The chemical composition of Earth's lower mantle can be constrained by combining seismological observations with mineral physics elasticity measurements. However, the lack of laboratory data for Earth's most abundant mineral, (Mg,Fe,Al)(Al,Fe,Si)O bridgmanite (also known as silicate perovskite), has hampered any conclusive result. Here we report single-crystal elasticity data on (Al,Fe)-bearing bridgmanite (MgFeSiAl)O measured using high-pressure Brillouin spectroscopy and X-ray diffraction. Our measurements show that the elastic behaviour of (Al,Fe)-bearing bridgmanite is markedly different from the behaviour of the MgSiO endmember. We use our data to model seismic wave velocities in the top portion of the lower mantle, assuming a pyrolitic mantle composition and accounting for depth-dependent changes in iron partitioning between bridgmanite and ferropericlase. We find excellent agreement between our mineral physics predictions and the seismic Preliminary Reference Earth Model down to at least 1,200 kilometres depth, indicating chemical homogeneity of the upper and shallow lower mantle. A high Fe/Fe ratio of about two in shallow-lower-mantle bridgmanite is required to match seismic data, implying the presence of metallic iron in an isochemical mantle. Our calculated velocities are in increasingly poor agreement with those of the lower mantle at depths greater than 1,200 kilometres, indicating either a change in bridgmanite cation ordering or a decrease in the ferric iron content of the lower mantle.

A new suite of 173 clinopyroxene grains from heavy-mineral concentrates of the diamondiferous Novinka kimberlite (Upper Muna field, Yakutia) has been analyzed for major and minor elements with an electron microprobe to perform a thermobarometric study and model the thermal structure of the Archean Upper Muna lithospheric mantle. Scrupulous evaluation of propagation of analytical uncertainties on pressure estimates revealed that (1) the single-clinopyroxene geobarometer can be very sensitive to analytical uncertainties for particular clinopyroxene compositions, and that (2) most clinopyroxenes from Novinka have compositions that are sensitive to analytical uncertainties, notwithstanding their apparent compositional suitability for single-clinopyroxene thermobarometry based on previously proposed application limits. A test on various mantle clinopyroxenes containing different proportions of the sensitive elements Cr, Na, and Al allowed us to identify clinopyroxene compositions that produce unacceptably high propagated errors and to define appropriate analytical conditions (i.e., higher beam currents and longer counting times for specific elements) that allow precise P-T estimates to be obtained for sensitive compositions. Based on the results of our analytical test, and taking into account the intrinsic limitations of the single-clinopyroxene thermobarometer, we have designed a new protocol for optimum thermobarometry, which uses partly revised compositional filters. The new protocol permits precise computation of the conductive paleogeotherm at Novinka with the single-clinopyroxene thermobarometer of Nimis and Taylor (2000). Thermal modeling of the resulting P-T estimates indicates a ~34 mW/m2 surface heat flow, a thermal lithosphere thickness of ~225 km, and an over 100 km thick “diamond window” beneath Novinka in the middle Paleozoic (344–361 Ma). We estimate that appropriate analytical conditions may extend the applicability of single-clinopyroxene thermobarometry to over 90% of clinopyroxene-bearing garnet peridotites and pyroxenites and to ~70% of chromian-diopside inclusions in diamonds. In all cases, application to clinopyroxenes with Cr/(Cr+Al)mol < 0.1 is not recommended. We confirm the tendency of the single-clinopyroxene barometer to progressively underestimate pressure at P > 4.5 GPa

