Oxygen Barometer Research Articles

The Olivine-Spinel-aSiO2melt (OSaS) Oxybarometer: A New Method for Evaluating Magmatic Oxygen Fugacity in Olivine-Phyric Basalts

Abstract The compositions of cotectic olivine-spinel pairs in mafic magmas provide information on the oxygen fugacity of their host liquid, which can be accessed with a thermodynamic analysis of the olivine-spinel-liquid peritectic reaction: 3 F e 2 S i O 4 o l i v + O 2 s y s = 2 F e 3 O 4 s p + 3 S i O 2 m e l t The extraction of redox information from cotectic olivine-spinel pairs requires a well-defined silica activity value (aSiO2melt) for the melt of interest, as well as a method to calculate aFe2SiO4oliv and aFe3O4sp from chemical analyses of olivine and spinel, respectively. In this work, we develop a new olivine-spinel-aSiO2melt (OSaS) oxygen barometer that utilizes MELTS to obtain values of aSiO2melt, which are used with values aFe2SiO4oliv and aFe3O4sp determined from established solution models for olivine and spinel. We find that two implementations of the spinel-liquid peritectic equilibria can successfully generate magmatic oxygen fugacity values, (1) using a combination of mineral activity models from the literature (classical-OSaS) and aSiO2melt determined from MELTS, and (2) directly from chemical potentials obtained from MELTS, where a correction is added to the MELTS-derived chemical potentials for the magnetite component of the spinel (MELTS-OSaS). The two implementations of the OSaS were tested by using each model to recover the experimentally reported fO2 values for a dataset consisting of 50 olivine-spinel-glass assemblages derived from 14 published experimental studies. This dataset was filtered to remove potential disequilibrium phase assemblages, experiments with failed redox buffers, and poor-quality EMP analyses. Data quality metrics for the dataset filtration included Fe-Mg partitioning between olivine and melt, Fe-Mg partitioning between olivine-spinel, and an examination of whether aSiO2melt values were consistent with the reported phase assemblages. The classical-OSaS implementations reproduced the fO2 values reported from the experimental dataset with a standard error estimate (SEE) of ±0.39, root mean standard error (RMSE) of ±0.40 and average deviation of ±0.31. In testing the MELTS-OSaS model, we identified that the solution model for magnetite underpredicted the values of aFe3O4sp; therefore, we used the 50 experiments to assign a correction to the MELTS-predicted chemical potentials of magnetite. We tested 35 the MELTS-OSaS model with the magnetite correction on a dataset of 18 additional buffered experiments, filtered for redox equilibrium and not included in the original experimental dataset. We find that the MELTs-OSaS model, which includes the correction for the magnetite chemical potential, reproduces fO2 values for the 18 experiments with an SEE of ±0.20, root mean standard error (RMSE) of ±0.23 and average deviation of ±0.18. The OSaS oxybarometer can return magmatic fO2 values with a standard error of ± 0.20 to 0.39 log units, depending on the model selected, provided that the olivine-spinel cotectic temperature is known to an accuracy of ±25°C, the H2O content of the melt can be estimated within ±1.5wt%, and that the crystallization pressure of the olivine-spinel pair is < 500 MPa. We also propose that the OSaS models can be applied to experimental run products to determine or confirm oxygen fugacity values. We additionally suggest that the careful application of the OSaS oxybarometer can provide a reliable and robust alternative for performing redox studies on samples that do not contain sufficient glassy material to support the application of spectroscopic techniques (i.e., XANES and Mössbauer).

Petrogenesis of the U-rich Permian Akkulen syenite intrusion, Tien Shan, Kyrgyzstan: insights into its magmatic evolution and geodynamic setting

ABSTRACT Permian alkaline granitoids are widely distributed throughout the Tien Shan Orogen and adjacent region of the southern Central Asian Orogenic Belt. However, their petrogenesis and related tectonic setting remain equivocal. A detailed mineralogical, U-Pb zircon dating, in situ elemental and Sr-Nd-Hf isotopic studies of the uranium-rich Akkulen syenite intrusion in the Northern Tien Shan of Kyrgyzstan were undertaken to better understand its magmatic processes and geodynamic evolution. Four independent oxygen barometers have shown that the oxygen fugacity of the Akkulen syenitic magma evolved from initial low fO2 (<NNO +1, where NNO is the nickel-nickel oxide buffer) to relatively high fO2 (>NNO +1) during magma ascent and cooling; Apatite geochemical characteristics also indicate that the magma is relatively high F (2.9–5.1 wt.%), with low Cl (0.053–0.13 wt.%) and anhydrous (<4 wt %) contents. According to whole-rock geochemical data, the syenite samples have abnormally high U (38.5–57.1 ppm) and Th (96.2–137 ppm) concentrations, we suggest that high F content and moderate oxygen fugacity are beneficial for uranium enrichment. Zircon grains from a syenite sample yielded a weighted 206Pb/238U age of 283.5 ± 2.6 Ma. The intrusion has an A-type granite affinity with high alkali (Na2O + K2O) contents and Fe/(Fe+Mg) ratios, high LREE/HREE (~5), and low Sr, Ba, and Eu contents. They have negative εNd(t) (−5.2 to −3.6) values with Mesoproterozoic two-stage model ages (T DM2 = 1.35–1.47 Ga), and variable εHf(t) values (−4.6 to +2.4) with Mesoproterozoic two-stage model ages (T DM2 = 1. 2–1.59 Ga), which suggest these rock derivations from the relatively old crustal with minor contribution from juvenile crustal melts. In comparison with regional available dataset, we propose that the alkaline Permian granitoids in Kyrgyz Northern Tien Shan may have been originated from large-scale partial melting of Mesoproterozoic metamorphic basement with minor juvenile crustal material in a post-extensional setting. In contrast, the Early Permian granitoid magmatism in the Tarim Craton may have been caused by the partial melting of Neoproterozoic basement rocks associated with Permian mantle plume activities.

