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1. Trace and Rare Earth Element Compositions of Lawsonite as a Chemical Tracer of Metamorphic Processes in Subduction Zones

   https://doi.org/10.1093/petrology/egac065  

   Kang, Patricia; Whitney, Donna L; Martin, Laure A; Fornash, Katherine F (August 2022, Journal of Petrology)

   Abstract Lawsonite is a major host mineral of trace elements (TEs; e.g. REE, Sr, Pb, U, Th) and H2O in various rock types (metabasite, metasediment, metasomatite) over a wide range of depths in subduction zones. Consequently, the composition of lawsonite is a useful archive to track chemical exchanges that occurred during subduction and/or exhumation, as recorded in high-pressure/low-temperature (HP/LT) terranes. This study provides an extensive dataset of major element and TE compositions of lawsonite in HP/LT rocks from two mélanges (Franciscan/USA; Rio San Juan/Dominican Republic), two structurally coherent terranes (Tavşanlı/Turkey; Alpine Corsica/France), and the eclogite blocks of the Pinchi Lake/Canada complex. Bulk major and TE compositions were also determined for lawsonite-bearing host rocks to understand petrogenesis and assess compositional evolution. Most analyzed mélange and coherent-terrane metabasalts have normal mid-ocean ridge/back-arc basin basalt signatures and they preserve compositional evidence supporting interactions with (meta)sediment ± metagabbro/serpentinite (e.g. LILE/LREE enrichments; Ni/Cr enrichments). Most lawsonite grains analyzed are compositionally zoned in transition-metal elements (Fe, Ti, Cr), other TEs (e.g. Sr, Pb), and/or REE, with some grains showing compositional variations that correlate with zoning patterns (e.g. Ti-sector zoning, core-to-rim zoning in Fe, Cr-oscillatory zoning). Our results suggest that compositional variations in lawsonite formed in response to crystallographic control (in Ti-sector zoning), fluid–host rock interactions, modal changes in minerals, and/or element fractionation with coexisting minerals that compete for TEs (e.g. epidote, titanite). The Cr/V and Sr/Pb ratios of lawsonite are useful to track the compositional influence of serpentinite/metagabbro (high Cr/V) and quartz-rich (meta)sediment (low Sr/Pb). Therefore, lawsonite trace and rare earth element compositions effectively record element redistribution driven by metamorphic reactions and fluid–rock interactions that occurred in subduction systems. 

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2. Redox and mineral controls on Fe and Ti isotopic fractionations during calc-alkaline magmatic differentiation

   https://doi.org/10.1016/j.gca.2023.06.016  

   Johnson, Aleisha C.; Zhang, Zhe J.; Dauphas, Nicolas; Rudnick, Roberta L.; Foden, John D.; Toc, Magali (August 2023, Geochimica et Cosmochimica Acta)

   Titanium and Fe isotopic compositions of lavas from a calc-alkaline differentiation suite and corresponding mineral separates from the Rindjani Volcano, Indonesia show that Fe and Ti isotopic fractionations between minerals and melts are lower than those recorded in other suites at all stages of differentiation. The limited isotopic fractionation for Ti is likely due to low-Ti magnetite and clinopyroxene being the dominant carriers of Ti in Rindjani lavas, as these minerals are thought to have limited equilibrium Ti isotopic fractionation relative to silicate magmas. Other magmatic differentiation suites controlled by removal of Ti-rich magnetite and characterized by a lesser role of clinopyroxene have larger Ti isotopic fractionations. This effect is an indirect consequence of the elevated Fe3+/Fe2+ ratio of calc-alkaline magmas such as Rindjani, which promotes Fe3+ incorporation into magnetite at the expense of Fe2+-Ti4+ pairs, such that increased oxygen fugacity will subdue Ti isotopic fractionation in global magmatic series. Similarly, we find negligible Fe isotopic fractionation in Rindjani bulk rocks and mineral separates, unlike previous studies. This is also likely due to the oxidized nature of the Rindjani differentiation suite, which leads to similar Fe3+/Fe2+ ratios in melt and minerals and decreases overall mineral-melt Fe fractionation factors. Paired Ti and Fe isotopic analyses may therefore represent a powerful tool to assess oxygen fugacity during differentiation, independent from Fe 3+ determinations of erupted samples. 

