The Effect of Fe-Al Substitution on the Crystal Structure of MgSiO3 Bridgmanite

The crystal chemistry of ten well-characterized bridgmanite single-crystals with Fe and Al contents ranging from 0 to 0.40 atoms per two-cation formula units were investigated by single-crystal X-ray diffraction. Structural refinements indicate that Fe3+ and Al mainly occupy the Mg and Si sites, respectively, when present in similar proportions. Molar volumes of bridgmanite endmember components were refined using data from this and previous studies and found to decrease in the order Fe3+Fe3+O3 > MgFe3+O2.5 > Fe3+AlO3 > MgAlO2.5 > AlAlO3 > Fe2+SiO3 > MgSiO3. Fe3+AlO3 charge-coupled substitution leads to an anisotropic increase of B-O bond distances, resulting in more distorted octahedral B sites and in a more significant increase of the c-axis with respect to the a- and b-axes. Valence bond calculations indicate that the A site is more compressible than the B site for all bridgmanite samples studied, implying that octahedral tilting and distortion will dominate the bridgmanite compression mechanism. Guided by these crystal chemical observations, bulk moduli of bridgmanite endmember components were estimated using results of previous studies. The volume changes of equilibria controlling the speciation of bridgmanite components were then calculated at conditions relevant to the top of Earth's lower mantle. The proportion of oxygen vacancy components is predicted to decrease with pressure. While the stability of the bridgmanite Fe3+AlO3 component will drive charge disproportionation to produce iron metal at the top of the lower mantle, this appears to be much less favorable by 50 GPa. An increase in the proportion of the Fe3+Fe3+O3 bridgmanite component, however, may favor the formation of iron metal at higher pressures

Effect of Fe3+ on Phase Relations in the Lower Mantle : Implications for Redox Melting in Stagnant Slabs

Recent studies have revealed that Earth's deep mantle may have a wider range of oxygen fugacities than previously thought. Such a large heterogeneity might be caused by material subducted into the deep mantle. However, high-pressure phase relations are poorly known in systems including Fe3+ at the top of the lower mantle, where the subducted slab may be stagnant. We therefore conducted high-pressure and high-temperature experiments using a multi-anvil apparatus to study the phase relations in a Fe3+-bearing system at 26 GPa and 1573–2073 K, at conditions prevailing at the top of the lower mantle. At temperatures below 1923 K, MgSiO3-rich bridgmanite, an Fe3+-rich oxide phase, and SiO2 coexist in the recovered sample. Quenched partial melt was observed above 1973 K, which is significantly lower than the solidus temperature of an equivalent Fe3+-free bulk composition. The partial melt obtained from the Fe3+-rich bulk composition has a higher iron content than coexisting bridgmanite, similar to the Fe2+-dominant system. The results suggest that strong mantle oxygen fugacity anomalies might alter the subsolidus and melting phase relations under lower mantle conditions. We conclude that (1) a small amount of melt may be generated from an Al-depleted region of a stagnant slab, such as subducted former banded-iron-formation, and (2) Fe3+ is not transported into the deep part of the lower mantle because of its incompatibility during melting

Local structural properties of (Mn,Fe)Nb2O6 from Mössbauer and X-ray absorption spectroscopy

The MnNb2O6–FeNb2O6 solid solution has been investigated by Fe–K- and Mn–K-edge X-ray absorption (XANES and EXAFS), and Mössbauer spectroscopy. The first-shell M—O bond lengths deduced from EXAFS show a fairly small compositional dependence. A degree of static disorder, which increases with increasing manganese content, is clearly seen by the loss of correlation for the next-neighbour (NN) interaction. Hyperfine parameters from Mössbauer spectra are consistent with variations in the average environment, as recorded by X-ray data. Line broadening of the Mössbauer spectra provides evidence for next-neighbour effects and is consistent with there being no significant clustering of Fe or Mn within the samples. There appear to be differences in the way the columbite structure accommodates Fe2+ and Mn2+ ions. In ferrocolumbite all the Fe octahedra are close to being identical, while there are local structural heterogeneities at a longer length scale, presumably in ordering the precise topology of polyhedra immediately adjacent to the octahedron. By contrast, the manganocolumbite seems to have some diversity in the precise coordination at the MnO6 octahedra, but a greater uniformity in how the adjacent polyhedra are configured around them

Perioperative pain management and opioid-reduction in head and neck endocrine surgery: An American Head and Neck Society Endocrine Surgery Section consensus statement