Natural ilmenite reference material for trace elemental in situ microanalysis

Ilmenite is a commonly occurring mineral in both igneous and metamorphic rocks and its major and trace elements have various applications in geology, including as a geothermometer, oxygen barometer, and geochemical tracer. In this study, a 500 g ilmenite megacryst sample (LY) was developed as a reference material for in situ element microanalysis. Twenty-two ilmenite fragments, with grain sizes ranging from 1 to 8 mm, were subjected to major and trace element analysis using electron microprobe analysis (EMPA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in four different laboratories. The results indicate that the ilmenite sample is homogeneous with respect to TiO2, FeO, Mg, Sc, V, Cr and Mn, whereas Co and Nb are minor inhomogeneous. Consequently, this sample can be used as a reliable reference material for in situ microanalysis.

Age and Petrogenesis of Ultramafic Lamprophyres of the Arbarastakh Alkaline-Carbonatite Complex, Aldan-Stanovoy Shield, South of Siberian Craton (Russia): Evidence for Ultramafic Lamprophyre-Carbonatite Link

Abstract In this study, we discuss mineral chemistry data, melt inclusion study results, and report Ar–Ar phlogopite age for the aillikite dikes of the Arbarastakh alkaline-carbonatite complex on the Aldan-Stanovoy shield, Russia. Aillikite was crystallized at 631 ± 8.5 Ma, coeval with the intrusion age of the Arbarastakh rocks. The Arbarastakh complex was formed during the late Neoproterozoic epoch of rare earth element-Nb ore-bearing alkaline-carbonatite magmatic activity that was widespread on the southwestern and southern margins of the Siberian craton, related to rifting processes during the breakup of the supercontinent Rodinia. The aillikites show mineralogical characteristics of primitive magmas such as highly forsteritic olivine, Mg-ilmenite, and Cr-rich spinel. The variance in olivine zonation, morphologies, and chemical element distribution indicate that olivine in the aillikites is represented by several genetic types: xenogenic olivines (Fe-poor cores) from the sheared peridotite, olivine antecrysts (Fe-rich cores) related to mantle metasomatism by preceding proto-aillikite melt, and olivine phenocrysts formed during crystallization of aillikite melt. The latter shows decreasing Ni and Cr due to fractional crystallization of olivine, ilmenite, and chromite, along with increasing Mn and Ca concentrations that are consistent with enrichment of these elements in the residual melt. The olivine phenocrysts chemistry shows variations that are characteristic of the presence of phlogopite and carbonate in the mantle source (low 100*Ca/Fe (0.4–1.2) and 100*Mn/Fe (1–2), moderate 100*Ni/Mg (1.4–0.4)). Spinel shows a wide compositional variation with two compositional zoning trends, one of which follows the titanomagnetite trend, while the other follows the qandilite-rich magnesio-ulvöspinel-magnetite one. The latter trend indicates an increase in fO2 and attendant Fe oxidation to Fe3+ during crystallization. Ilmenite composition evolution (from Mg-rich to Mn-rich) also reflects the carbonate-rich nature of aillikite melt. We identify primary melt inclusions hosted in phlogopite and secondary melt inclusions in olivine; both melt inclusions types have daughter minerals dominated by dolomite, calcite, Na-Ca carbonates, phosphates, and phlogopite, consistent with the carbonate-rich nature of aillikite melt. The calculated temperatures reflect the early stage of aillikite crystallization, with values ranging from 1169 to 1296°C and fO2 values (olivine-spinel pair) varying from +0.40 to +1.03 ΔFMQ and from ΔNNO −0.9 to ΔNNO −2.0 (perovskite oxygen barometer); in contrast, the homogenization temperature of the secondary melt inclusions in olivine (700–720°C) characterizes late-stage aillikite melt evolution. The carbonate-rich nature of the Arbarastakh aillikite and its similar age to the carbonatites are consistent with a genetic relationship between them.

