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The Sheahan Diamond Literature Reference Compilation - Scientific and Media Articles based on Major Keyword - Redox
The Sheahan Diamond Literature Reference Compilation is compiled by Patricia Sheahan who publishes on a monthly basis a list of new scientific articles related to diamonds as well as media coverage and corporate announcements called the Sheahan Diamond Literature Service that is distributed as a free pdf to a list of followers. Pat has kindly agreed to allow her work to be made available as an online digital resource at Kaiser Research Online so that a broader community interested in diamonds and related geology can benefit. The references are for personal use information purposes only; when available a link is provided to an online location where the full article can be accessed or purchased directly. Reproduction of this compilation in part or in whole without permission from the Sheahan Diamond Literature Service is strictly prohibited. Return to Diamond Keyword Index
Sheahan Diamond Literature Reference Compilation - Scientific Articles by Author for all years
Each article reference in the SDLRC is tagged with one or more key words assigned by Pat Sheahan to highlight the main topics of the article. In an effort to make it easier for users to track down articles related to a specific topic, KRO has extracted these key words and developed a list of major key words presented in this Key Word Index to which individual key words used in the article reference have been assigned. In most of the individual Key Word Reports the references are in crhonological order, though in some such as Deposits the order is first by key word and then chronological. Only articles classified as "technical" (mainly scientific journal articles) and "media" (independent media articles) are included in the Key Word Index. References that were added in the most recent monthly update are highlighted in yellow.
Redox stands for "reduction-oxidation reaction" where electrons are lost or gained. When an atom or molecule loses electrons it has undergone oxidation whereas whatever gained the electrons underwent reduction. An atom or molecule is a reducing agent because it loses electrons which results in it being oxidized. An oxidizing agent causes other atoms or molecules to lose their electrons. Oxygen is the ultimate oxidizing agent. A dreaded topic at kimberlite conferences is oxygen fugacity which is related to rock formation in the mantle (see mineral redox buffer). Redox articles are exclusively of a scientific nature and are relevant to diamonds because they may deal with the behavior of carbon in the mantle which is, of course, from what diamonds form.
Variations of the oxygen conditions in mantle column beneath Siberian kimberlite pipes and it's application to lithospheric structure of feeding systems.
Vladykin: VI International Workshop, held Mirny, Deep seated magmatism, its sources and plumes, pp. 125-144.
Abstract: Chemical reduction-oxidation mechanisms within mantle rocks link to the terrestrial carbon cycle by influencing the depth at which magmas can form, their composition, and ultimately the chemistry of gases released into the atmosphere. The oxidation state of the uppermost mantle has been widely accepted to be unchanged over the past 3800 m.y., based on the abundance of redox-sensitive elements in greenstone belt-associated samples of different ages. However, the redox signal in those rocks may have been obscured by their complex origins and emplacement on continental margins. In contrast, the source and processes occurring during decompression melting at spreading ridges are relatively well constrained. We retrieve primary redox conditions from metamorphosed mid-oceanic ridge basalts (MORBs) and picrites of various ages (ca. 3000-550 Ma), using V/Sc as a broad redox proxy. Average V/Sc values for Proterozoic suites (7.0 ± 1.4, 2?, n = 6) are similar to those of modern MORB (6.8 ± 1.6), whereas Archean suites have lower V/Sc (5.2 ± 0.4, n = 5). The lower Archean V/Sc is interpreted to reflect both deeper melt extraction from the uppermost mantle, which becomes more reduced with depth, and an intrinsically lower redox state. The pressure-corrected oxygen fugacity (expressed relative to the fayalite-magnetite-quartz buffer, ?FMQ, at 1 GPa) of Archean sample suites (?FMQ -1.19 ± 0.33, 2?) is significantly lower than that of post-Archean sample suites, including MORB (?FMQ -0.26 ± 0.44). Our results imply that the reducing Archean atmosphere was in equilibrium with Earth's mantle, and further suggest that magmatic gases crossed the threshold that allowed a build-up in atmospheric O2 levels ca. 3000 Ma, accompanied by the first "whiffs" of oxygen in sediments of that age.
