evidence from microstructural observations, Fourier transform infrared measurements, thermodynamic modeling, and titanium‐in‐quartz thermometry that dry quartz in the leucosome‐poor domain deformed at high differential stress (50–100 MPa) by dislocation creep. High stresses are demonstrated by the small grain size (11–17 μm) of quartz in localized layers of recrystallized grains, where titanium‐in‐quartz thermometry yields 770°C–815°C. Dry and strong quartz forms a load‐bearing framework in the migmatitic gneisses, where ∼5% melt is present, but does not control the mechanical behavior because it is located in isolated pockets. The high stress deformation of quartz overprints an earlier, lower stress deformation, which is preserved particularly in the vicinity of segregated melt pockets. The grain‐scale melt distribution, water content and distribution, and the overprinting relationships of quartz microstructures indicate that biotite dehydration melting occurred during deformation by dislocation creep in quartz. The water partitioned into the segregated melt crystallizing in isolated pockets, in the vicinity of which quartz shows a higher intracrystalline water content and a large grain size. On the contrary, the leucosome‐poor domain of the rock, from which melt was removed, became dry and thereby mechanically stronger. Melt removal at larger scale will result in a lower crust which is dry enough to be mechanically strong. The application of flow laws derived for wet quartz is not appropriate to estimate the behavior of such granulite facies parts of the lower crust. Key Points Dry and strong quartz is a major constituent of felsic lower crust Dry and strong lower crust is formed by partial melting and melt removal Large portions of the lower crust are likely to be dry and mechanically strong

In the first two papers of this series [Behrens, Phys Chem Minerals 48:8, 2021a; Behrens, Phys Chem Minerals 48:27, 2021b], incorporation of hydrogen in the feldspar structure, partitioning of hydrogen between feldspars and gases/fluids and self-diffusion of hydrogen in feldspars have been discussed, with particular focus on sanidine. Here, the results of reactions between sanidine containing strongly bonded hydrogen defects and (Na,K)Cl are presented. Experiments were performed at ambient pressure at temperatures of 605–1000 °C, and hydrogen profiles were measured by IR microspectroscopy. Profiles can be interpreted by an incomplete dehydrogenation at the crystal surface or a strong concentration dependence of hydrogen diffusivity. Both are consistent with hydrogen located on interstitial sites and difficult to substitute by the larger alkali ions. Chemical diffusivities of hydrogen derived from fitting of the profiles or Boltzmann–Matano analysis are similar to self-diffusivities determined by D/H exchange experiments. Activation energies are also comparable. Comparison to sodium and potassium diffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363: 79–84, 2015; Hergemöller et al. in Phys Chem Minerals 44:345–351, 2017) supports a mechanism of proton diffusion charge-compensated by Na + diffusion for hydrogen removal in the sanidines under dry conditions.

