- PAR ID:
- 10409300
- Date Published:
- Journal Name:
- American Mineralogist
- Volume:
- 107
- Issue:
- 11
- ISSN:
- 0003-004X
- Page Range / eLocation ID:
- 2084 to 2100
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Oxygen fugacity is an important but difficult parameter to constrain for primitive arc magmas. In this study, the partitioning behavior of Fe3+/Fe2+ between amphibole and glass synthesized in piston cylinder and cold-seal apparatus experiments is developed as an oxybarometer using x-ray absorption spectroscopy. The amphibole oxybarometer is applicable to hydrous magmas at subduction zone settings, and is here applied to amphibole in mafic enclaves, cumulates, and a basaltic tephra erupted from Shiveluch volcano in Kamchatka with measured Fe3+/FeTotal. The fO2 of primitive melts at the volcano is approximately NNO+2 and is faithfully recorded in amphibole from an amphibole-rich cumulate and the basaltic tephra. Apparently higher fO2 recorded by amphibole in mafic enclaves likely results from partial dehydrogenation of amphibole during residence in a shallow andesite storage region. Using a combination of the new oxybarometer and diffusion modeling, we identify three pulses of mafic magma recharge within two weeks of, a month before, and two to three months before eruption, and find that, at each of these times, the host andesite was recharged by at least two magmas at varying stages of differentiation. Application of the amphibole oxybarometer not only gives insight to magmatic fO2 but also potentially details of shallow magmatic processes.more » « less
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null (Ed.)The oxygen fugacity (fO2) of the Earth’s upper mantle and its melting products is an important parameter in the geochemical evolution of arc magmas and their connection with the continental crustal construction and growth. Several works have focused on the fO2 of peridotite xenoliths, primitive melts in relatively young arc settings, and mid-ocean ridge basalts (MORB) but few studies have attempted to examine the early redox history of primitive magmas in mature arcs. Hence, our understanding of the nature and evolution of fO2 during the subduction cycle remains limited. Here, we investigate the basaltic tephra from the Los Hornitos monogenetic cones in central-southern Chile, which are among the most primitive materials reported in the Southern Andes (olivine Mg# 92.5, and Ni 5000 mgg1). These features offer a unique opportunity to explore the fO2 conditions below the Andean arc by studying olivine phenocrysts and their contained crystal and melt inclusions. We integrated EPMA, LA-ICP-MS, and m-XANES analyses to constrain the redox conditions recorded in the basaltic tephra by three different and self-reliant methods. First, we determined the fO2 based on the olivine-spinel equilibrium, yielding average values DFMQ + 1.3 ± 0.4 (1r). Second, we constrained the fO2 conditions of melt inclusions using Fe m-XANES data and the redox dependent olivine-melt vanadium partitioning. After correcting for post-entrapment crystallization and diffusive iron loss, the Fe m-XANES data indicate that the melt inclusions were trapped in average at DFMQ +2.5 ± 0.5 (1r). Results using the olivine-melt vanadium partitioning oxybarometer in melt inclusions are in agreement with Fe m-XANES data, yielding average DFMQ values of +2.6 ± 0.3 (1r). In order to test the potential effects of other postentrapment modifications of the melt inclusions that could have affected the fO2 prior to eruption, we assessed the residence time of these magmas using Mg-Fe interdiffusion modelling in olivine. The short residence times (<200 days) compared to vanadium re-equilibration models strongly suggest that the melt inclusions preserve the prevailing fO2 conditions during their entrapment. Correlations between melt inclusions major element composition and their fO2 determined by Fe m-XANES, as well as V/Sc modelling reveal a case of post-melting oxidation of the LHC magmas. We argue that primitive arc magmas behave as an open system with respect to fO2 during their early geochemical evolution. Our data indicate a complex fO2 early history of primitive melts in the southern Andes and provide a cautionary note on the direct extrapolation of primitive melts fO2 values to that of their mantle source.more » « less
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Titanium and Fe isotopic compositions of lavas from a calc-alkaline differentiation suite and corresponding mineral separates from the Rindjani Volcano, Indonesia show that Fe and Ti isotopic fractionations between minerals and melts are lower than those recorded in other suites at all stages of differentiation. The limited isotopic fractionation for Ti is likely due to low-Ti magnetite and clinopyroxene being the dominant carriers of Ti in Rindjani lavas, as these minerals are thought to have limited equilibrium Ti isotopic fractionation relative to silicate magmas. Other magmatic differentiation suites controlled by removal of Ti-rich magnetite and characterized by a lesser role of clinopyroxene have larger Ti isotopic fractionations. This effect is an indirect consequence of the elevated Fe3+/Fe2+ ratio of calc-alkaline magmas such as Rindjani, which promotes Fe3+ incorporation into magnetite at the expense of Fe2+-Ti4+ pairs, such that increased oxygen fugacity will subdue Ti isotopic fractionation in global magmatic series. Similarly, we find negligible Fe isotopic fractionation in Rindjani bulk rocks and mineral separates, unlike previous studies. This is also likely due to the oxidized nature of the Rindjani differentiation suite, which leads to similar Fe3+/Fe2+ ratios in melt and minerals and decreases overall mineral-melt Fe fractionation factors. Paired Ti and Fe isotopic analyses may therefore represent a powerful tool to assess oxygen fugacity during differentiation, independent from Fe 3+ determinations of erupted samples.more » « less
