The redox state of cerium in basaltic magmas: an experimental study of iron-cerium interactions in silicate melts

Ce(IV)-Ce(III) and Fe(III)-Fe(II) redox equilibria in Ca-Mg-Al-silicate melts have been individually measured with respect to the base composition, melt temperature, imposed oxygen fugacity, and multivalent element concentration (up to about 1.5 wt%). The mutual interaction of these two redox couples has been studied in analogous glasses which simultaneously contained iron and cerium. Analyses of Fe(III) concentrations in iron-cerium glasses by electron paramagnetic resonance and optical absorption spectroscopy indicate that Ce(IV) is stoichiometrically reduced by Fe(II) in the melt to produce Fe(III) and Ce(III) and that Ce(III)-O-Fe(III) complexes are formed in the melt. Consequently, it is concluded that cerium exists only as Ce(III) in basaltic magmas; cerium anomalies cannot be ascribed to the stabilization of Ce(IV) in magmas.     

Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

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 H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ 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 H₂O 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.     

Time evolution of chemical exchanges during mixing of rhyolitic and basaltic melts

We present the first set of chaotic mixing experiments performed using natural basaltic and rhyolitic melts. The mixing process is triggered by a recently developed apparatus that generates chaotic streamlines in the melts, mimicking the development of magma mixing in nature. The study of the interplay of physical dynamics and chemical exchanges between melts is carried out performing time series mixing experiments under controlled chaotic dynamic conditions. The variation of major and trace elements is studied in detail by electron microprobe and Laser Ablation ICP-MS. The mobility of each element during mixing is estimated by calculating the decrease in the concentration variance in time. Both major and trace element variances decay exponentially, with the value of exponent of the exponential function quantifying the element mobility. Our results confirm and quantify how different chemical elements homogenize in the melt at differing rates. The differential mobility of elements in the mixing system is considered to be responsible for the highly variable degree of correlation (linear, nonlinear, or scattered) of chemical elements in many published inter-elemental plots. Elements with similar mobility tend to be linearly correlated, whereas, as the difference in mobility increases, the plots become progressively more nonlinear and/or scattered. The results from this study indicate that the decay of concentration variance is in fact a robust tool for obtaining new insights into chemical exchanges during mixing of silicate melts. Concentration variance is (in a single measure) an expression of the influence of all possible factors (e.g., viscosity, composition, and fluid dynamic regime) controlling the mobility of chemical elements and thus can be an additional petrologic tool to address the great complexity characterizing magma mixing processes.     

In situ observations of bubble growth in basaltic,andesitic and rhyodacitic melts

Bubble growth strongly affects the physical properties of degassing magmas and their eruption dynamics. Natural samples and products from quench experiments provide only a snapshot of the final state of volatile exsolution, leaving the processes occurring during its early stages unconstrained. In order to fill this gap, we present in situ high-temperature observations of bubble growth in magmas of different compositions (basalt, andesite and rhyodacite) at 1,100 to 1,240 °C and 0.1 MPa (1 bar), obtained using a moissanite cell apparatus. The data show that nucleation occurs at very small degrees of supersaturaturation (<60 MPa in basalt and andesite, 200 MPa in rhyodacite), probably due to heterogeneous nucleation of bubbles occurring simultaneously with the nucleation of crystals. During the early stages of exsolution, melt degassing is the driving mechanism of bubble growth, with coalescence becoming increasingly important as exsolution progresses. Ostwald ripening occurs only at the end of the process and only in basaltic melt. The average bubble growth rate (G _R) ranges from 3.4 × 10^?6 to 5.2 × 10^?7 mm/s, with basalt and andesite showing faster growth rates than rhyodacite. The bubble number density (N _B) at nucleation ranges from 7.9 × 10⁴ mm^?3 to 1.8 × 10⁵ mm^?3 and decreases exponentially over time. While the rhyodacite melt maintained a well-sorted bubble size distribution (BSD) through time, the BSDs of basalt and andesite are much more inhomogeneous. Our experimental observations demonstrate that bubble growth cannot be ascribed to a single mechanism but is rather a combination of many processes, which depend on the physical properties of the melt. Depending on coalescence rate, annealing of bubbles following a single nucleation event can produce complex bubble size distributions. In natural samples, such BSDs may be misinterpreted as resulting from several separate nucleation events. Incipient crystallization upon cooling of a magma may allow bubble nucleation already at very small degrees of supersaturation and could therefore be an important trigger for volatile release and explosive eruptions.     