Hydrogen defects can strongly affect mechanical and chemical properties of feldspars. To get insight into the behavior of such defects, alkali feldspar and plagioclase of igneous origin were studied combining IR spectroscopy with heating experiments under well-controlled conditions. Near-infrared spectra show that OH groups are the predominant hydrous species in these feldspars but presence of minor amounts of molecular H 2 O cannot be excluded. Short-term annealing at 400–800 °C produces a small but significant irreversible change in the OH stretching vibration band which is attributed to relaxation of the feldspar structure. Polarized mid-infrared spectra of sanidine, adularia, and plagioclase recorded in situ at temperatures up to 600 °C show reversible shifts of maxima toward higher wavenumber and an overall decrease in integrated intensities. The pleochroic features of the OH vibration bands, i.e., the predominant orientation of OH dipoles along the crystallographic a axis in all feldspars and the additional band component perpendicular to the (010) plane in sanidine are still present in the high-temperature spectra. Different behavior during long-term annealing at high temperature was found for the alkali feldspars and the plagioclases. At 900–1000 °C, the Eifel sanidines rapidly lost about one quarter of the initial water content which is attributed to a weakly bound hydrogen species in the feldspar structure. The remaining hydrogen is very strongly bound and was still detectable in 0.7–0.9 mm thick sections after annealing for 108 days at 1000 °C in air dried by phosphorus pentoxide. In contrast, a 1-mm-thick section of plagioclase completely lost hydrogen during heating in air within 8 days at 1000 °C. After partial dehydration, the pleochroic behavior of the OH absorption bands of the feldspars was basically preserved except that the 3050 cm −1 band of the sanidine, oriented perpendicular to (010), becomes more pronounced than the 3400 cm −1 band, oriented parallel to the a direction. Annealing experiments at 1000 °C under controlled water pressures indicate equilibrium solubilities of several tens of ppm H 2 O in the plagioclases and more than 100 ppm H 2 O in the alkali feldspars already at 1 bar water pressure. The variation of the water content with H 2 O pressure and spectroscopic observations indicates that the water content in the feldspars is determined not only by the water pressure but also by already existing defects. Vacancies on alkali sites ( V A1 ) may accommodate H 2 O molecules, possibly with subsequent hydrolysis of network bonds to minimize local stress. A likely explanation for the strongly bound hydrogen in the sanidine is a coupled substitution of H +  + Al 3+ for Si 4+ (AlOH defect) where the protons are located on interstitial sites. This incorporation model is supported by the complete recovery of the defects in H 2 O vapor after previous proton/alkali exchange in alkali chloride vapor at 1000 °C.

It is known that the coordination number (CN) of atoms or ions in many materials increases through application of sufficiently high pressure. This also applies to glassy materials. In boron-containing glasses, trigonal BO 3 units can be transformed into tetrahedral BO 4 under pressure. However, one of the key questions is whether the pressure-quenched CN change in glass is reversible upon annealing below the ambient glass transition temperature ( T g ). Here we address this issue by performing 11 B NMR measurements on a soda lime borate glass that has been pressure-quenched at ~0.6 GPa near T g . The results show a remarkable phenomenon, i.e., upon annealing at 0.9 T g the pressure-induced change in CN remains unchanged, while the pressurised values of macroscopic properties such as density, refractive index and hardness are relaxing. This suggests that the pressure-induced changes in macroscopic properties of soda lime borate glasses compressed up to ~0.6 GPa are not attributed to changes in the short-range order in the glass, but rather to changes in overall atomic packing density and medium-range structures.

