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Mantle potential temperatures (Tp) provide insights into mantle circulation and tests of whether Earth is the only planet to exhibit thermally bi-modal volcanism-a distinctive signature of modern plate tectonics. Planets that have a stagnant lid, for example, should exhibit volcanism that is uni-modal with Tp, since mantle plumes would have a monopoly on the genesis of volcanism. But new studies of magmatic ferric-ferrous ratios (XliqFe2O3/XliqFeO) (Cottrell and Kelley 2011) and the olivine-liquid Fe-Mg exchange coefficient, KD(Fe-Mg)Ol-liq (or KD) (Matzen et al. 2011) indicate that re-evaluations of Tp are needed. New tests and calibrations are thus presented for oxygen fugacity (fO2), XliqFe2O3/XliqFeO, potential temperature (Tp), melt fraction (F), KD, and peridotite enthalpies of fusion (ΔHfus) and heat capacities (CP). The new models for XliqFe2O3/XliqFeO and fO2 reduce error by 25-30%, and residual error for all models appears random; this last observation supports the common, but mostly untested, assumption that equilibrium is the most probable of states obtained by experiment, and perhaps in nature as well. Aggregate 1σ error on Tp is as high as ∼±77 °C, and estimates of F, and mantle olivine composition, are the greatest sources of error. Pressure and ΔHfus account for smaller, but systematic uncertainties (a constant ΔHfus can under-predict Texcess = Tpplume - Tpambient; assumptions of 1 atm can under-predict Tp). However, assumptions about whether parental magmas are incremental, accumulated, or isobaric batch melts induces no additional systematic error. The new models show that maximum Tp estimates on the oldest samples from Earth, Mars, Moon, and Vesta, decrease as planet size decreases. This may be expected since Tp should scale with accretion energy and reflect the Clausius-Clapeyron slope for the melting of silicates and Fe-Ni alloys. This outcome, however, occurs only if shergottites (from Mars) are 4.3 Ga (e.g., Bouvier et al. 2009; Werner et al. 2014), and the highest MgO komatiites from Earth's Archean era (27-30% MgO; Green et al. 1975) are used to estimate Tp. With these assumptions, Earth and Mars exhibit monotonic cooling, and support for Stevenson's (2003) idea that smaller planets cool at similar rates (∼90 - 135 °C/Ga), but at lower absolute temperatures. Tp estimates for Mars and Earth are also important in two other ways: Mars exhibits non-linear cooling, with rates as high as 275-550 °C/Ga in its first 0.5 Ga, and Archean volcanism on Earth was thermally bi-modal. Several hundred Archean volcanic compositions are in equilibrium with Fo92-94 olivine, and yield Tp modes at 1940 and 1720 °C, possibly representing plume and ambient mantle, respectively. These estimates compare to modern Tp values of 1560-1670 °C at Mauna Loa (plume) and 1330-1450 °C at MORB (ambient). We conclude that plate tectonics was active in some manner in the Archean, and that assertions of an Archean \"thermal catastrophe\" are exaggerated. Our new models also show that the modern Hawaiian source, when compared at the same T, has a lower fO2 compared to MORB, which would discount a Hawaiian source rich in recycled pyroxenite.

Analyses by the CheMin X-ray diffraction instrument on Mars Science Laboratory show that gypsum, bassanite, and anhydrite are common minerals at Gale crater. Warm conditions (∼6 to 30 °C) within CheMin drive gypsum dehydration to bassanite; measured surface temperatures and modeled temperature depth profiles indicate that near-equatorial warm-season surface heating can also cause gypsum dehydration to bassanite. By accounting for instrumental dehydration effects we are able to quantify the in situ abundances of Ca-sulfate phases in sedimentary rocks and in eolian sands at Gale crater. All three Ca-sulfate minerals occur together in some sedimentary rocks and their abundances and associations vary stratigraphically. Several Ca-sulfate diagenetic events are indicated. Salinity-driven anhydrite precipitation at temperatures below ∼50 °C may be supported by co-occurrence of more soluble salts. An alternative pathway to anhydrite via dehydration might be possible, but if so would likely be limited to warmer near-equatorial dark eolian sands that presently contain only anhydrite. The polyphase Ca-sulfate associations at Gale crater reflect limited opportunities for equilibration, and they presage mixed salt associations anticipated in higher strata that are more sulfate-rich and may mark local or global environmental change. Mineral transformations within CheMin also provide a better understanding of changes that might occur in samples returned from Mars.

