Mössbauer spectroscopy studies of the valence state of iron in chromite from the Luobusa massif of Tibet: implications for a highly reduced deep mantle

Mössbauer spectroscopy was applied to study the valence state of iron in chromite from massive, nodular and disseminated podiform chromitite ores of the Luobasa ophiolite massif of Tibet. The results show that Fe³⁺/ΣFe = 0.42 in chromite from massive ore, and Fe³⁺/ΣFe = 0.22 in chromite from nodular and disseminated ores. The massive ore records traces of ultra high pressure mineralogical assemblages, such as diamond inclusions in OsIr alloys, exsolution lamellae of coesite and diopside in chromite, inclusions of metal‐nitrides, native iron and others, which suggests a strongly reducing environment. In contrast, chromite from nodular and disseminated ore contains abundant low‐pressure OH‐bearing mineral inclusions whose formation requires a more oxidizing environment. The high value of Fe³⁺/ΣFe in the ‘reduced’ massive ore is explained by crystallographic stabilization of Fe³⁺ in a high‐pressure polymorph of chromite deep in the upper mantle despite low ambient fO₂ conditions. The presence of high‐pressure phases within the massive chromitite ore requires that the latter, together with its host peridotite, was transported in the solid state from a highly reduced deep mantle environment to shallow depths beneath an ocean spreading centre. It is suggested that in the low‐pressure environment of the spreading centre, the deep‐seated, reduced, massive chromitites partially reacted with their host peridotite in the presence of hydrous melt, yielding the nodular and disseminated chromitite ores. The preponderance of evidence suggests that the latter interaction involved boninitic melts in a supra‐subduction zone environment as proposed previously.     

Oxidation Experiment of Natural Megacrystal Clinopyroxene: Implications for Assignment of Mössbauer Spectra

The Mössbauer spectra of natural megacrystal clinopyroxene are usually fitted by 4 sets of symmetric doublets, A‐A', B‐B', C‐C' and D‐D', respectively, in terms of increasing Qs value in literature. But the assignments of those doublets are quite different, except the D‐D' doublet assigned to Fe³⁺at the lattice site M***1 in previous papers. Particularly, the assignment and interpretation of the C‐C' doublet are diverse. The oxidation experiments of natural megacrystal clinopyroxene collected from the Hannuoba basalt, North China, were performed under controlled conditions of temperature at 1000°C and oxygen fugacity of FMQ buffer in 1, 2, ***3 and 5 days respectively. The oxidized samples were then measured by X‐ray diffraction spectrometry and Mössbauer spectrometry. The oxidation of clinopyroxene is characterized by Fe²⁺ → Fe³⁺at M1 under the subsolidus conditions, which is consistent with the increase of the area of the D‐D' doublet when the heating time increases. Accordingly, the area of the A‐A' and B‐B' doublets decreases with the increasing heating time. However, the area of C‐C' keeps almost constant. Therefore, the 4 sets of doublets can be assigned correctly as follows: A‐A' doublet to Fe⁺²at M1, B‐B' Fe²⁺at M1, C‐C' Fe²⁺at M2, and D‐D' Fe³⁺at M1. The M1 site splitting is due to the NNN (Next Nearest Neighbour) effect of the M2 site. The amount of Fe³⁺at the tetrohedral site of megacrystal clinopyroxene is negligible according to this study.     

Interactions between organic matter and minerals in two bituminous coals of different rank

The association between specific mineral and organic constituents in two Asturian bituminous coals of different rank was studied. For this, raw coals were fractionated by density and the variation of a number of parameters was followed in parallel. Results of coal chemical analyses, including analyses for 22 elements, were used to establish the elemental association with coal organic matter. Petrographic analyses determined the distribution of macerals among densimetric fractions, vitrinite reflectance being at a minimum in the intermediate density fractions. Mineral species were identified by X-ray diffraction, FT-IR spectroscopy and Mössbauer spectroscopy. Comparison of trends for different parameters determined using this set of techniques allowed classification of the various minerals according to their association with organic matter. Carbonates seem to be specifically associated with the organic matter of the low-volatile bituminous coal whereas sulfides concentrate in the organic matter of the high-volatile bituminous coal. Vitrinite is the maceral exhibiting the most probable association with inorganic matter. The possibility of a merely physical association of fine-grained detrital minerals with organic matter cannot be excluded; nevertheless, one must bear in mind that even this type of interaction is important due to its effect on various coal preparation and utilization processes.     