Late Neoproterozoic A-type granites in the northernmost Arabian-Nubian Shield formed by fractionation of basaltic melts

Geochemical, isotopic and age constraints support a comagmatic origin for Ghuweir Mafics and the Feinan A-type granites. The two rocks types, named collectively in this paper as the Feinan Ghuweir Magmatic Suite (FGMS), formed between 556 and 572 Ma ago according to Rb-Sr whole-rock dating. FGMS has low Sr initial ratios, which preclude a significant contribution of much older crust in the magma genesis.The FGMS has a wide range of silica contents, with a gap at 55-65 wt% SiO₂. It has a transalkaline to alkaline character; belongs to the medium to high K calc-alkaline series; it ranges from metaluminous to mildly peraluminous character and belongs to the alkali and alkali-calcic series. The Feinan granites and the Ghuweir rhyolites and rhyodacites are classified as A-type granites and belong to group A2 of Eby [Eby, N.G., 1992. Chemical subdivision of the A-type granitoids: petrogenetic and tectonic iplications. Geology 20, 641-644].According to geochemical modeling the Ghuweir Mafics were derived from a subduction modified lithospheric mantle by 10% batch modal partial melting of a phlogopite-bearing spinel lherzolite. The intra-suite geochemical variations can be ascribed to fractional crystallization of olivine, pyroxene, and plagioclase. The accumulation of apatite in the most evolved samples is responsible for the high concentrations of REE.The Feinan granites and the Ghuweir rhyolites and rhyodacites were derived from the mafic magma by the fractional crystallization of ≈78% of the original magma to the mineral assemblage olivine+pyroxene+plagioclase+magnetite. The intra-suite geochemical variations in the Feinan A-type granites are due to the fractional crystallization of the mineral phases: amphibole +Na and K-feldspar+apatite +magnetite+zircon+allanite.The FGMS correlates with time-equivalent rocks in many parts of the Arabian-Nubian Shield and the surrounding areas.     

Investigation into the petrogenesis of Apollo 14 high-Al basaltic melts through crystal stratigraphy of plagioclase

The petrogenesis of Apollo 14 high-Al basaltic melts was studied using crystal stratigraphy, which involves textural (crystal size distributions — CSDs) and chemical analyses (electron microprobe and laser ablation inductively coupled plasma mass spectrometry). The samples studied here include pristine basalt 14072 and basaltic clasts from breccia 14321, and impact-generated crystalline samples 14073, 14276 and 14310. Plagioclase was the focus of this study because of its relatively high modal abundances and because it was on the liquidus for much of the melt cooling histories. Plagioclase crystals were analyzed (core-to-rim compositions where possible) to test and refine petrogenetic models based upon whole-rock compositions (Groups A, B, and C designations) and to investigate basalt 14072 and impact-melt crystallization. Textural studies have shown that each basalt group has distinctive plagioclase CSDs, which are in turn distinctive from those of the impact melts. Evolution of the individual basaltic melts was studied by comparing the equilibrium-melt compositions (calculated from plagioclase compositions using relevant partition coefficients) to fractional crystallization (FC) and assimilation and fractional crystallization (AFC) models. Petrogenetic modeling of trace elements in Group A basalts revealed that petrogenesis continued beyond 40% total crystallization required to model whole-rock compositions, and that there were open-system processes that affected the magma during plagioclase crystallization. Petrogenetic modeling of pristine high-Al basalts (14072 and Groups A, B and C) using trace elements shows that the equilibrium-melt compositions do not fall on a single AFC or FC trajectory. This is consistent with fluctuating degrees of assimilation (i.e., variable r-values) and/or variable assimilant compositions during petrogenesis. Petrogenetic modeling reveals that the impact melts experienced only closed-system fractional crystallization. This work demonstrates the importance of crystal stratigraphy in revealing the intricacies of lunar basalt petrogenesis.     

Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts

The speciation of sulfur as a function of oxygen fugacity was calculated in glasses of basaltic composition saturated experimentally with either sulfide or sulfate phases. The experiments were conducted on mixtures of synthetic and natural materials equilibrated at 1300 °C and 1 GPa in a piston-cylinder apparatus. Sulfur speciation was calculated by measuring the peak shift of the sulfur Kα radiation relative to a sulfide standard, whereas oxygen fugacity was calculated from the composition of olivine and spinel present in the assemblages. The results are consistent with sulfur being present as sulfite (S⁴⁺) in addition to sulfate (S⁶⁺) in oxidized melts. Therefore, sulfur speciation derived from SKα peak shifts should be seen as ”sulfate mole fraction equivalents“ (X(S⁶⁺)_eq.). Using the data available, an empiric function:

X(S6+)_eq.=0.86/(1+exp(2.89−2.23ΔFMQ))     

Rate of hydrogen-iron redox exchange in silicate melts and glasses

A kinetic model for the rate of iron-hydrogen redox exchange in silicate glasses and melts has been derived from time-series experiments performed on natural rhyolitic obsidians. Cylinders of the starting glasses were exposed to reducing mixtures composed of H₂-Ar-CO₂-CO in 1-atm furnaces and H₂-Ar in a cold seal pressure vessel. Overall, runs covered the temperature range 300 to 1000°C. The progression of a front of ferric iron reduction within the quenched melt was observed optically through a change of color. For all run conditions, the advancement of the front (ξ) was proportional to the square root of time, revealing the reaction as a diffusion-limited process. Iso-fO₂ runs performed in CO₂-CO, H₂-Ar, and H₂-CO₂ gases have shown that fH₂ rather than fO₂ is the dominant parameter controlling the reaction rate. The fH₂ dependence of the rate constant was characterized in the range 0.02 to 70 bar. The growth of the reduced layer, which is accompanied by an increase in reaction-derived OH-group content, was fitted considering that the reaction rate is controlled by the migration of a free mobile species (H₂) immobilized in the form of OH subsequent to reaction with ferric iron. The reaction rate is thus a function of both solubility and diffusivity of H₂ weighted by the concentration of its sink (ferric iron). We extracted a single law for both solubility and diffusivity of H₂ in amorphous silicates that applies over a range of temperatures below and above the glass transition temperature. Melt/glass structure (degree of polymerization) does not seem to significantly affect both solubility and diffusivity of H₂. We therefore provide a model that allows the prediction of oxidation-reduction rates in the presence of hydrogen for a wide range of compositions of amorphous glasses and melts. Comparisons with previous work elucidating rate of redox exchange in dry systems allow us to anticipate the fH₂-T domains where different redox mechanisms may apply. We conclude that equilibration of redox potential in nature should be dominated by H₂ transfer at a rate controlled by both H₂ solubility and diffusion. Numerical applications of the model illustrate redox exchanges in natural magmas and in glasses exposed to weathering under near surface conditions. We show that crustal events such as magmas mixing should not modify the iron redox state of magmas. In the case of nuclear-waste-bearing glasses, the fH₂ conditions in the host terrain are clearly a parameter that must be taken into account to predict glass durability.     

