AMPHIBOLE AND HERCYNITE SPINEL IN SHERGOTTY AND ZAGAMI: MAGMATIC WATER,DEPTH OF CRYSTALLIZATION,AND METASOMATISM

Amphibole and spinel occur in the Shergotty and Zagami meteorites only in magmatic inclusions in pigeonite. The trapped magma is essentially identical to the parental magmas for Shergotty and Zagami. The amphibole is a kaersutite with minimal halogen content; by inference, it must have been hydrous. If so, the Shergotty and Zagami melts contained at least 0.2 wt % H₂O and were probably H₂O-undersaturated. Pressures in excess of 1 kilobar seem necessary for the formation of amphibole. Spinel replaces magnetite in the inclusions, and olivine replaces magnetite elsewhere in the meteorites. To stabilize spinel, the melt in the inclusions must have become enriched in Al during fractionation, possibly because the small volume of the inclusions made nucleation of plagioclase unlikely. Pervasive replacement of magnetite through reduction reactions suggests that Shergotty and Zagami interacted with hydrogen-rich fluids during their cooling.     

Igneous and shock processes affecting chassignite amphibole evaluated using chlorine/water partitioning and hydrogen isotopes

Amphibole in chassignite melt inclusions provides valuable information about the volatile content of the original interstitial magma, but also shock and postshock processes. We have analyzed amphibole and other phases from NWA 2737 melt inclusions, and we evaluate these data along with published values to constrain the crystallization Cl and H₂O content of phases in chassignite melt inclusions and the effects of shock on these amphibole grains. Using a model for the Cl/OH exchange between amphibole and melt, we estimate primary crystallization OH contents of chassignite amphiboles. SIMS analysis shows that amphibole from NWA 2737 currently has 0.15 wt% H₂O. It has lost ~0.6 wt% H₂O from an initial 0.7–0.8 wt% H₂O due to intense shock. Chassigny amphibole had on average 0.3–0.4 wt% H₂O and suffered little net loss of H₂O due to shock. NWA 2737 amphibole has δD ≈ +3700‰; it absorbed Martian atmosphere‐derived heavy H in the aftermath of shock. Chassigny amphibole, with δD ≤ +1900‰, incorporated less heavy H. Low H₂O/Cl ratios are inferred for the primitive chassignite magma, which had significant effects on melting and crystallization. Volatiles released by the degassing of Martian magma were more Cl‐rich than on Earth, resulting in the high Cl content of Martian surface materials.     

Effect of chlorine on near‐liquidus crystallization of olivine‐phyric shergottite NWA 6234 at 1 GPa: Implication for volatile‐induced melting of the Martian mantle

Martian magmas are thought to be rich in chlorine compared with their terrestrial counterparts. Here, we experimentally investigate the effect of chlorine on liquidus depression and near‐liquidus crystallization of olivine‐phyric shergottite NWA 6234 and compare these results with previous experimental results on the effect of chlorine on near‐liquidus crystallization of the surface basalts Humphrey and Fastball. Previous experimental results showed that the change in liquidus temperature is dependent on the bulk composition of the basalt. The effect of chlorine on liquidus depression is greater for lower SiO₂ and higher Al₂O₃ magmas than for higher SiO₂ and lower Al₂O₃ magmas. The bulk composition for this study has lower Al₂O₃ and higher FeO contents than previous work; therefore, we provide additional constraints on the effect of the bulk composition on the influence of chlorine on near‐liquidus crystallization. High pressure and temperature crystallization experiments were performed at 1 GPa on a synthetic basalt, of the bulk composition of NWA 6234, with 0–4 wt% Cl added to the sample as AgCl. The results are consistent with previous notions that with increasing wt% Cl in the melt, the crystallization temperature decreases. Importantly, our results have a liquidus depression ?T (°C) from added chlorine that is consistent with the difference in bulk composition and suggest a dependence on both the bulk Al₂O₃ and FeO content. Our results suggest that the addition of chlorine to the Martian mantle may lower magma genesis temperatures and potentially aid in the petrogenesis of Martian magmas.     