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null (Ed.)Abstract Volcán Quizapu, Chile, is an under-monitored volcano that was the site of two historical eruptions: an effusive eruption in 1846–1847 and a Plinian eruption in 1932, both of which discharged ∼5 km3 (dense rock equivalent) of lava and/or tephra. The majority of material erupted in both cases is trachydacite, nearly identical for each event. We present H2O-saturated, phase equilibrium experiments on this end-member dacite magma, using a pumice sample from the 1932 eruption as the main starting material. At an oxygen fugacity (fO2) of ∼NNO + 0·2 (where NNO is the nickel–nickel oxide buffer), the phase assemblage of An25–30 plagioclase + amphibole + orthopyroxene, without biotite, is stable at 865 ± 10 °C and 110 ± 20 MPa H2O pressure (PH2O), corresponding to ∼4 km depth. At these conditions, experiments also reproduce the quenched glass composition of the starting pumice. At slightly higher PH2O and below 860 °C, biotite joins the equilibrium assemblage. Because biotite is not part of the observed Quizapu phase assemblage, its presence places an upper limit on PH2O. At the determined storage PH2O of ∼110 MPa, H2O undersaturation of the magma with XH2Ofluid = 0·87 would align Ptotal to mineral-based geobarometry estimates of ∼130 MPa. However, XH2Ofluid < 1 is not required to reproduce the Quizapu dacite phase assemblage and compositions. A second suite of experiments at lower fO2 shows that the stability fields of the hydrous silicates (amphibole and biotite) are significantly restricted at NNO – 2 relative to NNO + 0·2. Additional observations of Quizapu lava and pumice samples support the existing hypothesis that rapid pre-eruptive heating drove the effusive 1846–1847 eruption, with important refinements. We demonstrate that microlites in the end-member dacite lavas are consistent with in situ crystallization (during ascent), rather than transfer from an andesite. In one end-member dacite lava, newly identified reverse zoning in orthopyroxene and incipient destabilization of amphibole are consistent with small degrees of heating. Our work articulates a clear direction for future Quizapu studies, which are warranted given the active nature of the Cerro Azul–Descabezado Grande volcanic axis.more » « less
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Abstract The conditions under which halogens partition in favor of an exsolved fluid relative to the coexisting melt are key for understanding many magmatic processes, including volcanic degassing, evolution of crustal melt bodies, and ore formation. We report new F, Cl, and Br fluid/melt partition coefficients for intermediate to silicic melts, for which F and Br data are particularly lacking; and for varying CO2-H2O contents to assess the effects of changing fluid composition (XH2O) on Br fluid/melt partitioning for the first time. The experiments were conducted at pressures 50–120 MPa, temperatures 800–1100 °C, and volatile compositions [molar XH2O = H2O/(H2O +CO2)] of 0.55 to 1, with redox conditions around the Nickel-Nickel Oxygen buffer (fO2 ≈ NNO). Experiments were not doped with Cl, Br, or F and were conducted on natural crystal-bearing volcanic products at conditions close to their respective pre-eruptive state. The experiments therefore provide realistic constraints on halogen partitioning at naturally occurring, brine-undersaturated conditions. Measurements of Br, Cl, and F were made by Secondary Ion Mass Spectrometry (SIMS) on 13 experimental glass products spanning andesite to rhyolitic compositions, together with their natural starting materials from Kelud volcano, Indonesia, and Quizapu volcano, Chile. Fluid compositions were constrained by mass balance. Average bulk halogen fluid/melt partition coefficients and standard deviations are: DClfluid/melt = 3.4 (±3.7 1 s.d.), DFfluid/melt = 1.7 (±1.7), and DBrfluid/melt = 7.1 (±6.4) for the Kelud starting material (bulk basaltic andesite), and DClfluid/melt = 11.1 (±3.5), DFfluid/melt = 0.8 (±0.8), and DBrfluid/melt = 31.3 (±20.9) for Quizapu starting material (bulk dacite). The large range in average partition coefficients is a product of changing XH2O, pressure and temperature. In agreement with studies on synthetic melts, our data show an exponential increase of halogen Dfluid/melt with increasing ionic radius, with partitioning behavior controlled by melt composition according to the nature of the complexes forming in the melt (e.g., SiF4, NaCl, KBr). The fundamental chemistry of the different halogens (differing ionic size and electronegativities) controls the way in which partitioning responds to changes in melt composition and other variables. Experimental results confirm that more Cl partitions into the fluid at higher bulk Cl contents, higher melt Na, higher fluid XH2O ratios, and lower temperatures. Bromine shows similar behavior, though it seems to be more sensitive to temperature and less sensitive to Na content and XH2O. In contrast, F partitioning into the fluid increases as the melt silica content decreases (from 72 to 56 wt% SiO2), which we attribute to the lower abundance of Si available to form F complexes in the melt. These new data provide more insights into the conditions and processes that control halogen degassing from magmas and may help to inform the collection and interpretation of melt inclusions and volcano gas data.