Impact of pore water conductivity and porosity on the electrical conductivity of kaolinite

The purpose of this study is to quantify the magnitudes of surface conduction and pore water conduction from the measured electrical conductivity of kaolinite, with the ultimate goal of estimating the electrical conductivity of kaolinite with a wide range of pore water conductivities (σ _w = 0.013–3.356 S/m) and porosities (n = 0.368–1.0). Therefore, the theoretical background of the electrical conductivity in soils was reviewed, and electrical conductivity measurements on kaolinite were performed using both slurry and consolidation tests in this study. The results of this study demonstrate that the variations of measured electrical conductivity (σ _mix) with n are debatable according to the values of σ _w, because a decrease in n results in both an increase in surface conduction (K _s) and a decrease in pore water conduction (K _w); this causes the relative magnitude of K _s compared to that of K _w to vary with σ _w and n. Consequently, this study develops the relation between the porosity-normalized K _s/K _w and 1/σ _w. Additionally, the surface conductivity of the tested kaolinite is back-calculated and compared with the previous relationship between K _s and zeta potential of kaolinite. The measured and estimated σ _mix values are compared with the varying pore water conductivity and porosity values.     

Experiments and models of anhydrous,basaltic olivine-plagioclase-augite saturated melts from 0.001 to 10 kbar

 A new method for modeling fractional crystallization processes that involve olivine (ol), plagioclase (plag) and augite (aug) is presented. This crystallization assemblage is the major control on the chemical variations in mid-ocean ridge basalts. The compositional and temperature variations in ol-plag-aug saturated basalts over a range of pressures are described using empirical expressions. A data base of 190 experiments in natural and basalt-analog chemical systems is used to describe temperature, Al, Ca and Mg molar fractions as functions of Si, Fe, Na, Ti and K molar fractions and pressure. Increases in the abundances of Na and K cause Ca and Mg abundances to decrease and Al abundance to increase in ol-plag-aug saturated melts. The equations can be used to predict pressure and temperature and thus provide a useful thermobarometer. A model is described to calculate ol-plag-aug fractional crystallization as a function of pressure and melt composition, using melt and augite models developed here, combined with existing models for olivine-melt and plagioclase-melt equilibria. We compare the fractional crystallization sequence of ALV-2004-3-1 predicted from the models presented in this paper, Langmuir et al. (1992) modified by Reynolds (1995), Ghiorso and Sack (1995) and Ariskin et al. (1993) at 0.001 and 4 kbar. As an example the model is applied to estimate pressure of crystallization of glasses from the east flank of the East Pacific Rise at 11°45′N. Received: 24 July 1995 / Accepted: 12 January 1996     

Nature of electrical conductivity of the ancient crystalline base

The generalized popular image of conductivity structure of the crystalline as a tripartite section (high-low-high conductivity of top, middle, and bottom of the base, respectively) is disqualified significantly by recent soundings, in the USSR and elsewhere, by too many exceptions to the rule. The most plausible explanation of such three-dimensional exceptions is the presence of electron-conducting minerals and formations in different positions at great depths, which may affect conductivities of the entire profile.     

Effects of experimental reheating of natural basaltic ash at different temperatures and redox conditions

A set of experiments have been performed on volcanic materials from Etna, Stromboli and Vesuvius in order to evaluate how the exposure to thermal and redox conditions close to that of active craters affects the texture and composition of juvenile pyroclasts. Selected samples were placed within a quartz tube, in presence of air or under vacuum, and kept at T between 700 and 1,130 °C, for variable time (40 min to 12 h). Results show that reheating reactivates the melt, which, through processes of chemical and thermal diffusion, reaches new equilibrium conditions. In all the experiments performed at T = 700–750 °C, a large number of crystal nuclei and spherulites grows in the groundmass, suggesting conditions of high undercooling. This process creates textural heterogeneities at the scale of few microns but only limited changes of groundmass composition, which remains clustered around that of the natural glasses. Reheating at T = 1,000–1,050 °C promotes massive groundmass crystallization, with a different mineral assemblage as a function of the redox conditions. Morphological modifications of clasts, from softening to sintering as temperature increases, occur under these conditions, accompanied by progressive smoothing of external surfaces, and a reduction in size and abundance of vesicles, until the complete obliteration of the pre-existing vesicularity. The transition from sintering to welding, characteristic of high temperature, is influenced by redox conditions. Experiments at T = 1,100–1,130 °C and under vacuum produce groundmass textures and glass compositions similar to that of the respective starting material. Collapse and welding of the clasts cause significant densification of the whole charge. At the same temperature, but in presence of air, experimental products at least result sintered and show holocrystalline groundmass. In all experiments, sublimates grow on the external surfaces of the clasts or form a lining on the bubble walls. Their shape and composition is a function of temperature and fO₂ and the abundance of sublimates shows a peak at 1,000 °C. The identification of the features recorded by pyroclasts during complex heating–cooling cycles allows reconstructing the complete clasts history before their final emplacement, during weakly explosive volcanic activity. This has a strong implication on the characterization of primary juvenile material and on the interpretation of eruption dynamics.     