Determination of volatile concentrations in fluorapatite of Martian shergottite NWA 2975 by combining synchrotron FTIR,Raman spectroscopy,EMPA, and TEM,and inferences on the volatile budget of the apatite host‐magma

We combined the focused ion beam sample preparation technique with polarized synchrotron‐based FTIR (Fourier transform infrared) spectroscopy, laser‐Raman spectroscopy, electron microprobe analysis (EMPA), and transmission electron microscope (TEM) analysis to identify and quantify structurally bound OH, F, Cl, and CO₃ groups in fluorapatite from the Northwest Africa 2975 (NWA 2975) shergottite. In this study, the first FTIR spectra of the OH‐stretching region from a Martian apatite are presented that show characteristic OH‐bands of a F‐rich, hydroxyl‐bearing apatite. Depending on the method of apatite‐formula calculation and whether charge balance is assumed or not, the FTIR‐based quantification of the incorporated OH, expressed as wt% H₂O, is in variably good agreement with the H₂O concentration calculated from electron microprobe data. EMP analyses yielded between 0.35 and 0.54 wt% H₂O, and IR data yielded an average H₂O content of 0.31 ± 0.03 wt%, consistent with the lower range determined from EMP analyses. The TEM observations implied that the volatiles budget of fluorapatite is magmatic. The water content and the relative volatile ratios calculated for the NWA 2975 magma are similar to those established for other enriched or intermediate shergottites. It is difficult to define the source of enrichment: either Martian wet mantle or crustal assimilation. Comparing the environment of parental magma generation for NWA 2975 with the terrestrial mantle in terms of water content, it displays a composition intermediate between enriched and depleted MORB.     

A petrogenetic model for the origin and compositional variation of the martian basaltic meteorites

Abstract— The major element, trace element, and isotopic compositional ranges of the martian basaltic meteorite source regions have been modeled assuming that planetary differentiation resulted from crystallization of a magma ocean. The models are based on low to high pressure phase relationships estimated from experimental runs and estimates of the composition of silicate Mars from the literature. These models attempt to constrain the mechanisms by which the martian meteorites obtained their superchondritic CaO/Al₂O₃ ratios and their source regions obtained their parent/daughter (⁸⁷Rb/⁸⁶Sr, ¹⁴⁷Sm/¹⁴⁴Nd, and ¹⁷⁶Lu/¹⁷⁷Hf) ratios calculated from the initial Sr, Nd, and Hf isotopic compositions of the meteorites. High pressure experiments suggest that majoritic garnet is the liquidus phase for Mars relevant compositions at or above 12 GPa. Early crystallization of this phase from a martian magma ocean yields a liquid characterized by an elevated CaO/Al₂O₃ ratio and a high Mg#. Olivine‐pyroxene‐garnet‐dominated cumulates that crystallize subsequently will also be characterized by superchondritic CaO/Al₂O₃ ratios. Melting of these cumulates yields liquids with major element compositions that are similar to calculated parental melts of the martian meteorites. Furthermore, crystallization models demonstrate that some of these cumulates have parent/daughter ratios that are similar to those calculated for the most incompatible‐element‐depleted source region (i.e., that of the meteorite Queen Alexandra [QUE] 94201). The incompatible‐element abundances of the most depleted (QUE 94201‐like) source region have also been calculated and provide an estimate of the composition of depleted martian mantle. The incompatible‐element pattern of depleted martian mantle calculated here is very similar to the pattern estimated for depleted Earth's mantle. Melting the depleted martian mantle composition reproduces the abundances of many incompatible elements in the parental melt of QUE 94201 (e.g., Ba, Th, K, P, Hf, Zr, and heavy rare earth elements) fairly well but does not reproduce the abundances of Rb, U, Ta and light rare earth elements. The source regions for meteorites such as Shergotty are successfully modeled as mixtures of depleted martian mantle and a late stage liquid trapped in the magma ocean cumulate pile. Melting of this hybrid source yields liquids with major element abundances and incompatible‐element patterns that are very similar to the Shergotty bulk rock.     