Abstract: Chemical reduction-oxidation mechanisms within mantle rocks link to the terrestrial carbon cycle by influencing the depth at which magmas can form, their composition, and ultimately the chemistry of gases released into the atmosphere. The oxidation state of the uppermost mantle has been widely accepted to be unchanged over the past 3800 m.y., based on the abundance of redox-sensitive elements in greenstone belt-associated samples of different ages. However, the redox signal in those rocks may have been obscured by their complex origins and emplacement on continental margins. In contrast, the source and processes occurring during decompression melting at spreading ridges are relatively well constrained. We retrieve primary redox conditions from metamorphosed mid-oceanic ridge basalts (MORBs) and picrites of various ages (ca. 3000-550 Ma), using V/Sc as a broad redox proxy. Average V/Sc values for Proterozoic suites (7.0 ± 1.4, 2?, n = 6) are similar to those of modern MORB (6.8 ± 1.6), whereas Archean suites have lower V/Sc (5.2 ± 0.4, n = 5). The lower Archean V/Sc is interpreted to reflect both deeper melt extraction from the uppermost mantle, which becomes more reduced with depth, and an intrinsically lower redox state. The pressure-corrected oxygen fugacity (expressed relative to the fayalite-magnetite-quartz buffer, ?FMQ, at 1 GPa) of Archean sample suites (?FMQ -1.19 ± 0.33, 2?) is significantly lower than that of post-Archean sample suites, including MORB (?FMQ -0.26 ± 0.44). Our results imply that the reducing Archean atmosphere was in equilibrium with Earth's mantle, and further suggest that magmatic gases crossed the threshold that allowed a build-up in atmospheric O2 levels ca. 3000 Ma, accompanied by the first "whiffs" of oxygen in sediments of that age.
Progress in Earth and Planetary Science, doi.org/10.1186/ s4065-018-0203-8 17p. Open access
Mantle
spectroscopy, redox
Abstract: The behavior of COH fluids, their isotopes (hydrogen and carbon), and their interaction with magmatic liquids are at the core of understanding formation and evolution of the Earth. Experimental data are needed to aid our understanding of how COH volatiles affect rock-forming processes in the Earth’s interior. Here, I present a review of experimental data on structure of fluids and melts and an assessment of how structural factors govern hydrogen and carbon isotope partitioning within and between melts and fluids as a function of redox conditions, temperature, and pressure. The solubility of individual COH components in silicate melts can differ by several orders of magnitude and ranges from several hundred ppm to several wt%. Silicate solubility in fluid can reach several molecular at mantle temperatures and pressures. Different solubility of oxidized and reduced C-bearing species in melts reflects different solution equilibria. These equilibria are 2CH4?+?Qn?=?2CH3??+?H2O?+?Qn?+?1 and 2CO32??+?H2O?+?2Qn +?1 =?HCO3??+?2Qn, under reducing and oxidizing conditions, respectively. In the Qn-notations, the superscript, n, denotes the number of bridging oxygen in the silicate species (Q-species). The structural changes of carbon and silicate in magmatic systems (melts and fluids) with variable redox conditions result in hydrogen and carbon isotope fractionation factors between melt, fluid, and crystalline materials that depend on redox conditions and can differ significantly from 1 even at magmatic temperatures. The ?H of D/H fractionation between aqueous fluid and magma in silicate-COH systems is between ??5 and 25 kJ/mol depending on redox conditions. The ?H values for 13C/12C fractionation factors are near ??3.2 and 1 kJ/mol under oxidizing and reducing conditions, respectively. These differences are because energetics of O-D, O-H, O-13C, and O-12C bonding environments are governed by different solution mechanisms in melts and fluids. From the above data, it is suggested that (COH)-saturated partial melts in the upper mantle can have ?D values 100%, or more, lighter than coexisting silicate-saturated fluid. This effect is greater under oxidizing than under reducing conditions. Analogous relationships exist for 13C/12C. At magmatic temperatures in the Earth’s upper mantle, 13C/12C of melt in equilibrium with COH-bearing mantle in the ??7 to ??30‰ range increases with temperature from about 40 to >?100‰ and 80-120‰ under oxidizing and reducing conditions, respectively.