Grain size effect on the electrical conductivity of clinopyroxene

Complex impedance spectra of polycrystalline samples (with grain size fractions ~5–63, 63–160 and 160–250 μm) and a single crystal sample (with orientation parallel to b), prepared from a natural megacryst augite, were measured in a piston cylinder apparatus at 10 kbar and 500–1,000°C and with a Solartron 1260 Impedance/Gain Phase analyzer over a frequency range of 0.1–10⁶ Hz. The main charge carriers are attributed to small polarons, and the activation enthalpy is 83 ± 3 to 90 ± 3 kJ/mol. The measured electrical conductivity shows no difference between the polycrystalline and single crystal samples, suggesting independence of electrical conductivity on grain size given a change above ~5 μm. The electrical conductivity of augite is much higher than that of olivine, indicating that, if regionally enriched, augites may lead to zones of high electrical conductivity and electrical anisotropy in the deep lithosphere.     

On the distribution of the electrical conductivity below the Eastern Alps

Along a profile Chiemsee—Hohe Tauern/Zillertaler Alpen-Drautal magnetotelluric measurements have been made at 65 sites and geomagnetic depth sounding has been made at 21 sites. From these registrations the distribution of the electrical conductivity at greater depths can be deduced by determining the distribution of the induced electric currents. We were mainly interested in the transition zone molasse basin/Calcareous Alps and in the conductivity distribution below the Hohe Tauern and the Zillertaler Alpen.The different rock units of the Calcareous Alps have on the average a low electrical conductivity. They are underlain by well conducting sediments (probably molasse) until 10 km south of the morphological border of the Alps. The well conducting sediments below the Calcareous Alps are rather thick. We assume a thickness of 3–4 km. The sediments decrease at the assumed southern border of the molasse basin within a short distance.The distribution of the electrical conductivity below the central eastern Alps has been investigated, to find perhaps an indication for an increased temperature in this area. A clear increase of the conductivity and as a consequence also of the temperature could not be found below the central eastern Alps. A small increase of the electrical conductivity, however, could be found in some areas as for example below the Hohe Tauern and below the upper valleys of the rivers Drau and Rienz. As the number of stations was too small in this area, no detailed information can be given about the extension and the depth range of these local conductivity anomalies.

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Zusammenfassung Entlang eines Profils vom Chjemsee über die Hohen Tauern und Zillertaler Alpen bis zum Drautal wurden an 65 Orten die zeitlichen Variationen des erdelektrischen Feldes und an 21 Orten die zeitlichen Variationen des erdmagnetischen Feldes registriert. Aus diesen Registrierungen kann die Verteilung der im Untergrund induzierten Ströme und daraus die Verteilung von Gesteinseinheiten unterschiedlicher elektrischer Leitfähigkeit abgeleitet werden. Besonders interessierte der Übergangsbereich Molassetrog—Nördliche Kalkalpen sowie der tiefere Untergrund unter den Hohen Tauern und den Zillertaler Alpen.Die — im Mittel gering leitfähigen — Gesteine der Kalkalpen sind im Bereich des Profils bis 10 km südlich des morphologischen Alpenrandes von gut leitfähigen Sedimenten (wohl überwiegend Molasse) unterlagert. Diese Sedimente sind unter den Kalkalpen noch mehrere km mächtig.Die Verteilung der elektrischen Leitfähigkeit unter den zentralen Ostalpen wurde untersucht, um vielleicht einen Hinweis auf eine erhöhte Temperatur in dem Gebiet zu erhalten. Eine deutliche Erhöhung der Leitfähigkeit und damit auch der Temperatur wurde unter den zentralen Ostalpen nicht gefunden. Eine geringe Erhöhung der elektrischen Leitfähigkeit ist jedoch in einigen Gebieten vorhanden, so z. B. unter den Hohen Tauern sowie unter dem Oberlauf der Flüsse Drau und Rienz. Genauere Angaben über die Ausdehnung und Tiefenlage dieser Anomalien können aber wegen der zu geringen Anzahl von Stationen noch nicht gemacht werden.