Phosphate minerals in ordinary chondrites provide a record of fluids that were present during metamorphic heating of the chondrite parent asteroids. We have carried out a petrographic study of the phosphate minerals, merrillite and apatite, in metamorphosed H group ordinary chondrites of petrologic type 4-6, to understand development of phosphate minerals and associated fluid evolution during metamorphism. In unbrecciated chondrites, apatite is Cl rich and shows textural evolution from fine-grained apatite-merrillite assemblages in type 4 toward larger, uniform grains in type 6. The Cl/F ratio in apatite shows a similar degree of heterogeneity in all petrologic types, and no systematic change in compositions with metamorphic grade, which suggests that compositions in each meteorite are dictated by localized conditions, possibly because of a limited fluid/rock ratio. The development of phosphate minerals in H chondrites is similar to that of L and LL chondrites, despite the fact that feldspar equilibration resulting from albitization is complete in H4 chondrites but not in L4 or LL4 chondrites. This suggests that albitization took place during an earlier period of the metamorphic history than that recorded by preserved apatite compositions, and chemical equilibrium was not achieved throughout the H chondrite parent body or bodies during the late stages of metamorphism. A relict igneous clast in the H5 chondrite, Oro Grande has apatite rims on relict phenocrysts of (possibly) diopside that have equilibrated with the host chondrite. Apatite in the Zag H3-6 regolith breccia records a complex fluid history, which is likely related to the presence of halite in this meteorite. The porous dark H4 matrix of Zag, where halite is observed, has a high apatite/merrillite ratio, and apatite is extremely Cl rich. One light H6 clast contains similarly Cl-rich apatite. In a second light H6 clast, apatite compositions are very heterogeneous and more F-rich. Apatites in both H4 matrix and H6 clasts have very low H2O contents. Heterogeneous apatite compositions in Zag record multiple stages of regolith processing and shock at the surface of the H chondrite parent body, and apatite records either the passage of fluids of variable compositions resulting from different impact-related processes, or the passage of a single fluid whose composition evolved as it interacted with the chondrite regolith. Unraveling the history of apatite can potentially help to interpret the internal structure of chondrite parent bodies, with implications for physical and mechanical properties of chondritic asteroids. The behavior of halogens recorded by apatite is important for understanding the behavior of volatile elements in general: if impact-melt materials close to the surface of a chondritic asteroid are readily degassed, the volatile inventories of terrestrial planets could be considerably more depleted than the CI carbonaceous chondrite abundances that are commonly assumed.

Crystal chemical algorithms were used to estimate the chemical composition of selected mineral phases observed with the CheMin X-ray diffractometer onboard the NASA Curiosity rover in Gale crater, Mars. The sampled materials include two wind-blown soils, Rocknest and Gobabeb, six mudstones in the Yellowknife Bay formation (John Klein and Cumberland) and the Murray formation (Confidence Hills, Mojave2, and Telegraph Peak), as well as five sandstones, Windjana and the samples of the unaltered Stimson formation (Big Sky and Okoruso) and the altered Stimson formation (Greenhorn and Lubango). The major mineral phases observed with the CheMin instrument in the Gale crater include plagioclase, sanidine, P21/c and C2/c clinopyroxene, orthopyroxene, olivine, spinel, and alunite-jarosite group minerals. The plagioclase analyzed with CheMin has an overall estimated average of An40(11) with a range of An30(8) to An63(6). The soil samples, Rocknest and Gobabeb, have an average of An56(8) while the Murray, Yellowknife Bay, unaltered Stimson, and altered Stimson formations have averages of An38(2), An37(5), An45(7), and An35(6), respectively. Alkali feldspar, specifically sanidine, average composition is Or74(17) with fully disordered Al/Si. Sanidine is most abundant in the Wind-jana sample (∼26 wt% of the crystalline material) and is fully disordered with a composition of Or87(5). The P21/c clinopyroxene pigeonite observed in Gale crater has a broad compositional range {[Mg0.95(12)-1.54(17)Fe0.18(17)-1.03(9)Ca0.00-0.28(6)]Σ2Si2O6} with an overall average of Mg1.18(19)Fe0.72(7)Ca0.10(9)Si2O6. The soils have the lowest Mg and highest Fe compositions [Mg0.95(5)Fe1.02(7)Ca0.03(4)Si2O6] of all of the Gale samples. Of the remaining samples, those of the Stimson formation exhibit the highest Mg and lowest Fe [average = Mg1.45(7)Fe0.35(13)Ca0.19(6)Si2O6]. Augite, C2/c