Contrasting oxidation states of low-Ti and high-Ti magmas control Ni-Cu sulfide and Fe-Ti oxide mineralization in Emeishan Large Igneous Province

Magmatic Ni-Cu-(PGE) sulfide and Fe-Ti oxide deposits in plume-related large igneous provinces (LIPs) are commonly related to low-Ti and high-Ti series magmas, respectively, but the major factors that control such a relationship of metallogenic types and magma compositions are unclear. Magma fO2 controls sulfur status and relative timing of Fe-Ti oxide saturation in mafic magmas, which may help clarify this issue. Taking the Emeishan LIP as a case, we calculated the magma fO2 of the high-Ti and low-Ti picrites based on the olivine-spinel oxygen barometer, and the partitioning of V in olivine. The obtained fO2 of the high-Ti series magma (FMQ + 1.1 to FMQ + 2.6) is higher than that of the low-Ti series magma (FMQ − 0.5 to FMQ + 0.5). The magma fO2 of the high-Ti and low-Ti picrites containing Fo > 90 olivine reveals that the mantle source of the high-Ti series is likely more oxidized than that of the low-Ti series. The results using the ‘lambda REE’ approach show that the high-Ti series may have been derived from relatively oxidized mantle with garnet pyroxenite component. The S contents at sulfide saturation (SCSS) of the two series magmas were calculated based on liquid compositions obtained from the alphaMelts modeling, and the results show that the low-Ti series magma could easily attain the sulfide saturation as it has low fO2 with S being dominantly as S2−. In contrast, the oxidized high-Ti series magma is difficult to attain the sulfide saturation, but could crystallize Fe-Ti oxides at magma MgO content of ∼7.0 wt.%. Thus, contrasting magma fO2 of low-Ti and high-Ti series in plume-related LIPs may play an important role in producing two different styles of metallogeny.

Mantle source and magma oxygen fugacity of Permian Ni--Cu sulfide-bearing mafic-ultramafic intrusions in the Inner Mongolia, North China: Controls on the sulfide saturation of magmas in the Andean-style continental convergent margins

Permian Erbutu and Kebu Ni--Cu sulfide-bearing mafic-ultramafic intrusions in the central Asian orogenic belt (CAOB) formed in the Andean-style continental convergent margin adjacent to the northern margin of the North China Craton (NCC). The rocks of the two intrusions show arc-like affinity on the primitive mantle-normalized trace element patterns and have εNd(t) ranging from −8.7 to −4.2, which are interpreted to be related to derivation from the metasomatized, enriched, subcontinental lithospheric mantle (SCLM) beneath the NCC. Using the olivine-orthopyroxene-spinel oxygen barometer, the magma fO2 of the Erbutu and Kebu intrusions was calculated to be from FMQ-0.8 to FMQ + 0.2, and from FMQ + 1.3 to FMQ + 2.0, respectively. The sulfides in the rocks have δ34SCDT ranging from +5.3 to +7.5‰ for the Erbutu intrusion and from +2.0 to +4.5‰ for the Kebu intrusion, much higher than that of the MORB mantle (δ34SCDT = −1.5 to 0.6‰). The rocks of the Erbutu and Kebu intrusions have δ13C ranging from −26.1 to −20.4‰ and − 26.4 to −20.9‰, respectively, similar to that of organic carbon in the crust (δ13C = −28 to −20‰), but much lower than that of the MORB mantle (δ13C = −7 to −5‰). These may indicate the addition of externally derived sulfur (S) and organic carbon into the magmas, which would increase S contents and decrease S solubility of the magmas, respectively, triggering sulfide saturation of the magmas. It is noted that the sulfide saturation of the Erbutu intrusion was mainly related to the addition of externally derived sulfur in the magmas as sulfur is generally present as S2− species in the low-fO2 magmas. Both intrusions have trace element patterns and εNd(t) values nearly identical to those of the Permian Elitu volcanic rocks in the same region, indicating that they were likely genetically linked. The Elitu volcanic rocks show negative correlation of (Gd/Yb)N with >3.0 wt% MgO, which is interpreted as the primary magmas of the rocks may have experienced early garnet fractionation at high pressure (e.g., 0.8 to 2.0 GPa). The calculated thickness of the crust in this region is ~56 km, equivalent to ~1.7 GPa in pressure. The primary magmas of the Erbutu and Kebu intrusions were produced by partial melting of the enriched SCLM beneath the thickened crust and are likely Ni-enriched, which is also crucial to the economic Ni--Cu sulfide mineralization in the Andean-style continental convergent margin in the CAOB.