Frontier Mountain 93001: A coarse‐grained,enstatite‐augite‐oligoclase‐rich,igneous rock from the acapulcoite‐lodranite parent asteroid

Abstract— The Frontier Mountain (FRO) 93001 meteorite is a 4.86 g fragment of an unshocked, medium‐ to coarse‐grained rock from the acapulcoite‐lodranite (AL) parent body. It consists of anhedral orthoenstatite (Fs_{13.3 ± 0.4}Wo_{3.1 ± 0.2}), augite (Fs_{6.1 ± 0.7}Wo_{42.3 ± 0.9}; Cr₂O₃ = 1.54 ± 0.03), and oligoclase (Ab_{80.5 ± 3.3}Or_{3.1 ± 0.6}) up to >1 cm in size enclosing polycrystalline aggregates of fine‐grained olivine (average grain size: 460 ± 210 μm) showing granoblastic textures, often associated with Fe,Ni metal, troilite, chromite (cr# = 0.91 ± 0.03; fe# = 0.62 ± 0.04), schreibersite, and phosphates. Such aggregates appear to have been corroded by a melt. They are interpreted as lodranitic xenoliths. After the igneous (the term “igneous” is used here strictly to describe rocks or minerals that solidified from molten material) lithology intruding an acapulcoite host in Lewis Cliff (LEW) 86220, FRO 93001 is the second‐known silicate‐rich melt from the AL parent asteroid. Despite some similarities, the silicate igneous component of FRO 93001 (i.e., the pyroxene‐plagioclase mineral assemblage) differs in being coarser‐grained and containing abundant enstatite. Melting‐crystallization modeling suggests that FRO 93001 formed through high‐degree partial melting (≥35 wt%; namely, ≥15 wt% silicate melting and ?20 wt% metal melting) of an acapulcoitic source rock, or its chondritic precursor, at temperatures ≥1200 °C, under reducing conditions. The resulting magnesium‐rich silicate melt then underwent equilibrium crystallization; prior to complete crystallization at ?1040 °C, it incorporated lodranitic xenoliths. FRO 93001 is the highest‐temperature melt from the AL parent‐body so far available in laboratory. The fact that FRO 93001 could form by partial melting and crystallization under equilibrium conditions, coupled with the lack of quench‐textures and evidence for shock deformation in the xenoliths, suggests that FRO 93001 is a magmatic rock produced by endogenic heating rather than impact melting.     

Lithium isotopes and light lithophile element abundances in shergottites: Evidence for both magmatic degassing and subsolidus diffusion

Degassed magmatic water was potentially the major source of surficial water on Mars. We measured Li, B, and Be abundances and Li isotope profiles in pyroxenes, olivines, and maskelynite from four compositionally different shergottites—Shergotty, QUE 94201, LAR 06319, and Tissint—using secondary ion mass spectrometry (SIMS). All three light lithophile elements (LLE) are incompatible: Li and B are soluble in H₂O‐rich fluids, whereas Be is insoluble. In the analyzed shergottites, Li concentration decreases and Be concentration increases from cores to rims in pyroxenes. However, B concentrations do not vary consistently with Li and Be abundances, except in QUE 94201 pyroxenes. Additionally, abundances of these three elements in olivines show a normal igneous‐fractionation trend consistent with the crystallization of olivine before magma ascent and degassing. We expect that kinetic effects would lead to fractionation of ⁶Li in the vapor phase compared to ⁷Li during degassing. The Li isotope profiles, with increasing δ⁷Li from cores to rims, as well as Li and B profiles indicate possible degassing of hydrous fluids only for the depleted shergottite QUE 94201, as also supported by degassing models. Conversely, Shergotty, LAR 06319, and Tissint appear to have been affected by postcrystallization diffusion, based on their LLE and Li isotope profiles, accompanied by diffusion models. This process may represent an overlay on a degassing pattern. The LLE profiles and isotope profiles in QUE 94201 support the hypothesis that degassing of some basaltic shergottite magmas provided water to the Martian surface, although evidence may be obscured by subsolidus diffusion processes.     

