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In the last two decades, boron has gained significance as a geochemical tracer in mantle studies, particularly related to fluid-mediated processes. In our investigation, we explore how boron and its stable isotopes distribute between basaltic melt and hydrous fluid under conditions relevant to magmatic degassing in the shallow crust (1000–1250 °C, 150–250 MPa). We utilized a synthetic MORB-like composition with added boric-acid isotope standard (NIST-SRM951a) and additional trace elements, subjecting it to varying pressure, temperature, and melt-fluid ratios using an internally heated pressure vessel. The B isotope composition in the quenched glasses were determined through femtosecond laser ablation coupled to a multi-collector inductively-coupled-plasma mass spectrometer. Our experiments revealed that, even at the highest temperatures, boron strongly partitions into the fluid phase, accompanied by significant B isotope fractionation. This leads to an enrichment of the heavy B isotope in the fluid, with a constrained Δ11Bmelt-fluid range of -1.7 ± 0.9‰, consistent with ab-initio modeling results. These findings highlight the potential of B isotopes to trace geochemical processes at elevated temperatures with . Our results have implications for predicting the δ11B of degassed, water-bearing basaltic magmas and estimating the B isotope composition of their mantle source. Key points: • fs-LA MC ICP MS yields high precision B stable isotope results in glasses • Resolvable fluid-mediated B isotope fractionation occurs at igneous temperatures • Constrained Dfluid/melt and Δ11Bmelt−fluid based on experimental data are consistent with literature estimates • Our data have implications for the interpretation of the δ11B of degassed, water-bearing basaltic magmas [ABSTRACT FROM AUTHOR]

The effect of CaO, NaO, and KO on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450-1550 °C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe/Fe ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca < Na < K. Some old controversial conceptions concerning the effect of potassium on Fe/Fe ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO-TiO-AlO-FeO-FeO-MgO-CaO-NaO-KO-PO melts at air conditions. [ABSTRACT FROM AUTHOR]

Mafic enclaves in the 1991-1995 dacite of Unzen volcano show chemical and textural variability, such as bulk SiO contents ranging from 52 to 62 wt% and fine- to coarse-grained microlite textures. In this paper, we investigated the mineral chemistry of plagioclase and hornblende microlites and distinguished three enclave types. Type-I mafic enclaves contain high-Mg plagioclase and low-Cl hornblende as microlites, whereas type-III enclaves include low-Mg plagioclase and high-Cl hornblende. Type-II enclaves have an intermediate mineral chemistry. Type-I mafic enclaves tend to show a finer-grained matrix, have slightly higher bulk rock SiO contents (56-60 wt%) when compared with the type-III mafic enclaves (SiO = 53-59 wt%), but the overall bulk enclave compositions are within the trend of the basalt-dacite eruptive products of Quaternary monogenetic volcanoes around Unzen volcano. The origin of the variation of mineral chemistry in mafic enclaves is interpreted to reflect different degree of diffusion-controlled re-equilibration of minerals in a low-temperature mushy dacitic magma reservoir. Mafic enclaves with a long residence time in the dacitic magma reservoir, whose constituent minerals were annealed at low-temperature to be in equililbrium with the rhyolitic melt, represent type-III enclaves. In contrast, type-I mafic enclaves result from recent mafic injections with a mineral assemblage that still retains the high-temperature mineral chemistry. Taking temperature, Ca/(Ca + Na) ratio of plagioclase, and water activity of the hydrous Unzen magma into account, the Mg contents of plagioclase indicate that plagioclase microlites in type-III enclaves initially crystallized at high temperature and were subsequently re-equilibrated at low-temperature conditions. Compositional profiles of Mg in plagioclase suggest that older mafic enclaves (Type-III) had a residence time of ~100 years at 800 °C in a stagnant magma reservoir before their incorporation into the mixed dacite of the 1991-1995 Unzen eruption. Presence of different types of mafic enclaves suggests that the 1991-1995 dacite of Unzen volcano tapped mushy magma reservoir intermittently replenished by high-temperature mafic magmas. [ABSTRACT FROM AUTHOR]

The effect of alkalis on the solubility of HO and CO in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with HO/(HO + CO) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/ T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in HO solubility (melt equilibrated with pure HO fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO content in melts equilibrated with CO-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/ T = 0.17) to 0.45 wt % for shoshonite (NBO/ T = 0.38) to 0.90 wt % for AH2 (NBO/ T = 0.55). The highest CO contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/ T, CO solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO solubility at 500 MPa and 1,100-1,300 °C in various silicate melts as a function of the NBO/ T, (Na + K)/∑cations and Na/(Na + K) parameters: $${\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.$$ This model is valid for melt compositions with NBO/ T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz-fayalite-magnetite buffer and above. [ABSTRACT FROM AUTHOR]