Abstract: Of great importance in the problem of redox evolution of mantle rocks is the reconstruction of scenarios of alteration of Fe0- or Fe3C-bearing rocks by oxidizing mantle metasomatic agents and the evaluation of stability of these phases under the influence of fluids and melts of different compositions. Original results of high-temperature high-pressure experiments (P = 6.3 GPa, T = 13001500°?) in the carbideoxidecarbonate systems (Fe3CSiO2(Mg,Ca)CO3 and Fe3CSiO2Al2O3(Mg,Ca)CO3) are reported. Conditions of formation of mantle silicates with metallic or metalcarbon melt inclusions are determined and their stability in the presence of CO2-fluid representing the potential mantle oxidizing metasomatic agent are estimated. It is established that garnet or orthopyroxene and CO2-fluid are formed in the carbideoxidecarbonate system through decarbonation, with subsequent redox interaction between CO2 and iron carbide. This results in the formation of assemblage of Fe-rich silicates and graphite. Garnet and orthopyroxene contain inclusions of a FeC melt, as well as graphite, fayalite, and ferrosilite. It is experimentally demonstrated that the presence of CO2-fluid in interstices does not affect on the preservation of metallic inclusions, as well as graphite inclusions in silicates. Selective capture of FeC melt inclusions by mantle silicates is one of the potential scenarios for the conservation of metallic iron in mantle domains altered by mantle oxidizing metasomatic agents.
Abstract: We wished to advance the knowledge of speciation among volatiles during melting and crystallization in the Earth's interior; therefore, we explored the nature of carbon-, nitrogen-, and hydrogen-bearing species as determined in COHN fluids and dissolved in coexisting aluminosilicate melts. Micro-Raman characterization of fluids and melts were conducted in situ while samples were at a temperature up to 825 °C and pressure up to ?1400 MPa under redox conditions controlled with the Ti-TiO2-H2O hydrogen fugacity buffer. The fluid species are H2O, H2, NH3, and CH4. In contrast, under oxidizing conditions, the species are H2O, N2, and CO2. The equilibria among silicate structures (Q-species) and reduced carbon and nitrogen species are, 2NH3 + 4Qn ? 2Qn-1(NH2) + 2Qn-1(OH), and 2CH4 + 4Qn ? 2Qn-1(CH3) + 2Qn-1(OH). The Qn and Qn-1 denote silicate species with, respectively, n and n-1 bridging O atoms. The formulation in parentheses, (NH2), (CH3), and (OH), is meant to indicate that those functional groups replace one or more oxygen in the silicate tetrahedra. There is no evidence for O-NH2 or O-CH3 bonding. Therefore, a solution of reduced C- and N-species species in the COHN system results in depolymerization of silicate melts. The ?H values derived from the XNH2/XNH3 and XCH3/XCH4 evolution with temperature, respectively, were 8.1 ± 2.3 kJ/mol and between -4.9 ± 1.0 and -6.2 ± 2.2 kJ/mol. The fluid/melt partition coefficients, Kfluid/melt, of the reduced species, H2O, H2, NH3, and CH4, remain above unity at all temperatures. For example, for carbon it is in the 6-15 range with a ?H = -13.4 ± 2.4 KJ/mol. These values compare with a 0.8-3 range with ?H = -19 ± 2.4 kJ/mol in N-free silicate-COH systems. The Kfluid/melt values for reduced nitrogen and molecular hydrogen are in the 6-10 and 6-12 range with ?H values of -5.9 ± 0.9 and = 8 ± 6 kJ/mol, respectively. A change in redox conditions during melting and crystallization in the Earth sufficient to alter oxidized to reduced carbon- and nitrogen-bearing species will affect all melt properties that depend on melt polymerization. This suggestion implies that changing redox conditions during melting of a COHN-bearing mantle can have a profound effect on physical and chemical properties of melts and on melting and melt aggregation processes.