The water content and parental magma of the second chassignite NWA 2737: Clues from trapped melt inclusions in olivine

NWA 2737, the second known chassignite, mainly consists of cumulate olivine crystals of homogeneous composition (Fo = 78.7 ± 0.9). These brown colored olivine grains exhibit two sets of perpendicular planar defects due to shock. Two forms of trapped liquids, interstitial melts and magmatic inclusions, have been examined. Mineral assemblages within the olivine‐hosted magmatic inclusions include low‐Ca pyroxene, augite, kaersutite, fluorapatite, biotite, chromite, sulfide, and feldspathic glass. The reconstructed parental magma composition (A^#) of the NWA 2737 is basaltic and resembles both the experimentally constrained parental melt composition of chassiginites and the Gusev basalt Humphrey, albeit with lower Al contents. A^# also broadly resembles the average of shergottite parent magmas or LAR 06319. However, we suggest that the mantle source for the chassignite parental magmas was distinct from that of the shergottite meteorites, particularly in CaO/Al₂O₃ ratio. In addition, based on the analysis of the volatile contents of kaersutite, we derived a water content of 0.48–0.67 wt% for the parental melt. Finally, our MELTS calculations suggest that moderate pressure (approximately 6.8 kb) came closest to reproducing the crystallized melt‐inclusion assemblages.     

Northwest Africa 10414, a pigeonite cumulate shergottite

Northwest Africa (NWA) 10414 is an unusual shergottite with a cumulate texture. It contains 73% coarse prismatic pigeonite, plus 18% interstitial maskelynite, 2% Si‐rich mesostasis, 2% merrillite, and minor chromite‐ulvöspinel. It contains no olivine, and only ~3% augite. Phase compositions are pigeonite (En_68‐43Fs_27‐48Wo_5‐15) and maskelynite An_~54‐36, more sodic than most maskelynite in shergottites. Chromite‐ulvöspinel composition plots between the earliest and most fractionated spinel‐group minerals in olivine‐phyric shergottites. NWA 10414 mineralogically resembles the contact facies between Elephant Moraine 79001 lithologic units A and B, with abundant pigeonite phenocrysts, though it is coarser grained. Its most Mg‐rich pigeonite also has a similar composition to the earliest crystallized pyroxenes in several other shergottites, including Shergotty. The Shergotty intercumulus liquid composition crystallizes pigeonite with a similar composition range to NWA 10414 pigeonite, using PETROLOG. Olivine‐phyric shergottite NWA 6234, with a pure magma composition, produces an even better match to this pigeonite composition range, after olivine crystallization. These observations suggest that after the accumulation of olivine from an olivine‐phyric shergottite magma, the daughter liquid could precipitate pigeonite locally to form this pigeonite cumulate, before the crystallization of overlying liquid as a normal basaltic shergottite.     

Laboratory experiments bearing on the origin and evolution of olivine‐rich chondrules

Abstract– Evaporation rates of K₂O, Na₂O, and FeO from chondrule‐like liquids and the associated potassium isotopic fractionation of the evaporation residues were measured to help understand the processes and conditions that affected the chemical and isotopic compositions of olivine‐rich type IA and type IIA chondrules from Semarkona. Both types of chondrules show evidence of having been significantly or totally molten. However, these chondrules do not have large or systematic potassium isotopic fractionation of the sort found in the laboratory evaporation experiments. The experimental results reported here provide new data regarding the evaporation kinetics of sodium and potassium from a chondrule‐like melt and the potassium isotopic fractionation of evaporation residues run under various conditions ranging from high vacuum to pressures of one bar of H₂+CO₂, or H₂, or helium. The lack of systematic isotopic fractionation of potassium in the type IIA and type IA chondrules compared with what is found in the vacuum and one‐bar evaporation residues is interpreted as indicating that they evolved in a partially closed system where the residence time of the surrounding gas was sufficiently long for it to have become saturated in the evaporating species and for isotopic equilibration between the gas and the melt. A diffusion couple experiment juxtaposing chondrule‐like melts with different potassium concentrations showed that the diffusivity of potassium is sufficiently fast at liquidus temperatures (D_K > 2 × 10^?4cm² s^?1 at 1650 °C) that diffusion‐limited evaporation cannot explain why, despite their having been molten, the type IIA and type IA chondrules show no systematic potassium isotopic fractionation.     