Magma oxygen fugacity of mafic-ultramafic intrusions in convergent margin settings: Insights for the role of magma oxidation states on magmatic Ni-Cu sulfide mineralization

AbstractOxygen fugacities (fO2) of mantle-derived mafic magmas have important controls on the sulfur status and solubility of the magmas, which are key factors to the formation of magmatic Ni-Cu sulfide deposits, particularly those in convergent margin settings. To investigate the fO2 of mafic magmas related to Ni-Cu sulfide deposits in convergent margin settings, we obtained the magma fO2 of several Ni-Cu sulfide-bearing mafic-ultramafic intrusions in the Central Asian Orogenic Belt (CAOB), North China, based on the olivine-spinel oxygen barometer and the modeling of V partitioning between olivine and melt. We also calculated the mantle fO2 on the basis of V/Sc ratios of primary magmas of these intrusions.Ni-Cu sulfide-bearing mafic-ultramafic intrusions in the CAOB include arc-related Silurian-Carboniferous ones and post-collisional Permian-Triassic ones. Arc-related intrusions formed before the closure of the paleo-Asian ocean and include the Jinbulake, Heishan, Kuwei, and Erbutu intrusions. Post-collisional intrusions were emplaced in extensional settings after the closure of the paleo-Asian ocean and include the Kalatongke, Baixintan, Huangshandong, Huangshan, Poyi, Poshi, Tulaergen, and Hongqiling No. 7 intrusions. It is clear that the magma fO2 values of all these intrusions in both settings range mostly from FMQ+0.5 (FMQ means fayalite-magnetite-quartz oxygen buffer) to FMQ+3 and are generally elevated with the fractionation of magmas, much higher than that of MORBs (FMQ-1 to FMQ+0.5). However, the mantle fO2 values of these intrusions vary from ~FMQ to ~FMQ+1.0, just slightly higher than that of mid-ocean ridge basalts (MORBs) (≤FMQ). This slight difference is interpreted as the intrusions in the CAOB may have been derived from the metasomatized mantle wedges where only minor slab-derived, oxidized components were involved. Therefore, the high-magma fO2 values of most Ni-Cu sulfide-bearing mafic-ultramafic intrusions in the CAOB were attributed to the fractionation of magmas derived from the slightly oxidized metasomatized mantle. In addition, the intrusions that host economic Ni-Cu sulfide deposits in the CAOB usually have magma fO2 of &amp;gt;FMQ+1.0 and sulfides with mantle-like δ34S values (–1.0 to +1.1‰), indicating that the oxidized mafic magmas may be able to dissolve enough mantle-derived sulfur to form economic Ni-Cu sulfide deposits. Oxidized mafic magmas derived from metasomatized mantle sources may be an important feature of major orogenic belts.

Magmatic haggertyite in olivine lamproites of the West Kimberley region, Western Australia

Abstract We report the first occurrence of magmatic haggertyite (BaFe6Ti5MgO19) from the Miocene lamproites of the West Kimberley region of Western Australia. This contrasts with the metasomatic formation reported in an olivine lamproite host at the type locality, Prairie Creek, Arkansas. Haggertyite occurs in the groundmass of a diamondiferous olivine lamproite pipe in the Ellendale field, and within the large zoned Walgidee Hills lamproite where it forms part of an extensive suite of Ba- and K-bearing titanate and Ti-rich silicate minerals. The haggertyite co-exists with chromian spinel, perovskite, and ilmenite in the Ellendale lamproite, and with priderite and perovskite and, in one locality, with priderite, jeppeite, ilmenite, and perovskite, in the Walgidee Hills lamproite. Unlike priderite and perovskite, which are common groundmass phases in the Ellendale olivine lamproites and present throughout the Walgidee Hills lamproite, haggertyite appears restricted in its occurrence and crystallization interval, with sparse ilmenite apparently mostly crystallizing as an alternative phase. In the Walgidee Hills lamproite the haggertyite-bearing assemblage is succeeded by the Ba-titanate assemblage priderite plus jeppeite in the evolved central part of the body. The haggertyite in the main zone of the Walgidee Hills lamproite has an average composition of (Ba0.7K0.3)1.0(Ti5.0Fe2.13+Cr0.1Fe3.82+Mn0.2Mg0.6Na0.1)12O19 and is thus very similar to the original haggertyite described from xenoliths in the Prairie Creek lamproite apart from being poorer in Cr and Ni. Haggertyite in the groundmass of the Ellendale olivine lamproite and the central zone of the Walgidee Hills lamproite, in addition to variations in Mg and Cr, show significant variation in Ti and Fe contents and in calculated Fe3+ and Fe2+. A linear inverse relationship between Ti and Fe, and Ti and Fe3+, indicates that Fe3+ is accommodated by the coupled substitution Ti4+ + Fe2+ ⇆ 2 Fe3+. A marked trend to higher Fe3+ in the haggertyite in Ellendale 9 olivine lamproite is ascribed to increasing oxidation during crystallization, with fO2 estimated from the olivine-spinel thermometer and oxygen barometer at Dlog FMQ = –1 to +3 at temperatures of 790–660 °C. The haggertyite in the central zone of the Walgidee Hills lamproite, in contrast, shows a marked trend to Fe2+ enrichment, which is associated with decreasing Fe in perovskite. This is inferred to indicate formation under more reducing conditions, but sufficiently oxidized to permit Fe3+ in co-existing priderite and jeppeite. Trace-element analysis by LA-ICP-MS shows the Walgidee Hills haggertyite contains minor amounts of Na, Si, Ca, V, Co, Zn, Sr, Zr, Nb, and Pb, and only traces of Al, P, Sc, Rb, REE, Hf, and Ta. Moreover, the haggertyite is preferentially enriched in certain lithophile (Ba, Sr), siderophile (Mn, Fe, Co, Ni), and chalcophile (Zn, Pb) elements relative to co-existing priderite. Haggertyite crystallization appears to be a consequence not only of the very high Ba, Ti, and K contents of the lamproite, but of relatively high-Fe concentrations and low temperatures in evolved olivine lamproite magma with the Fe3+/Fe2+ ratio determined by the prevailing fO2. The new data suggest that haggertyite might also be present but previously unrecognized in the evolved groundmass of other olivine lamproites. Haggertyite is one of an increasing number of new minerals in upper mantle rocks and volcanics derived from the upper mantle hosting large-ion-lithophile and high field strength cations.