Geochemical Perspectives Letters, Vol. 10, pp. 51-55.
Mantle
redox
Abstract: Among redox sensitive elements, carbon is particularly important because it may have been a driver rather than a passive recorder of Earth’s redox evolution. The extent to which the isotopic composition of carbon records the redox processes that shaped the Earth is still debated. In particular, the highly reduced deep mantle may be metal-saturated, however, it is still unclear how the presence of metallic phases in?uences the carbon isotopic compositions of super-deep diamonds. Here we report ab initio results for the vibrational properties of carbon in carbonates, diamond, and Fe3C under pressure and temperature conditions relevant to super-deep diamond formation. Previous work on this question neglected the effect of pressure on the equilibrium carbon isotopic fractionation between diamond and Fe3C but our calculations show that this assumption overestimates the fractionation by a factor of ~1.3. Our calculated probability density functions for the carbon isotopic compositions of super-deep diamonds derived from metallic melt can readily explain the very light carbon isotopic compo- sitions observed in some super-deep diamonds. Our results therefore support the view that metallic phases are present during the formation of super-deep diamonds in the mantle below ~250 km.
Abstract: Diamonds are key messenger from the deep Earth because someare sourced from the longest isolated and deepest accessible regions of the Earth’s mantle. They are prime recorders of the carbon isotopic compositionof the Earth. The C isotope composition (d13C) of natural diamonds showsa widevariationfrom -41‰ to +3‰ with the primary mode at -5 ± 3‰ [1]. In comparison, the d13C values of chondrites and other planetary bodies range between -26‰ and -15‰ [2]. It is possible that some of the low d13C values were inherited from the Earth’s building blocks,but this is unlikely to be the sole explanation for all low d13C values that can reach as low as -41‰. Organic matter at the Earth’s surface that has low d13C values[3] has been regarded as a possible origin for low d13C values. However, organic carbon is usually accompanied by carbonate with higher d13C values (~0 ‰),and it is not clear why this d13C value does not appear frequently in diamonds. Low d13C diamonds were also formed by deposition from C-O-H fluids,but the equilibrium fractionationinvolved between diamonds and fluids issmall at mantle temperatures [1] and the low d13C values of diamonds can only be achieved after extensive Rayleigh distillation. One unique feature of the Earth isactive plate tectonics driven by mantle convection. Relatively oxidized iron and carbon species at the surface, such as carbonate, Fe2+-and Fe3+-bearing silicatesand oxides, are transported to the deep mantle by subducted slabs and strongly involved inthe redox reactions that generatediamonds [4]. The extent to which the isotopic compositionof C duringdiamond formation recordsredox processes that shaped the Earth is still controversial. Here we report onvibration properties of C andFe at high pressure in carbonates, diamond and Fe3C,based on nuclear resonant inelastic X-ray scattering measurements and density functional theory calculationsand further calculate equilibrium C isotope fractionations among these C-bearing species. Our results demonstrate that redox reactions in subducted slabs could generate eclogitic diamonds with d13C values as low as -41‰ if C in diamonds was sourced from the oxidation of a Fe-C liquid. The large C isotopic fractionation and potentially fast separation between diamonds and a Fe-C melt could enable diamond formation as high as 2%with d13C lower than -40‰.