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3. Fe-Ti vs. Fe-Fe charge transfers: A comprehensive review and its applications in minerals and glasses

   https://doi.org/10.2138/am-2025-9835  

   Vigier, Maxence; Evans, Helen; Rossman, George R; Jobic, Stéphane; Fritsch, Emmanuel (August 2025, American Mineralogist)

   Tomascak, P; Nestola, F (Ed.)

   Abstract Iron-titanium (Fe-Ti) charge transfer is mentioned in numerous articles as the source of the coloration of many natural minerals and some man-made materials, but no global review of this phenomenon has been provided so far. Iron and titanium are ubiquitous in nature and are often found in the same material as Fe2+ and Fe3+, and Ti4+ (more rarely Ti3+). When Fe and Ti ions are in close geometric proximity in an oxide or (alumino)silicate structure, charge transfer can occur between the two ions, even though their concentration might be below 100 ppm. This results in a variety of absorption features that contributes to the color of minerals. Adebate remains on the exact nature of Fe/Ti electronic transition, i.e. Fe2+ + Ti4+ → Fe3+ + Ti3+ or the reverse, but solving this issue is not within the scope of the present work. Ascertaining a metal-metal charge transfer is often not straightforward. This review compiles existing knowledge on Fe-Ti charge transfer in both crystalline and amorphous materials and identifies several key characteristics in more than 40 different materials. A charge transfer is associated with broad, intense, optical absorption bands that decrease in intensity at elevated temperatures. It is also strongly pleochroic in non-isotropic materials. Until now, Fe-Ti charge transfer transitions have been primarily described in the 2.25 to 3.1 eV range, corresponding to yellow to orange to brown colors, with notable exceptions such as blue sapphire or kyanite, and green andalusite. This review suggests that Fe-Ti charge transfer can occur across the entire visible spectrum, and the position of the absorption band correlates with the Fe-Ti nteratomic distance. This correlation highlights the presence of multiple crystallographic sites for both Fe and Ti in many oxides, leading to multiple Fe-Ti bands within these materials (e.g. sapphire, ilmenite, pseudobrookite). Finally, the use of metal-metal distances is suggested to differentiate this heteronuclear Fe-Ti charge transfer from the common homonuclear charge transfer Fe2+-Fe3+. 

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4. Fe2+/Fe3+ Intervalence Charge Transfer and Enhanced d - d Absorption in Mixed Valence Iron Minerals at Elevated Temperatures

   https://doi.org/10.2138/am-2024-9724  

   Evans, Helen V; Rossman, George R (July 2025, American Mineralogist)

   Tomascak, P; Nestola, F (Ed.)

   Abstract The absorption of light by Fe/Ti and Fe/Fe intervalence charge transfer (IVCT) bands has previously been found in aluminum oxide and Al2SiO5 aluminosilicate minerals to decrease markedly at elevated temperatures. Given the abundance of iron at depth in the Earth, assessing the generality with which and extent to which IVCT mineral phases become more optically transparent at temperature than they are under ambient conditions has potentially significant implications for the modeling of mantle geophysical processes such as radiative conductivity. A broad experimental survey of the optical absorption spectra at elevated temperatures of various mixed valence iron minerals has been conducted. The minerals considered here are cordierite, chloritoid, lazulite, dumortierite, jeremejevite, beryl, osumilite, biotite (mica), pargasite (amphibole) and aegirine (pyroxene). All samples transiently lose significant Fe/Fe IVCT feature intensity at temperature. In beryl, osumilite, biotite, pargasite and aegirine, spin-allowed Fe2+d-d features also decrease in integral intensity at temperature; in all but beryl, the intensity loss is significant. This trend is consistent with d-d band enhancement via Fe2+/Fe3+ exchange coupling, which has not previously been identified in the majority of these minerals. It is contrasted against the behavior of ordinary spinallowed Fe2+d-d bands in non-IVCT minerals forsterite (olivine) and elbaite (tourmaline). The depletion of Fe/Fe IVCT and enhanced Fe2+d-d band intensity at elevated temperatures may both be important mechanisms by which iron-bearing mineral phases become more optically transparent under conditions at depth. 

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5. Effects of composition and pressure on electronic states of iron in bridgmanite

   https://doi.org/10.2138/am-2020-7309  

   Dorfman, Susannah M.; Potapkin, Vasily; Lv, Mingda; Greenberg, Eran; Kupenko, Ilya; Chumakov, Aleksandr I.; Bi, Wenli; Alp, E. Ercan; Liu, Jiachao; Magrez, Arnaud; et al (July 2020, American Mineralogist)

   null (Ed.)

   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. 

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