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Résumé Afin de déterminer les courants électriques induits et la distribution de la conductivité électrique, on a, le long d'un profil s'étendant du Chiemsee jusqu'à la vallée de la Drau, enregistré les variations temporelles du champ tellurique en 65 localités et les variations du champ magnétique en 21 localités.Pour la région de transition entre la Molasse et les Alpes Calcaires du Nord les résultats indiquent la présence de couches sédimentaires à bonne conductivité sous les Alpes Calcaires, dont les roches ont une conductivité généralement faible. Ces couches qui s'étendent jusqu'à 10 km au sud du bord morphologique des Alpes, ont une épaisseur de plusieurs km et sont probablement constituées surtout de Molasse.Pour la région centrale des Alpes Orientales les résultats ne donnent pas d'indication pour un accroissement général de la conductivité et par conséquent de la température. Sous les Hohe Tauern et sous les cours supérieurs de la Drau et de la Rienz des accroissements locaux relativement faibles ont été trouvés. Des résultats quantitatifs concernant ces anomalies ne peuvent pas encore être fournis à cause de la trop faible densité des stations d'enrégistrement.

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Mutual interaction of redox pairs in silicate melts: Equilibria involving metallic phases

Mutual interaction of redox pairs resulting in the origin or decomposition of a metal phase is analyzed based on the concept of intrinsic oxygen fugacity. Reactions are suggested that may be responsible for the synthesis (or decomposition) of submicrometer-sized metal nuggets when experimental melts are quenched and can explain the possible crystallization of Pt—Fe alloys when basaltic melts cool and elucidate the nature of color of Au-bearing ruby glass. Possible disproportionation reactions of certain lower oxides into a higher oxide and respective metal in cooled silicate melts are discussed.     

Laser Ablation ICPMS study of trace element partitioning between plagioclase and basaltic melts: an experimental approach

Plagioclase-melt partition coefficients (D) for 34 trace elements at natural concentration levels were determined experimentally in a natural MORB composition at atmospheric pressure using thin Pt-wire loops. Experiments were carried out at three temperatures (1,220, 1,200, and 1,180°C), and at three different oxygen fugacities (fO₂ = IW, QFM, air) in order to assess the effect of fO₂ on the partitioning of elements with multiple valence (Fe, Eu, Cr). Run products were analyzed by laser-ablation ICP-MS. Most trace element Ds increase slightly as temperature decreases, except for D _Zr, D _Fe, D _Eu and D _Cr that vary systematically with fO₂. Applying the Lattice Strain Model to our data suggests the presence of Fe²⁺ entirely in the octahedral site at highly to moderate reducing conditions, while Fe³⁺ was assigned wholly to the tetrahedral site of the plagioclase structure. Furthermore, we provide a new quantitative framework for understanding the partitioning behaviour of Eu, which occurs as both 2+ and 3+ cations, depending on fO₂and confirm the greater compatibility of Eu²⁺, which has an ionic radius similar to Sr, relative to Eu³⁺ in plagioclase and the higher Eu²⁺/ Eu³⁺ under reducing conditions. For petrogenetic basaltic processes, a combined fractionation of Eu²⁺–Sr and Fe–Mg by plagioclase has considerable potential as an oxybarometer for natural magmatic rocks.     

Mantle redox evolution and the oxidation state of the Archean atmosphere

Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.