Petrological and geochemical modeling of magmas erupted at Vulcano Island in the period 54–8 ka: Quantitative constraints on the sub-volcanic architecture of the plumbing system

In this study, we present new mineralogical and petrological data from fifteen eruptive products erupted at Vulcano Island (Aeolian Arc, Italy) over a period of time from 54 to 8 ka and representative of the Eruptive Epochs from 5 to 8 of this volcanic system. These rocks show shoshonitic (SHO) to high-K calc-alkaline (HKCA) affinity, with compositions changing from primitive basalts-shoshonites (Mg#35–60) to intermediate latites (Mg#32–54) to evolved trachytes-rhyolites (Mg#23–40). The intensive variables driving the crystallization path of magmas were reconstructed through mineral-melt equilibrium and thermodynamic models, as well as barometers, thermometers, hygrometers and oxygen barometers. The stability of olivine (Fo59–91), as first phase on the liquidus, is more favored at low-P (100–300 MPa) and high-H2O (4 wt%) contents dissolved in the melt. Afterwards, the melt is co-saturated with clinopyroxene (Mg#92, diopside), whose composition progressively evolves (Mg#71, augite) as the temperature decreases to 1100 °C. The crystallization pressure recorded by clinopyroxene decreases from basalts (550–750 MPa) to shoshonites-latites-trachytes (100–450 MPa) to rhyolites (~50 MPa). The melt-H2O content (0.5–4.2 wt%) is sensitive to either pressure or melt composition, thereby controlling the plagioclase stability and chemistry (An13–77) within a thermal path of ~860–1100 °C. Titanomagnetite (Usp11–39) equilibrates with progressively more oxidized melts as the magma composition changes from basalt (ΔQFM+1.5) to rhyolite (ΔQFM+3). Mass balance calculations and trace element modeling indicate that basaltic to trachytic magmas are prevalently controlled by fractional crystallization processes, in concert with variable degrees of assimilation of crustal rocks. Conversely, rhyolitic and highly differentiated trachytic magmas are generated by extraction of interstitial melts from shallow mush zones dominated by feldspar and titanomagnetite saturation. We conclude that the architecture of the plumbing system at Vulcano Island is characterized by multiple reservoirs in which compositionally distinct magmas pond and undergo polybaric-polythermal differentiation, before erupting to the surface.

Harzburgite found in the Hegenshan ophiolite, southeastern Central Asian Orogenic Belt: Petrogenesis and geological implications

This paper reports detailed studies on harzburgite and serpentinite in the Hegenshan ophiolitic mélange. Harzburgite consists mainly of olivine and orthopyroxene with trace amounts of clinopyroxene and chromian spinel. Clinopyroxene occurs as isolated crystals or in the intergrowth of chromian spinel–clinopyroxene–orthopyroxene. Harzburgite is moderately to highly depleted, displaying high Fo contents in olivine (90.8–92.2), moderate Al2O3 contents in orthopyroxene (1.59–2.79 wt%), low heavy REE abundances in clinopyroxene, and moderate Cr# values of spinel (0.50–0.62). The modal proportions of olivine and orthopyroxene pseudomorph grains imply that the parent of the Hegenshan serpentinite should be harzburgite. Whole-rock compositions of the harzburgite and serpentinite samples are characterized by depletions in Al2O3 and CaO and enrichments in light REE, Sr, and U. Geochemical modeling suggests that the Hegenshan harzburgite represents residues after 17–18% partial melting of the primitive mantle. The melt in equilibrium with clinopyroxene is more depleted than typical forearc basalt and boninite. Various pyroxene thermobarometers yield equilibrated temperatures of 945–1067 °C and pressures of 4.8–8.0 kbar for the Hegenshan harzburgite. The oxygen barometer yields results of +0.4 to +1.7 log units above the fayalite–magnetite–quartz buffer for the Hegenshan harzburgite. These petrological and geochemical characteristics, as well as the estimated P–T–fO2 conditions support a back-arc setting for the Hegenshan ophiolitic mélange.