The effect of TiO 2 and P 2O 5 on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe 2O 3 and variable amounts of TiO 2 (up to 30 wt %) or P 2O 5 (up to 20 wt %). Some compositions also contained higher SiO 2 concentrations to compare the role of SiO 2, TiO 2, and P 2O 5 on the Fe 3+/Fe 2+ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO 2, TiO 2, and P 2O 5 content results in a decrease in the ferric/ferrous ratio. The effects of TiO 2 and SiO 2 on the Fe 3+/Fe 2+ ratio was found to be almost identical. In contrast, adding P 2O 5 was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe 3+/Fe 2+ ratio. It was demonstrated that the effects of TiO 2 are minor but that the effects of P 2O 5 should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO 2 in magmas from the Fe 3+/Fe 2+ ratio in natural glasses using empirical equations published so far is discussed critically. [ABSTRACT FROM AUTHOR]

The crystallization sequence of a basaltic andesite from Bezymianny Volcano, Kamchatka, Russia, was simulated experimentally at 100 and 700 MPa at various water activities ( aHO) to investigate the compositional evolution of residual liquids. The temperature ( T) range of the experiments was 950-1,150 °C, aHO varied between 0.1 and 1, and the log of oxygen fugacity ( fO) varied between quartz-fayalite-magnetite (QFM) and QFM + 4.1. The comparison of the experimentally produced liquids and natural samples was used to constrain the pressure (P)- T- aHO- fO conditions of the Bezymianny parental magma in the intra-crustal magma plumbing system. The phase equilibria constraints suggest that parental basaltic andesite magmas should contain ~2-2.5 wt% HO; they can be stored in upper crustal levels at a depth of ~15 km, and at this depth they start to crystallize at ~1,110 °C. The subsequent chemical evolution of this parental magma most probably proceeded as decompressional crystallization occurred during magma ascent. The final depths at which crystallization products accumulated prior to eruption are not well constrained experimentally but should not be shallower than 3-4 km because amphibole is present in natural magmas (>150 MPa). Thus, the major volume of Bezymianny andesites was produced in a mid-crustal magma chamber as a result of decompressional crystallization of parental basaltic andesites, accompanied by mixing with silicic products from the earlier stages of magma fractionation. In addition, these processes are complicated by the release of volatiles due to magma degassing, which occurs at various stages during magma ascent. [ABSTRACT FROM AUTHOR]

Fluorine and chlorine play an important role in magmatic differentiation, hydrothermal alteration, and related mineralization processes, but tracing their evolution in magmatic and especially plutonic systems is not an easy task. The F and Cl in melts can be estimated from F and Cl concentrations in minerals, provided that partitioning between minerals and melts are constrained. Based on available partitioning models between mineral/melt, mineral/fluid, and melt/fluid, a set of equations has been derived to determine F and Cl concentrations in melts from the compositions of amphibole, biotite, and apatite. The new calculation procedure has been applied to a plutonic system, the Liujiawa pluton, eastern Dabie orogen (China). Cl and F concentrations in amphiboles, biotites, and apatites from different rock types (gabbronorite, two-pyroxene diorite, clinopyroxene diorite, and hornblende gabbro) have been determined by electron microprobe. Most amphiboles show a negative correlation between log(Cl/OH) and Mg-number and a positive correlation between log(F/OH) and A-site occupation. Biotites from the gabbronorite and two-pyroxene diorite show a slight positive correlation between log(Cl/OH) and Mg, which is however not the case for the clinopyroxene diorite. Apatites from all the samples are rich in F and show negative correlations between Cl and F concentrations. In our case study, we demonstrate that the Cl concentration in melt remains approximately constant at 1,000-2,000 ppm over the major crystallization interval, but decreases strongly at near solidus temperatures as a result of fluid exsolution. The F concentration in melt remains nearly constant at ca. 2,000-3,000 ppm at high temperatures as well as near solidus conditions, indicating that it is not largely affected by fluid exsolution because of its strongly preferred incorporation into melt. Interestingly, the evolution of Cl and F concentrations in melt with magmatic differentiation is similar to that determined in volcanic systems, suggesting that the evolution of Cl and F in melts during crystallization and late magmatic stages at depth (plutonic systems) is similar to that observed in volcanic systems during decompression and degassing. [ABSTRACT FROM AUTHOR]