Volatile compounds in shergottite and nakhlite meteorites

Abstract— Vacuum pyrolysis and quadrupole mass spectrometry were used to measure evolved-gas profiles and total concentrations of H₂O, CO₂, CO, SO₂, S₂, H₂S, HCl, Cl, and hydrocarbons in both exterior and interior samples of shergottites (ALHA77005, EETA79001, and Shergotty), a nakhlite (Nakhla), and eucrites (ALHA81001, EETA79004, and Pasamonte). Eucrites were analyzed as control samples to monitor effects of terrestrial weathering and contamination, relative to properties sought for the shergottite-nakhlite parent body. In contrast with eucrites, shergottites and Nakhla contain large proportions of their sulfur as oxidized sulfur compounds. Sulfate occurs in all shergottite and Nakhla samples and carbonate was confirmed in EETA79001 and Nakhla. Carbonate and sulfate abundances are inversely correlated but total chlorine abundance varies directly with fractional sulfate abundance. Most of the volatile compounds seem to be anhydrous, based on low bulk water contents in the meteorites (<0.1% H₂O), although Nakhla might contain significant water that is chemically associated with chlorine. Traces of saturated and unsaturated hydrocarbons in some samples are most likely terrestrial contaminants. The indigenous volatile compounds indicate that the shergottite-nakhlite parent body was highly oxidizing and supported aqueous geochemistry during at least part of its history.     

Water in tektites and impact glasses by fourier-transformed infrared spectrometry

Abstract— To improve the scarce data base of H₂O content in tektites and impact glasses, we analyzed 26 tektites from all four strewn fields and 25 impact glass samples for their H₂O content. We used the fourier-transformed infrared (FTIR) spectrometry method, which permits measurement of areas of ～40 μm in diameter. Our results show that the tektites have H₂O contents ranging from 0.002 to 0.030 wt% (average 0.014 ± 0.008 wt%). Ivory Coast tektites have the lowest H₂O abundances (0.002–0.003 wt%), and Muong Nong-type indochinites and some North American tektites having the highest contents (up to ～0.03 wt%). Impact glass samples (from the Zhamanshin, Aouelloul, and Rio Cuarto craters) yielded H₂O contents of 0.008 to 0.13 wt% H₂O. Typical impact glasses from the Aouelloul and Zhamanshin craters have low H₂O contents (0.008 to 0.063 wt%). Libyan Desert Glasses and Rio Cuarto glasses have higher H₂O contents (～0.11 wt%). We also analyzed glasses of unknown origin (e.g., urengoites; glass fragments from Tikal), which showed very low H₂O contents, in agreement with an origin by impact. Our data confirm that all tektites found on land have very low H₂O contents (<0.03 wt% H₂O), while impact glasses have slightly higher H₂O contents. Both glass types are very dry compared to volcanic glasses. This study confirms that the low H₂O contents (<0.05 wt%) of such glasses can be considered good evidence for an origin by impact.     

Ion microprobe uranium‐thorium‐lead dating of Shergotty phosphates

Abstract— We report ion microprobe U‐Th‐Pb dating of Shergotty phosphates by means of the sensitive high‐resolution ion microprobe (SHRIMP) recently installed at Hiroshima University, Japan. ten analyses of whitlockite (merrillite) and three analyses of apatite indicate a ²³⁸u/²⁰⁶pb isochron age of 225 ± 200 ma and a tera‐wasserburg concordia‐constrained linear three‐dimensional isochron age of 217 ± 110 ma in the ²³⁸u/²⁰⁶pb‐²⁰⁷pb/²⁰⁶pb²⁰⁴pb/²⁰⁶pb diagram. These ages agree well with the 232Th‐208pb age of 189 ± 83 Ma, which suggests that primary crystallization or a shock metamorphic event defined the formation age of the phosphate minerals. The average of the later two ages, 204 ± 68 Ma, is consistent with the previously published Rb‐Sr age of 165 ± 11 Ma and U‐Th‐Pb age of ～200 Ma. These show marginal agreement with the ⁴⁰Ar‐³⁹Ar age of 254 ± 10 Ma but are significantly different from the Sm‐Nd age of 360 ± 16 Ma. Taking into account the closure temperature of the U‐Pb system in apatite, we suggest the time that Shergotty last experienced a temperature of ～900 °C was 204 ± 68 Ma.     