Abstract: The composition of Earth’s atmosphere depends on the redox state of the mantle, which became more oxidizing at some stage after Earth’s core started to form. Through high-pressure experiments, we found that Fe2+ in a deep magma ocean would disproportionate to Fe3+ plus metallic iron at high pressures. The separation of this metallic iron to the core raised the oxidation state of the upper mantle, changing the chemistry of degassing volatiles that formed the atmosphere to more oxidized species. Additionally, the resulting gradient in redox state of the magma ocean allowed dissolved CO2 from the atmosphere to precipitate as diamond at depth. This explains Earth’s carbon-rich interior and suggests that redox evolution during accretion was an important variable in determining the composition of the terrestrial atmosphere.
Geochemistry International, Vol. 56, 13, pp. 1398-1404.
Mantle
redox
Abstract: We report the carbon isotope compositions of a set of diamond crystals recovered from an investigation of the experimental interaction of metal iron with Mg-Ca carbonate at high temperature and high pressure. Despite using single carbon source with ?13C equal to +0.2‰ VPDB, the diamond crystals show a range of ?13C values from -0.5 to -17.1‰ VPDB. Diamonds grown in the metal-rich part of the system are relatively constant in their carbon isotope compositions (from -0.5 to -6.2‰), whereas those diamonds recovered from the carbonate dominated part of the capsule show a much wider range of ?13C (from -0.5 to -17.1‰). The experimentally observed distribution of diamond’ ?13C using a single carbon source with carbon isotope ratio of marine carbonate is similar to that found in certain classes of natural diamonds. Our data indicate that the ?13C distribution in diamonds that resulted from a redox reaction of marine carbonate with reduced mantle material is hardly distinguishable from the ?13C distribution of mantle diamonds.
Abstract: The salt components of aqueous and aqueous-carbonic fluids are very important agents of metasomatism and partial melting of crustal and mantle rocks. The paper presents examples and synthesized data on mineral associations in granulite- and amphibolite-facies rocks of various composition in the middle and lower crust and in upper-mantle eclogites and peridotites that provide evidence of reactions involving salt components of fluids. These data are analyzed together with results of model experiments that reproduce some of these associations and make it possible to more accurately determine their crystallization parameters.
Nature Research Scientific Reports, https://doi.org/10.1038/ s41598-019-55743-1 11p. Pdf
Mantle
melting, redox
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Oxygen fugacity (fO2) is an intensive variable implicated in a range of processes that have shaped the Earth system, but there is controversy on the timing and rate of oxidation of the uppermost convecting mantle to its present fO2 around the fayalite-magnetite-quartz oxygen buffer. Here, we report Fe3+/?Fe and ƒf2 for ancient eclogite xenoliths with oceanic crustal protoliths that sampled the coeval ambient convecting mantle. Using new and published data, we demonstrate that in these eclogites, two redox proxies, V/Sc and Fe3+/?Fe, behave sympathetically, despite different responses of their protoliths to differentiation and post-formation degassing, seawater alteration, devolatilisation and partial melting, testifying to an unexpected robustness of Fe3+/?Fe. Therefore, these processes, while causing significant scatter, did not completely obliterate the underlying convecting mantle signal. Considering only unmetasomatised samples with non-cumulate and little-differentiated protoliths, V/Sc and Fe3+/?Fe in two Archaean eclogite suites are significantly lower than those of modern mid-ocean ridge basalts (MORB), while a third suite has ratios similar to modern MORB, indicating redox heterogeneity. Another major finding is the predominantly low though variable estimated fO2 of eclogite at mantle depths, which does not permit stabilisation of CO2-dominated fluids or pure carbonatite melts. Conversely, low-fO2 eclogite may have caused efficient reduction of CO2 in fluids and melts generated in other portions of ancient subducting slabs, consistent with eclogitic diamond formation ages, the disproportionate frequency of eclogitic diamonds relative to the subordinate abundance of eclogite in the mantle lithosphere and the general absence of carbonate in mantle eclogite. This indicates carbon recycling at least to depths of diamond stability and may have represented a significant pathway for carbon ingassing through time.