Modeling the Crystallization and Emplacement Conditions of a Basaltic Trachyandesitic Sill at Mt. Etna Volcano

This study documents the compositional variations of phenocrysts from a basaltic trachyandesitic sill emplaced in the Valle del Bove at Mt. Etna volcano (Sicily, Italy). The physicochemical conditions driving the crystallization and emplacement of the sill magma have been reconstructed by barometers, oxygen barometers, thermometers and hygrometers based on clinopyroxene, feldspar (plagioclase + K-feldspar) and titanomagnetite. Clinopyroxene is the liquidus phase, recording decompression and cooling paths decreasing from 200 to 0.1 MPa and from 1050 to 940 °C, respectively. Plagioclase and K-feldspar cosaturate the melt in a lower temperature interval of ~1000–870 °C. Cation exchanges in clinopyroxene (Mg-Fe) and feldspar (Ca-Na) indicate that magma ascent is accompanied by progressive H2O exsolution (up to ~2.2 wt. %) under more oxidizing conditions (up to ΔNNO + 0.5). Geospeedometric constraints provided by Ti–Al–Mg cation redistributions in titanomagnetite indicate that the travel time (up to 23 h) and ascent velocity of magma (up to 0.78 m/s) are consistent with those inferred for other eruptions at Mt. Etna. These kinetic effects are ascribed to a degassing-induced undercooling path caused principally by H2O loss at shallow crustal conditions. Rare earth element (REE) modeling based on the lattice strain theory supports the hypothesis that the sill magma formed from primitive basaltic compositions after clinopyroxene (≤41%) and plagioclase (≤12%) fractionation. Early formation of clinopyroxene at depth is the main controlling factor for the REE signature, whereas subsequent degassing at low pressure conditions enlarges the stability field of plagioclase causing trace element enrichments during eruption towards the surface.

Magmatic oxygen fugacity estimated using zircon-melt partitioning of cerium

Using a newly-calibrated relation for cerium redox equilibria in silicate melts (Smythe and Brenan, 2015), and an internally-consistent model for zircon-melt partitioning of Ce, we provide a method to estimate the prevailing redox conditions during crystallization of zircon-saturated magmas. With this approach, oxygen fugacities were calculated for samples from the Bishop tuff (USA), Toba tuff (Indonesia) and the Nain plutonic suite (Canada), which typically agree with independent estimates within one log unit or better. With the success of reproducing the fO2 of well-constrained igneous systems, we have applied our Ce-in-zircon oxygen barometer to estimating the redox state of Earth's earliest magmas. Using the composition of the Jack Hills Hadean zircons, combined with estimates of their parental magma composition, we determined the fO2 during zircon crystallization to be between FMQ −1.0 to +2.5 (where FMQ is the fayalite–magnetite–quartz buffer). Of the parental magmas considered, Archean tonalite–trondhjemite–granodiorite (TTG) compositions yield zircon-melt partitioning most similar to well-constrained modern suites (e.g., Sano et al., 2002). Although broadly consistent with previous redox estimates from the Jack Hills zircons, our results provide a more precise determination of fO2, narrowing the range for Hadean parental magmas by more than 8 orders of magnitude. Results suggest that relatively oxidized magmatic source regions, similar in oxidation state to that of 3.5 Ga komatiite suites, existed by ∼4.4 Ga.

Physicochemical parameters of deep-seated mantle plumes

Thermodynamic analysis of experimental data has demonstrated that FeO activity in silicate melts identical in composition to natural magmas can be described by the regular-solution model, which takes into account interactions of all cations with Si and interaction of Ca with Al. Using this model, we propose an oxygen barometer for spinel + magma phase association. In contrast to the earlier proposed methods for estimation of oxygen chemical potential, this barometer can work in the PJ-domain close to the liquidus of magmatic process. The new oxygen barometer has been applied to magmas related to mantle plume activity, including Siberian meimechites, Hawaiian picrites, and picrites from the Emeishan large igneous province (LIP) and Greenland. We have shown that most magmas related to the activity of deep-seated mantle plumes are characterized by a higher relative chemical potential of oxygen than magmas of mid-ocean ridges. Thermodynamically calculated stability fields of rocks with different carbon-containing phases show that under PJ-conditions of the lower mantle, the ascending mantle plumes are characterized by relatively high oxygen fugacity. Formation of diamond in the lower mantle requires more oxidizing conditions as compared with the major part of this geosphere, where the presence of Fe-Ni alloy is predicted. We have put forward a hypothesis that the main reason for the oxygen fugacity increase in particular domains of the lower mantle is a shift of redox equilibria toward a decrease in the amount of Fe-Ni alloy, up to its disappearance, with temperature growth.