Experimental constraints on the solidification of a hydrous lunar magma ocean

The identification of hydrogen in a range of lunar samples and the similarity of its abundance and isotopic composition with terrestrial values suggest that water could have been present in the Moon since its formation. To quantify the effect of water on early lunar differentiation, we present new analyses of a high‐pressure, high‐temperature experimental study designed to model the mineralogical and geochemical evolution of the solidification material equivalent to 700 km deep lunar magma oceans first reported in Lin et al. (2017a). We also performed additional experiments to better quantify water contents in the run products. Water contents in the melt phases in hydrous run products spanning a range of crystallization steps were quantified directly using a secondary ion mass spectrometry (SIMS). Results suggest that a significant but constant proportion (68 ± 5%) of the hydrogen originally added to the experiments was lost from the starting material independent of run conditions and run duration. The volume of plagioclase formed during our crystallization experiments can be combined with the measured water contents and the observed crustal thickness on the Moon to provide an updated lunar interior hygrometer. Our data suggest that at least 45–354 ppm H₂O equivalent was present in the Moon at the time of crust formation. These estimates confirm the inference of Lin et al. (2017a) that the Moon was wet during its magma ocean stage, with corrected absolute water contents now comparable to estimates derived from the water content in a range of lunar samples.     

SHERGOTTY METEORITE: MINERALOGY,PETROGRAPHY AND MINOR ELEMENTS

The unusual achondrite Shergotty resembles terrestrial diabases, and textural and chemical evidence indicates pre-settling and post-settling crystallization of zoned augite (En₄₈Fs₁₉Wo₃₃-En₂₅Fs₄₇Wo₂₈) and pigeonite (En₆₁Fs₂₆Wo₁₃-En₂₁Fs₆₁Wo₁₈) coupled with late crystallization of plagioclase (Ab₄₃An₅₆/Or₁-Ab₅₆An₄₁Or₃: now shocked to maskelynite), titanomagnetite-ilmenite composite grains, mesostasis (normative Qz₃₄Ab₂₁An₅Or₃₈Fs₂, assuming Fe as ferrous), whitlockite, pyrrhotite (Fe_0.94S), fayalite (Fo₁₀), baddeleyite and chlorapatite. The oxide compositions (Usp₆₂Mt₃₈, Al₂O₃ 2.4, Cr₂O₃ 0.8 wt %; Ilm₉₅Hm₅) indicate ～ 850 °C and log oxygen fugacity ? 14, while the occurrence of fayalite rims on mesostasis next to ilmenite indicates 890 °C. Bearing in mind experimental uncertainties, these data are consistent with late-stage crystallization under relatively high oxygen fugacity, as indicated by coexistence of fayalite, Ti-magnetite and a silica glass. The high alkali content of the maskelynite and mesostasis, coupled with the redox state, indicates that the Shergotty meteorite resembles terrestrial basalts more than any other meteorites. Nevertheless the absence of H₂O, as shown by the occurrence of phosphorus in whitlockite rather than in hydroxylapatite, distinguish the Shergotty achondrite from typical terrestrial diabases. Whereas the FeO/MnO ratios of pyroxenes from the Moon, Earth and several differentiated meteorites are independent of FeO, the ratio for Shergotty pyroxenes changes from 30 to 40 with increasing FeO, and the linear trend extrapolates to 0.2 MnO for zero iron. Hence caution is needed in using FeO/MnO as a planetary indicator. For pyroxenes, Na is almost independent of Fe/Mg while Ti increases and Cr decreases with increasing Fe/Mg. Maskelynite contains 0.5–0.25 wt % K₂O, 0.6 wt % FeO, 0.04 TiO₂, 0.04–0.07 MgO, ～ 0.01 BaO and 0.02–0.03 P₂O₅. A bulk analysis calculated from the mode and compositions of the minerals matches quite well with two bulk chemical analyses but not with a third.     

Shergottites Dhofar 019, SaU 005, Shergotty,and Zagami: 40Ar‐39Ar chronology and trapped Martian atmospheric and interior argon