Viscosity experiments were conducted with two flux-rich pegmatitic melts PEG0 and PEG2. The LiO, F, BO and PO contents of these melts were 1.04, 4.06, 2.30 and 1.68 and 1.68, 5.46, 2.75 and 2.46 wt%, respectively. The water contents varied from dry to 9.04 wt% HO. The viscosity was determined in internally heated gas pressure vessels using the falling sphere method in the temperature range 873-1,373 K at 200 and 320 MPa pressure. At 1,073 K, the viscosity of water-rich (~9 wt% HO) melts is in the range of 3-60 Pa s, depending on the melt composition. Extrapolations to lower temperature assuming an Arrhenian behavior indicate that highly fluxed pegmatite melts may reach viscosities of ~30 Pa s at 773 K. However, this value is a minimum estimation considering the strongly non-Arrhenian behavior of hydrous silicate melts. The experimentally determined melt viscosities are lower than the prediction of current models taking compositional parameters into account. Thus, these models need to be improved to predict accurately the viscosity of flux-rich water bearing melts. The data also indicate that Li influences significantly the melt viscosity. Decreasing the molar Al/(Na + K + Li) ratio results in a strong viscosity decrease, and highly fluxed melts with low Al/(Na + K + Li) ratios (~0.8) have a rheological behavior which is very close to that of supercritical fluids. [ABSTRACT FROM AUTHOR]

The behavior of tantalum and zirconium in pegmatitic systems has been investigated through the determination of Ta and Zr solubilities at manganotantalite and zircon saturation from dissolution and crystallization experiments in hydrous, Li-, F-, P- and B-bearing pegmatitic melts. The pegmatitic melts are synthetic and enriched in flux elements: 0.7–1.3 wt% Li2O, 2–5.5 wt% F, 2.8–4 wt% P2O5 and 0–2.8 wt% B2O3, and their aluminum saturation index ranges from peralkaline to peraluminous (ASILi = Al/[Na + K + Li] = 0.8 to 1.3) with various K/Na ratios. Dissolution and crystallization experiments were conducted at temperatures varying between 700 and 1,150°C, at 200 MPa and nearly water-saturated conditions. For dissolution experiments, pure synthetic, end member manganotantalite and zircon were used in order to avoid problems with slow solid-state kinetics, but additional experiments using natural manganotantalite and zircon of relatively pure composition (i.e., close to end member composition) displayed similar solubility results. Zircon and manganotantalite solubilities considerably increase from peraluminous to peralkaline compositions, and are more sensitive to changes in temperature or ASI of the melt than to flux content. A model relating the enthalpy of dissolution of manganotantalite to the ASILi of the melt is proposed: ∆ Hdiss (kJ/mol) = 304 × ASILi − 176 in the peralkaline field, and ∆ Hdiss (kJ/mol) = −111 × ASILi + 245 in the peraluminous field. The solubility data reveal a small but detectable competitivity between Zr and Ta in the melt, i.e., lower amounts of Zr are incorporated in a Ta-bearing melt compared to a Ta-free melt under the same conditions. A similar behavior is observed for Hf and Ta. The competitivity between Zr (or Hf) and Ta increases from peraluminous to peralkaline compositions, and suggests that Ta is preferentially bonded to non-bridging oxygens (NBOs) with Al as first-neighbors, whereas Zr is preferentially bonded to NBOs formed by excess alkalies. As a consequence Zr/Ta ratios, when buffered by zircon and manganotantalite simultaneously, are higher in peralkaline melts than in peraluminous melts. [ABSTRACT FROM AUTHOR]

Phase relations of basalts from the Kerguelen large igneous province have been investigated experimentally to understand the effect of temperature, fO2, and fugacity of volatiles (e.g., H2O and CO2) on the differentiation path of LIP basalts. The starting rock samples were a tholeiitic basalt from the Northern Kerguelen Plateau (ODP Leg 183 Site 1140) and mildly alkalic basalt evolved from the Kerguelen Archipelago (Mt. Crozier on the Courbet Peninsula), representing different differentiation stages of basalts related to the Kerguelen mantle plume. The influence of temperature, water and oxygen fugacity on phase stability and composition was investigated at 500 MPa and all experiments were fluid-saturated. Crystallization experiments were performed at temperatures between 900 and 1,160°C under oxidizing (log fO2 ~ ΔQFM + 4) and reducing conditions (log fO2 ~ QFM) in an internally heated gas-pressure vessel equipped with a rapid quench device and a Pt-Membrane for monitoring the fH2. In all experiments, a significant influence of the fO2 on the composition and stability of the Mg/Fe-bearing mineral phases could be observed. Under reducing conditions, the residual melts follow a tholeiitic differentiation trend. In contrast, melts have high Mg# [Mg2+/(Mg2+ + Fe2+)] and follow a calk-alkalic differentiation trend at oxidizing conditions. The comparison of the natural phenocryst assemblages with the experimental products allows us to constrain the differentiation and pre-eruptive conditions of these magmas. The pre-eruptive temperature of the alkalic basalt was about 950–1,050°C. The water content of the melt was below 2.5 wt% H2O and strongly oxidizing conditions (log fO2 ~ ΔQFM + 2) were prevailing in the magma chamber prior to eruption. The temperature of the tholeiitic melt was above 1,060°C, with a water content below 2 wt% H2O and a log fO2 ~ ΔQFM + 1. Early fractionation of clinopyroxene is a crucial step resulting in the generation of silica-poor and alkali-rich residual melts (e.g., alkali basalt). The enrichment of alkalis in residual melts is enhanced at high fO2 and low aH2O. [ABSTRACT FROM AUTHOR]