The redox geodynamics linking basalts and their mantle sources through space and time

The Earth's mantle redox state regulates the fate and transfer of metals by magmatism, buffers the igneous inputs of volcanic gases in the atmosphere and controls the depth of mantle melting. It therefore strongly affects ore forming processes, biogeochemical cycles and deep geodynamic processes. This paper reviews the current knowledge on the redox state of the upper mantle and of magmas produced by mantle melting. The geochemical processes likely to control and modify it through space and time are discussed.We analyze the link between the redox state of magma and that of their mantle source and we conclude that melts produced in the mantle may well all equilibrate in a narrow range of oxidation state, where the speciation of sulfur in basalts shifts from sulfide to sulfate, that is, FMQ+1±1 (1 log unit below and above the oxygen fugacity buffered by the assemblage fayalite–magnetite–quartz). Subsequently, degassing and partial crystallization of melts can affect their redox states, producing most of the range of redox states observed on magmas reaching Earth's surface. The asthenosphere sourcing basaltic magmas may therefore be more oxidized than the FMQ−1 value generally assumed.We also discuss redox transfers from the mantle to the atmosphere via volcanic degassing and the backward fluxes via subduction processes of the hydrothermalized oceanic lithosphere. Arc-magmas are oxidized (up to FMQ+4) but it is unclear when this feature is acquired since strongly oxidized primary arc-basalts have yet to be found. The oxidizing event may be the assimilation of slab-derived SO3-rich fluids by primary basalt generated by decompression melting in the mantle-wedge.Overall, subduction must result in a transfer of oxygen from the Earth's surface down to the mantle. This must imply that subduction and its initiation can hardly be the trigger of the great oxidation event at the end of the Archaean. In contrast, the cooling of the Earth's interior through time must have impacted on the redox state of basalts, by decreasing the depth of mantle melting. According to the long-established vertical stratification of the Earth's mantle, ancient primary magmas are therefore likely to have been more reduced (i.e. <FMQ−3) than present-day ones. However, geochemical observations on ancient basalts suggest a constant oxidation state since the early Archaean.We conclude that large uncertainties in the calibration of mineralogical oxygen barometer probably explains why we have difficulties in identifying (i) ancient primary basalts being more reduced than recent ones and (ii) primary basalts from subduction zones being as oxidized as arc-lavas reaching the surface. Finally, the degree of mantle melting is certainly a key issue for the interpretation of the mantle oxidation state. Extremely oxidized melts, enriched in C–H–S volatile species, produced by very low degrees of mantle melting may be indicative of an Earth's mantle more oxidized than usually considered.

New petrological constraints on the last eruptive phase of the Sabatini Volcanic District (central Italy): Clues from mineralogy, geochemistry, and Sr–Nd isotopes

We report results from mineralogical, geochemical and isotopic analyses of the three youngest pyroclastic products (ca. 86 ky) belonging to the Sabatini Volcanic District (Roman Province, central Italy). By means of thermometers, hygrometers and oxygen barometers, we have estimated that the crystallization temperature of magma progressively decreases over time (910–740 °C), whereas the amount of water dissolved in the melt and f O 2 progressively increases as compositions of magmas become more differentiated (4.5–6.4 wt.% H 2 O and 0.4–2.6 ΔQFM buffer, respectively). Thermodynamic simulations of phase equilibria indicate that geochemical trends in mafic magmas (MgO > 4 wt.%) can be reproduced by abundant fractionation of olivine and clinopyroxene (~ 50 wt.% crystallization), while the trends of more evolved magmas (MgO ≤ 4 wt.%) originated by fractional crystallization of plagioclase and sanidine (~ 45 wt.% crystallization). The behavior of trace elements highlights that magmatic differentiation is controlled by polybaric differentiation that includes: (1) prolonged fractionation of mafic, anhydrous minerals from a primitive, H 2 O-poor magma at depth and (2) extraction of a more evolved, H 2 O-rich magma that crystallizes abundant felsic and subordinated hydrous minerals at shallow crustal levels. Assimilation and fractional crystallization modeling also reveal that magmas interacted with the carbonate rocks of the subvolcanic basement. The effect of carbonate assimilation accounts for both trace element and Sr–Nd isotopic variations in magmas, suggesting a maximum degree of carbonate assimilation of less than 5 wt.%. • We studied the youngest pyroclastic products of the Sabatini Volcanic District. • The crystallization temperature of magma progressively decreased over time, whereas the melt–water-content increased. • Trace element and isotope data indicate a multi-stage process controlled by assimilation and fractional crystallization.

FeO activity and oxygen potential in magnesian magmas

An equation for the excess free energy of melts containing all major components is derived from published experimental data on equilibria between silicate liquids with either metallic iron or spinel at controlled oxygen partial pressure. The FeO activities in mafic and ultramafic magmas calculated with this equation were used to develop an oxygen barometer (geoxometer) for the association spinel + melt. Data derived with the application of the geoxometer confirm that meymechite magmas in the Siberian trap province had oxygen fugacities higher than in other magmatic systems. The origin of lower lithospheric domains with elevated redox potential can be explained by the intense diffusion of hydrogen from zones in which water-rich near-solidus melts from asthenospheric sources were emplaced into harzburgites, which had lost water and other incompatible elements in the course of earlier large-scale melting.