Diffusion of hydrogen in natural alkali feldspars (Eifel sanidine and adularia from unknown locality) containing strongly bonded OH defects was investigated by D/H isotope exchange in the T range 600–1050 °C at ambient pressure and at elevated pressures up to 8 kbar. Runs at 1 atm were performed in a fused silica tube connected to a liquid D 2 O reservoir at room temperature. In the high- pressure experiments samples were sealed with D 2 O in gold capsules and processed up to 4 kbar in externally heated pressure vessels using Ar/D 2 O as the pressure medium. Experiments at 6–8 kbar were performed in an internally heated gas pressure vessel using the double capsule technique to minimize isotopic contamination by the pressure medium. Diffusion coefficients were determined either by measuring concentration-distance profiles of OH and OD with an IR microscope or by measuring the total exchange of oriented plates after various run durations using a macroscopic IR technique. Both methods gave consistent data. D/H interdiffusion, D D/H , is almost identical in the adularia and in the sanidine implying that the chemical composition and the degree of Al/Si disorder have minor influence on the hydrogen isotope exchange in alkali feldspars. Furthermore, no effect of crystallographic orientation was found for D D/H in both feldspars. D D/H in sanidine, however, depends on the thermal pre-treatment. Heating for several days at 900 °C leads to a lowering of D by a factor of 2.3, indicating a corresponding decrease in mobile hydrogen species. Data for sanidine pre-annealed at 900 °C are well described in the T range 600–1050 °C by D D/H m 2 /s = 6.9 · 10 - 6 exp - 162 kJ / mol R · T The diffusivity is strongly enhanced by water pressures ( P H2O ), i.e., in the range of 0–2 kbar. At P H2O  = 2 kbar the following equation applies in the T -range of 645–800 °C: D D / H m 2 / s = 1.2 · 10 - 6 exp - 131 kJ / mol R · T Experiments with D 2 O/CO 2 mixture of ratio 1:1 gave smaller exchange rates compared to pure D 2 O fluids, confirming that that not the pressure but the water fugacity leads to the increase in the mobility of hydrogen species. At 720 °C and pressures of 4–8 kbar, chemical diffusivities of H 2 O, D ~ H 2 O , were determined by fitting the weighted sum of the absorbances of the OH and the OD band vs. distance. The D ~ H 2 O values are similar to those reported by Kronenberg et al. (Geochim Cosmochim Acta 60:4075–4094, 1996) for dehydration of Kristallina adularia at ambient pressure. It is concluded that in both cases high concentrations of H 2 O molecules on interstitial sites govern the transport of hydrogen. Comparison of D/H interdiffusion to O diffusion in sanidine (Freer et al. in Phil Mag A75:485–503, 1997) implies that not only interstitial H 2 O but also protons contribute to the transport of hydrogen under hydrothermal conditions. On the other hand, the high D D/H at ambient pressure is attributed to an interdiffusion of protons and Na + , which is supported by Na tracerdiffusion data for sanidine (Wilangowski et al. in Defect Diffus Forum 363:79–84, 2015). A basic conclusion of this research is that hydrogen storage capacity and hydrogen diffusion in feldspars are largely determined by extrinsic defects, such as substitutional defects (i.e., Al 3+ +  H + for Si 4+ ) and associates of water molecules with vacancies. The bonding of hydrogen species to the defects can vary greatly, depending on the genesis of the feldspars, so that quantitative predictions are difficult.

Axial melt lenses sandwiched between the lower oceanic crust and the sheeted dike sequences at fast-spreading mid-ocean ridges are assumed to be the major magma source of oceanic crust accretion. According to the widely discussed “gabbro glacier” model, the formation of the lower oceanic crust requires efficient cooling of the axial melt lens, leading to partial crystallization and crystal-melt mush subsiding down to lower crust. These processes are believed to be controlled by periodical magma replenishment and hydrothermal circulation above the melt lens. Here we quantify the cooling rate above melt lens using chemical zoning of plagioclase from hornfelsic recrystallized sheeted dikes drilled from the East Pacific at the Integrated Ocean Drilling Program Hole 1256D. We estimate the cooling rate using a forward modelling approach based on CaAl-NaSi interdiffusion in plagioclase. The results show that cooling from the peak thermal overprint at 1000–1050°C to 600°C are yielded within about 10–30 years as a result of hydrothermal circulation above melt lens during magma starvation. The estimated rapid hydrothermal cooling explains how the effective heat extraction from melt lens is achieved at fast-spreading mid-ocean ridges.

The effect of MgO and total FeO on ferric/ferrous ratio in model multicomponent silicate melts was investigated experimentally in the temperature range 1300–1500 °C at 1 atm total pressure in air. We demonstrate that the addition of these weak network modifier cations results in an increase of Fe3+/Fe2+ ratio in both mafic and silicic melts. Based on present and published experimental data, a new empirical equation is proposed to predict the ferric/ferrous ratio as a function of oxygen fugacity, temperature and melt composition. In contrast to previous equations, the compositional effect of melts on the Fe3+/Fe2+ ratio is not only modeled by the sum of the molar fraction of the individual oxide components. Additional interactions terms have also been incorporated. The main advantage of the proposed model is its applicability for a wide compositional range. However, its application to felsic melts (> 68 wt% SiO2) is not recommended. Other advantages of this equation and differences when compared with previous models are discussed.