Equilibrium iron isotope fractionation factors of minerals: Reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy

We have critically reevaluated equilibrium iron isotope fractionation factors for oxide and sulfide minerals using recently acquired data obtained by Mössbauer spectroscopy and inelastic nuclear resonant X-ray scattering (INRXS) synchrotron radiation. Good agreement was observed in the iron β-factors of metallic iron (α-Fe) and hematite calculated using both Mössbauer- and INRXS-derived data, which supports the validity and reliability of the calculations. Based on this excellent agreement, we suggest the use of the present data on the iron β-factors of hematite as a reference.The previous Mössbauer-derived iron β-factor for magnetite has been modified significantly based on the Fe-sublattice density of states obtained from the INRXS experiments. This resolves the disagreement between naturally observed iron isotope fractionation factors for mineral pairs involving magnetite and those obtained from the calculated β-factors. The correctness of iron β-factor for pyrite has been corroborated by the good agreement with experimental data of sulfur isotope geothermometers of pyrite-galena and pyrite-sphalerite. A good correlation between the potential energy of the cation site, the oxidation state of iron and the iron β-factor value has been established. Specifically, ferric compounds, which have a higher potential energy of iron than ferrous compounds, have higher β-factors. A similar dependence of β-factors on the oxidation state and potential energy could be extended to other transition metals. Extremely low values of INRXS-derived iron β-factors for troilite and Fe₃S significantly widen the range of iron β-factors for covalently bonded compounds.     

Redox state of iron in peralkaline rhyolitic glass/melt: X-ray absorption micro-spectroscopy experiments at high temperature

Assessing the ferric-ferrous ratio in magmas prior to eruption remains a challenging task. X-ray absorption near-edge structure (μXANES) spectra were collected at the iron K-edge in water-rich peralkaline silicic melt/glass inclusions trapped in quartz. These experiments were carried out between 800 and 20 °C. The chemical environment of iron was also determined in the naturally quenched samples (glass inclusions and matrix glass) and in the peralkaline rhyolitic reference glasses, with variable [Fe³⁺ / ∑Fe] ratios.In the reference glasses, both the intensity of the pre-peaks (Fe²⁺, Fe³⁺) and site geometry of iron change as the oxidation state increases. Fourfold-coordinated Fe³⁺ prevails in highly oxidised peralkaline silicic glasses, using alkalis for charge balance. The position of the pre-edge centroid of the 1s-3d transition correlates with the Fe³⁺ / ΣFe ratios that allowed calibration of the redox state of iron of our natural samples.At high temperatures, Fe²⁺ dominates in the pre-edge structure of melt inclusions. Upon cooling down to 20 °C, the intensity of the Fe³⁺ peak increases, the centroid position of the pre-edge features shifts by nearly 0.5 eV and the main edge moves slightly towards higher energies. The slower the cooling rate, the higher the ferric iron contribution. Iterative μXANES experiments performed on the same samples show that the process is reversible. However, this apparent oxidation of iron upon cooling is an artefact of changes in Fe coordination. It implies that the [Fe³⁺ / ΣFe] ratio of glassy samples, measured at 20 °C, may be overestimated by a factor > 1.7, and that this ratio cannot be reliably retrieved by probing naturally cooled glass inclusions, and most silicate glasses. High temperature μXANES experiments led first to an assessment of the ferric-ferrous ratio in the water-rich peralkaline melt in pre-eruptive magmatic conditions and second to the determination of the corresponding oxygen fugacity at 740 °C.     

Pressure effect on the electronic structure of iron in (Mg,Fe)(Si,Al)O3 perovskite: a combined synchrotron Mössbauer and X-ray emission spectroscopy study up to 100 GPa

We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg_0.88Fe_0.09)(Si_0.94Al_0.10)O₃ between 1 bar and 100 GPa and at 300 K, using diamond cells and synchrotron Mössbauer spectroscopy techniques. At pressures below 12 GPa, our Mössbauer spectra can be sufficiently fitted by a “two-doublet” model, which assumes one ferrous Fe²⁺-like site and one ferric Fe³⁺-like site with distinct hyperfine parameters. The simplest interpretation that is consistent with both the Mössbauer data and previous X-ray emission data on the same sample is that the Fe²⁺-like site is high-spin Fe²⁺, and the Fe³⁺-like site is high-spin Fe³⁺. At 12 GPa and higher pressures, a “three-doublet” model is necessary and sufficient to fit the Mössbauer spectra. This model assumes two Fe²⁺-like sites and one Fe³⁺-like site distinguished by their hyperfine parameters. Between 12 and 20 GPa, the fraction of the Fe³⁺-like site, Fe³⁺/∑Fe, changes abruptly from about 50 to 70%, possibly due to a spin crossover in six-coordinate Fe²⁺. At pressures above 20 GPa, the fractions of all three sites remain unchanged to the highest pressure, indicating a fixed valence state of iron within this pressure range. From 20 to 100 GPa, the isomer shift between the Fe³⁺-like and Fe²⁺-like sites increases slightly, while the values and widths of the quadruple splitting of all three sites remain essentially constant. In conjunction with the previous X-ray emission data, the Mössbauer data suggest that Fe²⁺ alone, or concurrently with Fe³⁺, undergoes pressure-induced spin crossover between 20 and 100 GPa.     