BACKGROUND: This American Head and Neck Society (AHNS) consensus statement focuses on evidence-based comprehensive pain management practices for thyroid and parathyroid surgery. Overutilization of opioids for postoperative pain management is a major contributing factor to the opioid addiction epidemic however evidence-based guidelines for pain management after routine head and neck endocrine procedures are lacking. METHODS: An expert panel was convened from the membership of the AHNS, its Endocrine Surgical Section, and ThyCa. An extensive literature review was performed, and recommendations addressing several pain management subtopics were constructed based on best available evidence. A modified Delphi survey was then utilized to evaluate group consensus of these statements. CONCLUSIONS: This expert consensus provides evidence-based recommendations for effective postoperative pain management following head and neck endocrine procedures with a focus on limiting unnecessary use of opioid analgesics

Spin transition of Fe 3+ in Al-bearing phase D: An alternative explanation for small-scale seismic scatterers in the mid-lower mantle

. An equation of state over the entire pressure range was calculated using the observed variation in low-spin fraction with pressure and a low-spin bulk modulus of K T0 = 253(30) GPa, derived from the data above 65 GPa. Pronounced softening in the bulk modulus occurs during the spin transition, reaching a minimum at 50 GPa (∼1500 km) where the bulk modulus of Fe-Al phase D is about 35% lower than Fe-Al-bearing silicate perovskite. Recovery of the bulk modulus at 50-65 GPa results in a structure that has a similar incompressibility as silicate perovskite above 65 GPa. Similarly, the bulk sound velocity of Fe-Al phase D reaches a minimum at ∼50 GPa, being about 10% slower than silicate perovskite. The potential association of Fe-Al phase D with subducted slabs entering the lower mantle, along with its elastic properties through the Fe 3+ spin transition predicted at 1200-1800 km, suggests that phase D may provide an alternative explanation for small-scale mid-lower mantle seismic scatterers and supports the presence of deeply recycled sediments in the lower mantle

Pressure tuning of charge ordering in iron oxide

A Verwey-type charge-ordering transition in magnetite at 120 K leads to the formation of linear units of three iron ions with one shared electron, called trimerons. The recently-discovered iron pentoxide (Fe$_4$O$_5$) comprising mixed-valent iron cations at octahedral chains, demonstrates another unusual charge-ordering transition at 150 K involving competing formation of iron trimerons and dimerons. Here, we experimentally show that applied pressure can tune the charge-ordering pattern in Fe$_4$O$_5$ and strongly affect the ordering temperature. We report two charge-ordered phases, the first of which may comprise both dimeron and trimeron units, whereas, the second exhibits an overall dimerization involving both the octahedral and trigonal-prismatic chains of iron in the crystal structure. We link the dramatic change in the charge-ordering pattern in the second phase to redistribution of electrons between the octahedral and prismatic iron chains, and propose that the average oxidation state of the iron cations can pre-determine a charge-ordering pattern

OCCURRENCE OF LOW-Ti AND HIGH-Ti FREUDENBERGITE IN ALKALI SYENITE

1609 Freudenbergite (Na2Fe 3+ 2Ti6O16) occurs in peralkaline alkali syenite dikes at Katzenbuckel, southwestern Germany, in association with lorenzenite, pyrochlore, landauite and Na–Zr silicates as rare, late-stage mineral phases. Freudenbergite shows a broad range in chemical composition; we recognize two varieties: 1) a “low-titanium ” type, with low concentrations of Ti and all iron in the trivalent state, as established by Mössbauer spectroscopy; this is the normal type of freudenbergite found in a syenite from the Katzenbuckel; 2) a “high-titanium ” type, with elevated concentrations of Ti and high contents of divalent cations (Mg 2+, Mn 2+, Zn 2+) substituting for Fe 2+. Increased concentrations of Nb are the cause of cation deficiency of sodium at the A site. Freudenbergite, up to 0.75 mm in size, is a sector-zoned mineral with selective enrichments in (Nb + Zr) and Ti in sectors (001) and (100), respectively. In one dike (Kb 45), freudenbergite metasomatically replaces primary ilmenite as well as thin exsolutionlamellae within hematite grains. Pseudobrookite, ilmenite, hematite or magnetite occur as Fe–Ti oxides in the freudenbergitebearing syenite samples. Ilmenite–hematite mineral pairs show large miscibility-gaps, and indicate conditions of formation in the range of 750–550°C at low pressures of about of 0.2–0.3 kbar. The unique occurrence of primary freudenbergite is mainly due to an efficient process of fractionation of the peralkaline syenitic melt, leading to a Na- and Ti-rich, but Ca-poor melt accompanied by a distinct enrichment in niobium and zirconium