Abstract— We report a high‐resolution ⁴⁰Ar‐³⁹Ar study of mineral separates and whole‐rock samples of olivine‐phyric (Dhofar 019, Sayh al Uhaymir [SaU] 005) and basaltic (Shergotty, Zagami) shergottites. Excess argon is present in all samples. The highest (⁴⁰Ar/³⁶Ar)_trapped ratios are found for argon in pyroxene melt inclusions (?1500), maskelynite (?1200), impact glass (?1800) of Shergotty and impact glass of SaU 005 (?1200). A high (⁴⁰Ar/³⁶Ar)_trapped component‐usually uniquely ascribed to Martian atmosphere‐can also originate from the Martian interior, indicating a heterogeneous Martian mantle composition. As additional explanation of variable high (⁴⁰Ar/³⁶Ar)_trapped ratios in shocked shergottites, we suggest argon implantation from a “transient atmosphere” during impact induced degassing. The best ⁴⁰Ar‐³⁹Ar age estimate for Dhofar 019 is 642 ± 72 Ma (maskelynite). SaU 005 samples are between 700–900 Ma old. Relatively high ⁴⁰Ar‐³⁹Ar ages of melt inclusions within Dhofar 019 (1086 ± 252 Ma) and SaU 005 olivine (885 ± 66 Ma) could date entrapment of a magmatic liquid during early olivine crystallization, or reflect unrecognized excess ⁴⁰Ar components. The youngest ⁴⁰Ar‐³⁹Ar age of Shergotty separates (maskelynite) is ?370 Ma, that of Zagami is ?200 Ma. The ⁴⁰Ar‐³⁹Ar chronology of Dhofar 019 and SaU 005 indicate >1 Ga ages. Apparent ages uncorrected for trapped (e.g., Martian atmosphere, mantle) argon components approach 4.5 Ga, but are not caused by inherited ⁴⁰Ar, because excess ⁴⁰Ar is supported by ³⁶Ar_trapped. Young ages obtained by ⁴⁰Ar‐³⁹Ar and other chronometers argue for primary rather than secondary events. The cosmic ray exposure ages calculated from cosmogenic argon are 15.7 ± 0.7 Ma (Dhofar 019), 1.0–1.6 Ma (SaU 005), 2.1–2.5 Ma (Shergotty) and 2.2–3.0 Ma (Zagami).     

Petrogenesis of the Dar al Gani (DaG) 1.1 Ma ejection-paired olivine-phyric shergottites and implications for ~470 Ma Martian volcanism

The Dar al Gani (DaG) olivine-phyric shergottites share mineralogical and geochemical characteristics, which confirm that these meteorites are derived from a single source. Bulk trace elements (La/Yb—0.12), in situ maskelynite ⁸⁷Sr/⁸⁶Sr (~0.7014) and redox estimates (FMQ ~ −2) indicate derivation from a depleted, reduced mantle reservoir; identical to all ~470 Ma shergottites ejected at 1.1 Ma. The DaG shergottites have been variably affected by terrestrial alteration, which precipitated carbonate along fractures and modified bulk-rock fluid mobile (e.g., Ba) elements. Nonetheless, sufficient data are available to construct a multi-stage formation model for the DaG shergottites and other 1.1 Ma ejection-paired shergottites that erupted at ~470 Ma. First, partial melting of a depleted mantle source occurred at 1540 ± 20°C and 1.2 ± 0.1 GPa, equivalent to > ~100 km depth. Then, initial crystallization in a staging chamber at ~85 km depth at the crust–mantle boundary took place, followed by magma evolution and variable incorporation of antecrystic olivine ± orthopyroxene. Subsequently, crystallization of olivine phenocrysts and re-equilibration of olivine antecrysts occurred within an ascending magma. Finally, magmas with variable crystal loads erupted at the surface, where varied cooling rates produced a range of groundmass textures. This model is similar to picritic flood basalt magmas erupted on Earth.     

Search for sulfates on the surface of Ceres

The formation of hydrated salts is an expected consequence of aqueous alteration of Main Belt objects, particularly for large, volatile‐rich protoplanets like Ceres. Sulfates, present on water‐bearing planetary bodies (e.g., Earth, Mars, and carbonaceous chondrite parent bodies) across the inner solar system, may contribute to Ceres’ UV and IR spectral signature along with phyllosilicates and carbonates. We investigate the presence and stability of hydrated sulfates under Ceres’ cryogenic, low‐pressure environment and the consequent spectral effects, using UV–Vis–IR reflectance spectroscopy. H₂O loss begins instantaneously with vacuum exposure, measured by the attenuation of spectral water absorption bands, and a phase transition from crystalline to amorphous is observed for MgSO₄·6H₂O by X‐ray powder diffraction. Long‐term (>40 h), continuous exposure of MgSO₄·nH₂O (n = 0, 6, 7) to low pressure (10^?3–10^?6 Torr) causes material decomposition and strong UV absorption below 0.5 μm. Our measurements suggest that MgSO₄·6H₂O grains (45–83 μm) dehydrate to 2% of the original 1.9 μm water band area over ~0.3 Ma at 200 K on Ceres and after ~42 Ma for 147 K. These rates, inferred from an Avrami dehydration model, preclude MgSO₄·6H₂O as a component of Ceres’ surface, although anhydrous and minimally hydrated sulfates may be present. A comparison between Ceres emissivity spectra and laboratory reflectance measurements over the infrared range (5–17 μm) suggests sulfates cannot be excluded from Ceres’ mineralogy.     