Dorfman, S.M., Potapkin, V., Lv, M., Greenberg, E., Kupenko, I., Chumakov, A.I., Bi, W., Alp, E.E., Liu, J., Magrez, A., Dutton, S.E., Cava, R.J., McCammon, C.A., Gillet, P.
American Mineralogist, Vol. 105, pp. 1030-1039. pdf
Mantle
redox
Abstract:
Electronic states of iron in the lower mantle's dominant mineral, (Mg,Fe,Al)(Fe,Al,Si)O3 bridgmanite, control physical properties of the mantle including density, elasticity, and electrical and thermal conductivity. However, the determination of electronic states of iron has been controversial, in part due to different interpretations of Mössbauer spectroscopy results used to identify spin state, valence state, and site occupancy of iron. We applied energy-domain Mössbauer spectroscopy to a set of four bridgmanite samples spanning a wide range of compositions: 10-50% Fe/total cations, 0-25% Al/total cations, 12-100% Fe3+/total Fe. Measurements performed in the diamond-anvil cell at pressures up to 76 GPa below and above the high to low spin transition in Fe3+ provide a Mössbauer reference library for bridgmanite and demonstrate the effects of pressure and composition on electronic states of iron. Results indicate that although the spin transition in Fe3+ in the bridgmanite B-site occurs as predicted, it does not strongly affect the observed quadrupole splitting of 1.4 mm/s, and only decreases center shift for this site to 0 mm/s at ~70 GPa. Thus center shift can easily distinguish Fe3+ from Fe2+ at high pressure, which exhibits two distinct Mössbauer sites with center shift ~1 mm/s and quadrupole splitting 2.4-3.1 and 3.9 mm/s at ~70 GPa. Correct quantification of Fe3+/total Fe in bridgmanite is required to constrain the effects of composition and redox states in experimental measurements of seismic properties of bridgmanite. In Fe-rich, mixed-valence bridgmanite at deep-mantle-relevant pressures, up to ~20% of the Fe may be a Fe2.5+ charge transfer component, which should enhance electrical and thermal conductivity in Fe-rich heterogeneities at the base of Earth's mantle.
Abstract: he interior of the Earth is an important reservoir for elements that are chemically bound in minerals, melts, and gases. Analyses of the proportions of redox-sensitive elements in ancient and contemporary natural rocks provide information on the temporal redox evolution of our planet. Natural inclusions trapped in diamonds, xenoliths, and erupted magmas provide unique windows into the redox conditions of the deep Earth, and reveal evidence for heterogeneities in the mantle’s oxidation state. By examining the natural rock record, we assess how redox boundaries in the deep Earth have controlled elemental cycling and what effects these boundaries have had on the temporal and chemical evolution of oxygen fugacity in the Earth’s interior and atmosphere.
Geochimica et Cosmochimica Acta, Vol. 30, pp. 110-136.