Small amounts of felsic, evolved plutonic rocks, often called oceanic plagiogranites, always occur as veins or small stocks within the gabbroic section of the oceanic crust. Four major models are under debate to explain the formation of these rocks: (1) late-stage differentiation of a parental MORB melt, (2) partial melting of gabbroic rocks, (3) immiscibility in an evolved tholeiitic liquid, and (4) assimilation and partial melting of previously altered dikes. Recent experimental data in hydrous MORB-type systems are used to evaluate the petrogenesis of oceanic plagiogranites within the deep oceanic crust. Experiments show that TiO2 is a key parameter for the discrimination between different processes: TiO2 is relatively low in melts generated by anatexis of gabbros which is a consequence of the low TiO2 contents of the protolith, due to the depleted nature of typical cumulate gabbros formed in the oceanic crust. On the other hand, TiO2 is relatively high in those melts generated by MORB differentiation or liquid immiscibility. Since the TiO2 content of many oceanic plagiogranites is far below that expected in case of a generation by simple MORB differentiation or immiscibility, these rocks may be regarded as products of anatexis. This may indicate that partial melting processes triggered by water-rich fluids are more common in the deep oceanic crust than believed up to now. At slow-spreading ridges, seawater may be transported via high-temperature shear zones deeply into the crust and thus made available for melting processes. [ABSTRACT FROM AUTHOR]

Phase relations of a phonolite (K1) and a tephri-phonolite (K2) from the Upper Miocene lavas in the Southeast Province of the Kerguelen Archipelago have been investigated in the P/T range 100–500 MPa and 700–900 °C at two fO2 conditions (~ NNO and ~ NNO+2.3) to clarify the differentiation and pre-eruptive conditions of these magmas. Crystallization experiments were performed in cold seal pressure vessels (CSPV) and internally heated pressure vessels (IHPV) at various XH2O, under reducing (log fO2 ~ NNO) and oxidizing conditions (log fO2 ~ NNO+2.3). Under reducing conditions, the resulting phase assemblage for K1 was: titanomagnetite, nepheline, alkali feldspar, clinopyroxene and biotite; under oxidizing conditions, the assemblage was: magnetite, plagioclase, alkali feldspar, nepheline, titanite (minerals given in the order of appearance with decreasing T at 200 MPa for 4 wt% water in the melt). It is emphasized that an effect of fO2 on the phase stability of feldspars and feldspathoides was observed. Comparison of the natural and experimental phase assemblages shows that the pre-eruptive conditions for K1 must have been in the log fO2 range ΔNNO+1-ΔNNO+2, at pressures above 200–250 MPa. Assuming a temperature of 800 °C, the water content of the melt is constrained to be between 4 and 6 wt% H2O. The pre-eruptive fO2 conditions for the less evolved sample K2 are more oxidizing with log fO2 close to ΔNNO+2.3. The experimental results show that the enrichment of alkalis in residual melts during differentiation of tephri-phonolites is enhanced at high fO2. [ABSTRACT FROM AUTHOR]

Investigates the water-undersaturated and dry Qz-Ab-Or system in liquidus phase relations. Determinants of liquidus temperatures in eclectic temperature and water content; Adiabatic decompressions in the quartz-alkali feldspar system; Importance of the evolution of dacitic and rhyolitic magmas.

Focuses on a study which compared the synthethic products to the natural phases to constrain pre-eruptive conditions in the Laacher See magma chamber in Germany. Background information on the Laacher See volcano; Starting material for the experiments; Experimental and analytical techniques; Experimental phase equilibria and composition of glasses and minerals.

Presents information on a study which determined water solubility in silicate melts coexisting with water-H2 fluids. Methodology of the study; Results and discussion on the study; Conclusions.

Provides information on a study of liquidus phase temperature and phase compostion in the system Qz-Ab-Or at 5 kbar. Methodology used to conduct the study; Results of the study; Detailed information on the experimental procedure and investigation of reaction kinetics; Discussion on the results of the study.

Investigates the influence of water-hydrogen fluids and redox conditions on melting temperatures in the haplogranite system. Good agreement of results from water-saturated solidi to previous studies; Suggestion that hydrogen has the behavior of an inert diluent of the fluid phase and has low solubility in aluminosilicate melts.

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. [ABSTRACT FROM AUTHOR]

In the original article, the Table 3 is published incorrectly. [ABSTRACT FROM AUTHOR]