Model of garnet oxygen barometer for mantle peridotites and potential diamodiferous ability estimation on its basis

191 The elaboration of monomineral thermobarome ters based on the composition of one phase is a chal lenging task in modern petrology. This is because xenoliths are lacking or rare, and only xenocrysts are available in many mantle derived rocks. Prospecting and exploration for diamonds are commonly con ducted with separate grains of mantle derived associ ated minerals. The estimation of their formation oxy gen fugacity is important both for theoretical petrol ogy and applied purposes. Nowday the oxygen fugacity estimation sensors for garnet olivine orthopyroxene parageneses are known [8, 10]. There is a model of garnet olivine orthopy roxene oxybarometer [4, 10] based on the equilibrium from [2]:

Deciphering lava flow post-eruption differentiation processes by means of geochemical and isotopic variations: A case study from Mt. Etna volcano

We report results from geochemical and isotopic analyses conducted on nine samples collected from the vertical section of a pahoehoe lava flow unit from Mt. Etna volcano. Textural observations in the field show that, during lava emplacement, volatile exsolution and degassing allowed the nucleation and growth of bubbles, which subsequently rose from the base towards the uppermost lava crust. The amount of phenocrysts is low (about 12vol.%) and their compositions are comparable to intratelluric crystals analyzed for from historical and recent products. In contrast, from the basal zone to the uppermost lava crust, groundmass microlites are characterized by progressively more primitive compositions, i.e., olivines and clinopyroxenes show increasing Mg#, plagioclases are enriched in anorthite, and the ulvospinel content in titanomagnetites increases. Calculations based on thermodynamic models, thermometers and oxygen barometers indicate that, during post-eruption conditions, crystals formed at higher crystallization temperatures with increasing vertical height. The redox state of the melt progressively increased from the base towards the uppermost crust of the lava flow as is attested by increasing Fe2O3/FeO ratios in clinopyroxene and titanomagnetite. The lowest fO2 is recorded at the basal zone and suggests that this part of the lava was inaccessible to diffusion of atmospheric oxygen at the time of emplacement; whereas, the highest fO2 measured for the uppermost lava crust testifies to post-eruptive hydrogen loss, mainly transported by carrier gas phases.Whole-rock analyses of lava samples also indicate higher Fe2O3/FeO ratios with increasing vertical height as well as substantial enrichments in MgO and transitional elements. Results from both mass balance and Rayleigh fractionation calculations show that about 6vol.% of titanomagnetite and olivine microlites accumulated in the upper parts of the lava flow during emplacement. At the same time, due to progressive volatile exsolution, concentrations of Cl, F and Cs in whole rock decreased from the base towards the uppermost lava crust; indeed, oxygen isotopes indicate a substantial 22wt.% of CO2 degassing. From this, we conclude that even short-term exposure to post-eruptive conditions results in significant local compositional changes for lava flows at Mt. Etna volcano.

Erratum to: Iron in monticellite as an oxygen barometer for kimberlite magmas

Erratum to: Iron in monticellite as an oxygen barometer for kimberlite magmas

Iron in monticellite as an oxygen barometer for kimberlite magmas

Monticellite is a common magmatic mineral in the groundmass of kimberlites. A new oxygen barometer for kimberlite magmas is calibrated based on the Fe content of monticellite, CaMgSiO4, in equilibrium with kimberlite liquids in experiments at 100 kPa from 1,230 to 1,350°C and at logfO2 from NNO-4.1 to NNO+5.3 (where NNO is the nickel–nickel oxide buffer). The XFeMtc/XFeliq was found to decrease with increasing fO2, consistent with only Fe2+ entering the monticellite structure. Although the XFe-in-monticellite varies with temperature and composition, these dependencies are small compared to that with fO2. The experimental data were fitted by weighted least square regression to the following relationship: $$ \Updelta {\text{NNO}} = \frac{{\left\{ {\log \left[ {0.858( \pm 0.021)\frac{{X_{\text{Fe}}^{\text{Liq}} }}{{X_{\text{Fe}}^{\text{Mtc}} }}} \right] - 0.139( \pm 0.022)} \right\}}}{0.193( \pm 0.004)} $$ where ΔNNO is the fO2 relative to that of the Nickel-bunsenite (NNO) buffer and XFeliq/XFeMtc is the ratio of mole fraction of Fe in liquid and Fe-in-monticellite (uncertainties at 2σ). The application of this oxygen barometer to natural kimberlites from both the literature and our own investigations, assuming the bulk rock FeO is that of their liquid FeO, revealed a range in fO2 from NNO-3.5 to NNO+1.7. A range of Mg/(Mg + Fe2+) (Mg#) for kimberlite melts of 0.46–0.88 was derived from the application of the experimentally determined monticellite-liquid Kd Fe2+–Mg to natural monticellites. The range in Mg# is broader and less ultramafic than previous estimates of kimberlites, suggesting an evolution under a wide range of petrologic conditions.