Mantle
redox
Abstract: The chemistry of bridgmanite (Brg), especially the oxidation state of iron, is important for understanding the physical and chemical properties, as well as putting constraints on the redox state, of the Earth’s lower mantle. To investigate the controls on the chemistry of Brg, the Fe3+ content of Brg was investigated experimentally as a function of composition and oxygen fugacity (fo2) at 25 GPa. The Fe3+/?Fe ratio of Brg increases with Brg Al content and fo2 and decreases with increasing total Fe content and with temperature. The dependence of the Fe3+/?Fe ratio on fo2 becomes less steep with increasing Al content. Thermodynamic models were calibrated to describe Brg and ferropericlase (Fp) compositions as well as the inter-site partitioning of trivalent cations in Brg in the Al-Mg-Si-O, Fe-Mg-Si-O and Fe-Al-Mg-Si-O systems. These models are based on equilibria involving Brg components where the equilibrium thermodynamic properties are the main adjustable parameters that are fit to the experimental data. The models reproduce the experimental data over wide ranges of fo2 with a relatively small number of adjustable terms. Mineral compositions for plausible mantle bulk compositions can be calculated from the models as a function of fo2 and can be extrapolated to higher pressures using data on the partial molar volumes of the Brg components. The results show that the exchange of Mg and total Fe (i.e., ferric and ferrous) between Brg and Fp is strongly fo2 dependent, which allows the results of previous studies to be reinterpreted. For a pyrolite bulk composition with an upper mantle bulk oxygen content, the fo2 at the top of the lower mantle is ?0.86 log units below the iron-wüstite buffer (IW) with a Brg Fe3+/?Fe ratio of 0.50 and a bulk rock ratio of 0.28. This requires the formation of 0.7?wt.% Fe-Ni alloy to balance the raised Brg ferric iron content. With increasing pressure, the model predicts a gradual increase in the Fe3+/?Fe ratio in Brg in contrast to several previous studies, which levels off by 50 GPa. Oxygen vacancies in Brg decrease to practically zero by 40 GPa, potentially influencing elasticity, diffusivity and rheology in the top portion of the lower mantle. The models are also used to explore the fo2 recorded by inclusions in diamonds, which likely crystallized as Brg in the lower mantle, revealing oxygen fugacities which likely preclude the formation of some diamonds directly from carbonates, at least at the top of the lower mantle.
Annual Review of Earth and Planetary Sciences, Vol. 49, pp. 337-366.
Mantle
redox
Abstract: The rise of molecular oxygen (O2) in the atmosphere and oceans was one of the most consequential changes in Earth's history. While most research focuses on the Great Oxidation Event (GOE) near the start of the Proterozoic Eon—after which O2 became irreversibly greater than 0.1% of the atmosphere—many lines of evidence indicate a smaller oxygenation event before this time, at the end of the Archean Eon (2.5 billion years ago). Additional evidence of mild environmental oxidation—probably by O2—is found throughout the Archean. This emerging evidence suggests that the GOE might be best regarded as the climax of a broader First Redox Revolution (FRR) of the Earth system characterized by two or more earlier Archean Oxidation Events (AOEs). Understanding the timing and tempo of this revolution is key to unraveling the drivers of Earth's evolution as an inhabited world—and has implications for the search for life on worlds beyond our own. Many inorganic geochemical proxies suggest that biological O2 production preceded Earth's GOE by perhaps more than 1 billion years. Early O2 accumulation may have been dynamic, with at least two AOEs predating the GOE. If so, the GOE was the climax of an extended period of environmental redox instability. We should broaden our focus to examine and understand the entirety of Earth's FRR.
Earth and Planetary Science Letters, Vol. 575, 12p.
Mantle
redox
Abstract: The Earth's mantle hosts a variety of reduced and oxidized phases, including iron-bearing alloys, diamond, and sulfide and carbonate melts. In the upper mantle, increasing pressure favors the stabilization of reduced iron-bearing phases via disproportionation of ferrous iron into ferric and metallic iron. Pressure-driven disproportionation is thought to continue into the transition zone, based on the extrapolation of experiments conducted at lower pressures. To test this hypothesis, we performed high-temperature and high-pressure experiments on basaltic and peridotitic compositions at pressures of 10 to 20 GPa, buffered at different oxygen fugacities. Under these conditions, majoritic garnet is the dominant ferric-iron bearing phase. We analyze our experimental run products for their ferric iron concentrations with EELS and Mössbauer spectroscopy. Contrary to expectations, results show that at iron saturation, ferric iron content of majorite peaks in the upper transition zone and then decreases between 500 and 650 km depth, destabilizing and resorbing reduced phases. This peak can be explained by decreases in the effective volume of ferrous minerals in transition zone assemblages. We also show that natural diamond-hosted majorite inclusions that equilibrated in the sublithospheric mantle grew from variably reduced fluids. These results are consistent with the idea that these diamonds formed during progressive reduction of an originally carbonatitic melt.