We performed thermodynamic calculations based on model and natural peridotitic compositions at pressure and temperature conditions relevant to the Earth’s upper mantle, using well-established free energy minimization techniques. The model is consistent with the available experimental data in Cr-bearing peridotitic systems and can therefore be used to predict phase relations and mineral compositions in a wide range of realistic mantle compositions. The generated phase diagrams for six different bulk compositions, representative of fertile, depleted and ultra-depleted peridotitic mantle, shown that the garnet - spinel stability field is always broad at low temperatures and progressively narrows with increasing temperatures. In lithospheric sections with hot geotherms (ca. 60 mW/m2), garnet coexists with spinel across an interval of 10–15 km, at ca. 50–70 km depths. In colder, cratonic, lithospheric sections (e.g. along a 40 mW/m2 geotherm), the width of the garnet–spinel transition strongly depends on bulk composition: In fertile mantle, spinel can coexist with garnet to about 120 km depth, while in an ultra-depleted harzburgitic mantle, it can be stable to over 180 km depth. The formation of chromian spinel inclusions in diamonds is restricted to pressures between 4.0 and 6.0 GPa. The modes of spinel decrease rapidly to less than 1 vol % when it coexists with garnet; hence, spinel grains can be easily overlooked during the petrographical characterization of small mantle xenoliths. The very Cr-rich nature of many spinels from xenoliths and diamonds from cratonic settings may be simply a consequence of their low modes in high-pressure assemblages; thus, their composition does not necessarily imply an extremely refractory composition of the source rock. The model also shows that large Ca and Cr variations in lherzolitic garnets in equilibrium with spinel can be explained by variations of pressure and temperature along a continental geotherm and do not necessarily imply variations of bulk composition. The slope of the Cr# [i.e. Cr/(Cr + Al)mol] isopleths in garnet in equilibrium with spinel changes significantly at high temperatures, posing serious limitations to the applicability of empirical geobarometric methods calibrated on cratonic mantle xenoliths in hotter, off-craton, lithospheric mantle sections

The Fe–Mg exchange coefficient between olivine (ol) and melt (m), defined as $${\text{Kd}}_{{{\text{Fe}}^{T} {-} {\text{Mg}}}}$$ Kd Fe T - Mg  = (Feol/Fem)·(Mgm/Mgol), with all FeT expressed as Fe2+, is one of the most widely used parameters in petrology. We explore the effect of redox conditions on $${\text{Kd}}_{{{\text{Fe}}^{T} {-} {\text{Mg}}}}$$ Kd Fe T - Mg using experimental, olivine-saturated basaltic glasses with variable H2O (≤ 7 wt%) over a wide range of fO2 (iron-wüstite buffer to air), pressure (≤ 1.7 GPa), temperature (1025–1425 °C) and melt composition. The ratio of Fe3+ to total Fe (Fe3+/∑Fe), as determined by Fe K-edge µXANES and/or Synchrotron Mössbauer Source (SMS) spectroscopy, lies in the range 0–0.84. Measured Fe3+/∑Fe is consistent (± 0.05) with published algorithms and appears insensitive to dissolved H2O. Combining our new data with published experimental data having measured glass Fe3+/∑Fe, we show that for Fo65–98 olivine in equilibrium with basaltic and basaltic andesite melts, $${\text{Kd}}_{{{\text{Fe}}^{T} {-} {\text{Mg}}}}$$ Kd Fe T - Mg decreases linearly with Fe3+/∑Fe with a slope and intercept of 0.3135 ± 0.0011. After accounting for non-ideal mixing of forsterite and fayalite in olivine, using a symmetrical regular solution model, the slope and intercept become 0.3642 ± 0.0011. This is the value at Fo50 olivine; at higher and lower Fo the value will be reduced by an amount related to olivine non-ideality. Our approach provides a straightforward means to determine Fe3+/∑Fe in olivine-bearing experimental melts, from which fO2 can be calculated. In contrast to $${\text{Kd}}_{{{\text{Fe}}^{T} {-} {\text{Mg}}}}$$ Kd Fe T - Mg , the Mn–Mg exchange coefficient, $${\text{Kd}}_{{{\text{Mn}} {-} {\text{Mg}}}}$$ Kd Mn - Mg , is relatively constant over a wide range of P–T–fO2 conditions. We present an expression for $${\text{Kd}}_{{{\text{Mn}} {-} {\text{Mg}}}}$$ Kd Mn - Mg that incorporates the effects of temperature and olivine composition using the lattice strain model. By applying our experimentally-calibrated expressions for $${\text{Kd}}_{{{\text{Fe}}^{T} {-} {\text{Mg}}}}$$ Kd Fe T - Mg and $${\text{Kd}}_{{{\text{Mn}} {-} {\text{Mg}}}}$$ Kd Mn - Mg to olivine-hosted melt inclusions analysed by electron microprobe it is possible to correct simultaneously for post-entrapment crystallisation (or dissolution) and calculate melt Fe3+/∑Fe to a precision of ≤ 0.04.