clinopyroxene, is detected in just three samples, the soil samples [average = Mg0.92(5)Ca0.72(2)Fe0.36(5)Si2O6] and Windjana (Mg1.03(7)Ca0.75(4)Fe0.21(9)Si2O6). Orthopyroxene was not detected in the soil samples and has an overall average composition of Mg0.79(6)Fe1.20(6)Ca0.01(2)Si2O6 and a range of [Mg0.69(7)-0.86(20)Fe1.14(20)-1.31(7)Ca0.00-0.04(4)]Σ2Si2O6, with Big Sky exhibiting the lowest Mg content [Mg0.69(7)Fe1.31(7)Si2O6] and Okoruso exhibiting the highest [Mg0.86(20)Fe1.14(20)Si2O6]. Appreciable olivine was observed in only three of the Gale crater samples, the soils and Windjana. Assuming no Mn or Ca, the olivine has an average composition of Mg1.19(12)Fe0.81(12)SiO4 with a range of 1.08(3) to 1.45(7) Mg apfu. The soil samples [average = Mg1.11(4)Fe0.89SiO4] are significantly less magnesian than Windjana [Mg1.35(7)Fe0.65(7)SiO4]. We assume magnetite (Fe3O4) is cation-deficient (Fe3-x∎xO4) in Gale crater samples [average = Fe2.83(5)∎0.14O4; range 2.75(5) to 2.90(5) Fe apfu], but we also report other plausible cation substitutions such as Al, Mg, and Cr that would yield equivalent unit-cell parameters. Assuming cation-deficient magnetite, the Murray formation [average = Fe2.77(2)∎0.23O4] is noticeably more cation-deficient than the other Gale samples analyzed by CheMin. Note that despite the presence of Ti-rich magnetite in martian meteorites, the unit-cell parameters of Gale magnetite do not permit significant Ti substitution. Abundant jarosite is found in only one sample, Mojave2; its estimated composition is (K0.51(12)Na0.49)(Fe2.68(7)Al0.32)(SO4)2(OH)6. In addition to providing composition and abundances of the crystalline phases, we calculate the lower limit of the abundance of X-ray amorphous material and the composition thereof for each of the samples analyzed with CheMin. Each of the CheMin samples had a significant proportion of amorphous SiO2, except Windjana that has 3.6 wt% SiO2. Excluding Windjana, the amorphous materials have an SiO2 range of 24.1 to 75.9 wt% and an average of 47.6 wt%. Windjana has the highest FeOT (total Fe content calculated as FeO) at 43.1 wt%, but most of the CheMin samples also contain appreciable Fe, with an average of 16.8 wt%. With the exception of the altered Stimson formation samples, Greenhorn and Lubango, the majority of the observed SO3 is concentrated in the amorphous component (average = 11.6 wt%). Furthermore, we provide average amorphous-component compositions for the soils and the Mount Sharp group formations, as well as the limiting element for each CheMin sample.

Many igneous rocks contain mineral assemblages that are not appropriate for application of common mineral equilibria or oxybarometers to estimate oxygen fugacity. Spinel-structured oxides, common minerals in many igneous rocks, typically contain sufficient V for XANES measurements, allowing use of the correlation between oxygen fugacity and V K pre-edge peak intensity. Here we report V pre-edge peak intensities for a wide range of spinels from source rocks ranging from terrestrial basalt to achondrites to oxidized chondrites. The XANES measurements are used to calculate oxygen fugacity from experimentally produced spinels of known fO2. We obtain values, in order of increasing fO2, from IW-3 for lodranites and acapulcoites, to diogenites, brachinites (near IW), ALH 84001, terrestrial basalt, hornblende-bearing R chondrite LAP 04840 (IW+1.6), and finally ranging up to IW+3.1 for CK chondrites (where the ΔIW notation = logfO2 of a sample relative to the logfO2 of the IW buffer at specific T). To place the significance of these new measurements into context we then review the range of oxygen fugacities recorded in major achondrite groups, chondritic and primitive materials, and planetary materials. This range extends from IW-8 to IW+2. Several chondrite groups associated with aqueous alteration exhibit values that are slightly higher than this range, suggesting that water and oxidation may be linked. The range in planetary materials is even wider than that defined by meteorite groups. Earth and Mars exhibit values higher than IW+2, due to a critical role played by pressure. Pressure allows dissolution of volatiles into magmas, which can later cause oxidation or reduction during fractionation, cooling, and degassing. Fluid mobility, either in the sub-arc mantle and crust, or in regions of metasomatism, can generate values >IW+2, again suggesting an important link between water and oxidation. At the very least, Earth exhibits a higher range of oxidation than other planets and astromaterials due to the presence of an O-rich atmosphere, liquid water, and hydrated interior. New analytical techniques and sample suites will revolutionize our understanding of oxygen fugacity variation in the inner solar system, and the origin of our solar system in general.