Polycyclic aromatic hydrocarbons as evidence of hydrocarbon migration in marine and lagoon sediments of a recent rift zone (Skjálfandi and Öxarfjörður), Iceland

Polycyclic aromatic hydrocarbons (PAHs) content and distribution was studied in the northern part of modern rift zone. All samples analysed represent slightly altered clastic deposits and hot water discharging in springs and from wells. To study PAH in present-day gas emission traps with diatomite absorbent were installed in the Skógalón geothermal field. All samples were analysed by the method of Shpol'sky spectroscopy. Hydrothermally altered deposits show the highest amount of PAH. Data obtained allow to believe that the distribution of PAH is closely associated with the dynamics of the hydrothermal environment. The fissure formation and temperature fluctuation in hydrothermal systems can govern both the processes of PAH synthesis and sorption. The evidences of PAH migration up through the Skjálfandi and Öxarfjörður sedimentary basins show that hydrocarbons associate mainly with hydrothermal minerals and deep ground waters. Studying PAH associations can be used as an indicator of hydrocarbons distribution, ways of migration and possible zones of accumulation in the land and marine sedimentary basins in active and ancient rift zones of Iceland.     

Submarine fan and slope-apron deposition in a Cretaceous Forearc Basin: The Gürsökü Formation (Kavak–Samsun, N. Turkey)

The Late Cretaceous Gürsökü Formation represents the proximal fill of the Sinop–Samsun Forearc Basin that was probably initiated by extension during the Early Cretaceous. The succession records sedimentation in two contrasting depositional systems: a slope-apron flanking a faulted basin margin and coarse-grained submarine fans. The slope-apron deposits consist of thinly bedded turbiditic sandstones and mudstones, interbedded with non-channelized chaotic boulder beds and intraformational slump sheets representing a spectrum of processes ranging from debris flow to submarine slides. The submarine fan sediments are represented by conglomerates and sandstones interpreted as deposited from high density turbidity currents and non-cohesive debris flows. The occurrence of both slope apron and submarine fan depositional systems in the Gürsökü Formation may indicates that the region was a tectonically active basin margin during the Late Cretaceous.     

Geochemical and Sr–Nd–Pb isotopic compositions of the Eocene Dölek and Sariçiçek Plutons, Eastern Turkey: Implications for magma interaction in the genesis of high-K calc-alkaline granitoids in a post-collision extensional setting

The major and trace elements and Sr–Nd–Pb isotopes of the host rocks and the mafic microgranular enclaves (MME) gathered from the Dölek and Sariçiçek plutons, Eastern Turkey, were studied to understand the underlying petrogenesis and geodynamic setting. The plutons were emplaced at  43 Ma at shallow depths ( 5 to 9 km) as estimated from Al-in hornblende geobarometry. The host rocks consist of a variety of rock types ranging from diorite to granite (SiO₂ = 56.98–72.67 wt.%; Mg# = 36.8–50.0) populated by MMEs of gabbroic diorite to monzodiorite in composition (SiO₂ = 53.21–60.94 wt.%; Mg# = 44.4–53.5). All the rocks show a high-K calc-alkaline differentiation trend. Chondrite-normalized REE patterns are moderately fractionated and relatively flat [(La/Yb)_N = 5.11 to 8.51]. They display small negative Eu anomalies (Eu/Eu = 0.62 to 0.88), with enrichment of LILE and depletion of HFSE. Initial Nd–Sr isotopic compositions for the host rocks are ε_Nd(43 Ma) = − 0.6 to 0.8 and mostly I_Sr = 0.70482–0.70548. The Nd model ages (T_DM) vary from 0.84 to 0.99 Ga. The Pb isotopic ratios are (²⁰⁶Pb/²⁰⁴Pb) = 18.60–18.65, (²⁰⁷Pb/²⁰⁴Pb) = 15.61–15.66 and (²⁰⁸Pb/²⁰⁴Pb) = 38.69–38.85. Compared with the host rocks, the MMEs are relatively homogeneous in isotopic composition, with I_Sr ranging from 0.70485 to 0.70517, ε_Nd(43 Ma) − 0.1 to 0.8 and with Pb isotopic ratios of (²⁰⁶Pb/²⁰⁴Pb) = 18.58–18.64, (²⁰⁷Pb/²⁰⁴Pb) = 15.60–15.66 and (²⁰⁸Pb/²⁰⁴Pb) = 38.64–38.77. The MMEs have T_DM ranging from 0.86 to 1.36 Ga. The geochemical and isotopic similarities between the MMEs and their host rocks indicate that the enclaves are of mixed origin and are most probably formed by the interaction between the lower crust- and mantle-derived magmas. All the geochemical data, in conjunction with the geodynamic evidence, suggest that a basic magma derived from an enriched subcontinental lithospheric mantle, probably triggered by the upwelling of the asthenophere, and interacted with a crustal melt that originated from the dehydration melting of the mafic lower crust at deep crustal levels. Modeling based on the Sr–Nd isotope data indicates that  77–83% of the subcontinental lithospheric mantle involved in the genesis. Consequently, the interaction process played an important role in the genesis of the hybrid granitoid bodies, which subsequently underwent a fractional crystallization process along with minor amounts of crustal assimilation, en route to the upper crustal levels generating a wide variety of rock types ranging from diorite to granite in an extensional regime.