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Magmatic rocks from the Dolomites, Carnic and Julian Alps, Italy, have been sampled to investigate the origin and geodynamic setting of Triassic magmatism in the Southern Alps. Basaltic, gabbroic and lamprophyric samples have been characterized for their petrography, mineral chemistry, whole-rock major and trace elements, and Sr, Nd and Pb isotopic compositions. Geothermobarometric estimates suggest that the basaltic magmas crystallized mostly at depths of 14–20 km. Isotopic data show variable degrees of crustal contamination decreasing westwards, probably reflecting a progressively more restitic nature of the crust, which has been variably affected by melting during the Permian period. Geochemical and isotopic data suggest that the mantle source was metasomatized by slab-derived fluids. In agreement with previous studies and based on geological evidence, we argue that this metasomatism was not contemporaneous with the Ladinian–Carnian magmatism but was related to previous subduction episodes. The lamprophyres, which likely originated some 20 Ma later by lower degrees of melting and at higher pressures with respect to the basaltic suite, suggest that the mantle source regions of Triassic magmatism in the Dolomites was both laterally and vertically heterogeneous. We conclude that the orogenic signatures of the magmas do not imply any coeval subduction in the surrounding of Adria. We rather suggest that this magmatism is related to the Triassic rifting episodes that affected the western Mediterranean region and that were ultimately connected to the rifting events that caused the break-up of Pangea during the Late Triassic – Early Jurassic period.

General rights This document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms 1 On the-fO2 stability of Fe 4 O 5 , Fe 5 O 6 and Fe 4 O 5-rich solid solutions. ABSTRACT The high pressure phases Fe4O5 and Fe5O6 have recently been added to the list of known iron oxides. As mixed valence phases, it has been suggested that they could form in the Earth's mantle once the dominant minerals become saturated in ferric iron. The possibility that Fe4O5 could exist in the mantle is also supported by the fact that it forms extensive solid solutions with both Mg 2+ and Cr 3+. In this study, we present the results of high pressure and temperature multi-anvil experiments performed between 5 and 24 GPa at 1000-1400˚C1400˚C aimed at constraining the stability field of the Fe4O5 phase. We combine these results with published phase equilibria, equation of state and Fe-Mg partitioning data to estimate the thermodynamic properties of Fe4O5, Fe5O6 and the (Mg,Fe)2Fe2O5 solid solution. Using our thermodynamic model the oxygen fugacity at which the high pressure iron oxides become stable are calculated and the redox stability of (Mg,Fe)2Fe2O5 in an assemblage of olivine and pyroxene is calculated as a function of the bulk Fe/(Fe+Mg) ratio. Fe4O5 and (Mg,Fe)2Fe2O5 are stable at oxygen fugacities higher than the diamond stability field and are, therefore, unlikely to be found as inclusions in diamonds. The stability field of Fe5O6, on the other hand, extends to oxygen fugacities compatible with diamond formation. Using the Mg-Fe solid solution model, we show that Fe4O5-structured phases would be restricted to aluminum-poor environments in the mantle such as dunites or silica-iron oxide-rich sediments transported into the mantle via subduction.

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