Most extraterrestrial samples feature the two accessory Ca-phosphates (apatite-group minerals and merrillite), which are important carrier phases of the rare earth elements (REE). The trace-element concentrations (REE, Sc, Ti, V, Cr, Mn, Co, As, Rb, Sr, Y, Zr, Nb, Ba, Hf, Ta, Pb, Th, and U) of selected grains were analyzed by LA-ICP-MS and/or SIMS (REE only). This systematic investigation includes 99 apatite and 149 merrillite analyses from meteorites deriving from various asteroidal bodies including 1 carbonaceous chondrite, 8 ordinary chondrites, 3 acapulcoites, 1 winonaite, 2 eucrites, 5 shergottites, 1 ureilitic trachyandesite, 2 mesosiderites, and 1 silicate-bearing IAB iron meteorite.Although Ca-phosphates predominantly form in metamorphic and/or metasomatic reactions, some are of igneous origin. As late-stage phases that often incorporate the vast majority of their host's bulk REE budget, the investigated Ca-phosphates have REE enrichments of up to two orders of magnitude compared to the host rock's bulk concentrations. Within a single sample, each phosphate species displays a uniform REE-pattern, and variations are mainly restricted to their enrichment, therefore indicating similar formation conditions. Exceptions are brecciated samples, i.e., the Adzhi-Bogdo (LL3-6) ordinary chondrite. Despite this uniformity within single samples, distinct meteorite groups do not necessarily have unique REE-patterns. Four basic shapes dominate the REE patterns of meteoritic Ca-phosphates: (1) flat patterns, smoothly decreasing from La-Lu with prominent negative Eu anomalies (acapulcoites, eucrites, apatite from the winonaite and the ureilitic trachyandesite, merrillite from ordinary chondrites); (2) unfractionated patterns, with only minor or no anomalies (mesosiderites, enriched shergottites, IAB-iron meteorite); (3) LREE-enriched patterns, with either positive or slightly negative Eu anomalies (chondritic apatite); and (4) strongly LREE-depleted patterns, with negative Eu anomalies (depleted shergottites). The patterns do not correlate with the grade of metamorphism (petrologic type), specific adjacent mineral assemblages or with Ca-phosphate grain size. Neither the proportions of different REE, nor particular REE patterns themselves are universally correlated to a specific formation mechanism yet Eu (i.e., magnitude of the Eu anomaly) is a sensitive indicator to evaluate the timing of plagioclase and phosphate crystallization. Based on our data, U and Th abundances in apatite increase (almost linearly) with the grade of metamorphism, as well as with the differentiation of their host rock.

Chenmingite (FeCr2O4; IMA 2017-036) is a high-pressure mineral, occurring as micrometer- to submicrometer-sized lamellae within precursor chromite grains along with xieite and Fe,Cr-rich ulvospinel next to shock-induced melt pockets, from the Tissint martian meteorite. The composition of type chenmingite by electron probe analysis shows an empirical formula of (Fe2+0.75Mg0.23Mn0.02) (Cr1.60Al0.29Fe3+0.06Fe2+0.04Ti0.02)Σ2.01O4. The general and end-member formulas are (Fe,Mg)(Cr,Al)2O4 and FeCr2O4. Synchrotron X-ray diffraction reveals that chenmingite has an orthorhombic Pnma CaFe2O4-type (CF) structure with unit-cell dimensions: a=9.715(6) Å, b=2.87(1) Å, c=9.49(7) Å, V=264.6(4) Å3, and Z=4. Both chenmingite and xieite formed by solid-state transformation of precursor chromite under high pressure and high temperature during the Tissint impact event on Mars. The xieite regions are always in contact with melt pockets, whereas chenmingite lamellae only occur within chromite, a few micrometers away from the melt pockets. This arrangement suggests that chenmingite formed under similar pressures as xieite but at lower temperatures, in agreement with experimental studies.