Evidence for high‐temperature fractionation of lithium isotopes during differentiation of the Moon

Lithium isotope and abundance data are reported for Apollo 15 and 17 mare basalts and the LaPaz low‐Ti mare basalt meteorites, along with lithium isotope data for carbonaceous, ordinary, and enstatite chondrites, and chondrules from the Allende CV3 meteorite. Apollo 15 low‐Ti mare basalts have lower Li contents and lower δ⁷Li (3.8 ± 1.2‰; all uncertainties are 2 standard deviations) than Apollo 17 high‐Ti mare basalts (δ⁷Li = 5.2 ± 1.2‰), with evolved LaPaz mare basalts having high Li contents, but similar low δ⁷Li (3.7 ± 0.5‰) to Apollo 15 mare basalts. In low‐Ti mare basalt 15555, the highest concentrations of Li occur in late‐stage tridymite (>20 ppm) and plagioclase (11 ± 3 ppm), with olivine (6.1 ± 3.8 ppm), pyroxene (4.2 ± 1.6 ppm), and ilmenite (0.8 ± 0.7 ppm) having lower Li concentrations. Values of δ⁷Li in low‐ and high‐Ti mare basalt sources broadly correlate negatively with ¹⁸O/¹⁶O and positively with ⁵⁶Fe/⁵⁴Fe (low‐Ti: δ⁷Li ≤4‰; δ⁵⁶Fe ≤0.04‰; δ¹⁸O ≥5.7‰; high‐Ti: δ⁷Li >6‰; δ⁵⁶Fe >0.18‰; δ¹⁸O <5.4‰). Lithium does not appear to have acted as a volatile element during planetary formation, with subequal Li contents in mare basalts compared with terrestrial, martian, or vestan basaltic rocks. Observed Li isotopic fractionations in mare basalts can potentially be explained through large‐degree, high‐temperature igneous differentiation of their source regions. Progressive magma ocean crystallization led to enrichment in Li and δ⁷Li in late‐stage liquids, probably as a consequence of preferential retention of ⁷Li and Li in the melt relative to crystallizing solids. Lithium isotopic fractionation has not been observed during extensive differentiation in terrestrial magmatic systems and may only be recognizable during extensive planetary magmatic differentiation under volatile‐poor conditions, as expected for the lunar magma ocean. Our new analyses of chondrites show that they have δ⁷Li ranging between ?2.5‰ and 4‰. The higher δ⁷Li in planetary basalts than in the compilation of chondrites (2.1 ± 1.3‰) demonstrates that differentiated planetary basalts are, on average, isotopically heavier than most chondrites.     

K2O‐rich trapped melt in olivine in the Nakhla meteorite: Implications for petrogenesis of nakhlites and evolution of the Martian mantle

We used new analytical and theoretical methods to determine the major and minor element compositions of the primary trapped liquid (PTLs) represented by melt inclusions in olivine and augite in the Martian clinopyroxenite, Nakhla, for comparison with previously proposed compositions for the Nakhla (or nakhlite) parent magma. We particularly focused on obtaining accurate K₂O contents, and on testing whether high K₂O contents and K₂O/Na₂O ratios obtained in previous studies of melt inclusions in olivine in Nakhla could have been due to unrepresentative sampling, systematic errors arising from electron microprobe techniques, late alteration of the inclusions, and/or boundary layer effects. Based on analyses of 35 melt inclusions in olivine cores, the PTL in olivine, PTL_oliv, contained (by wt) approximately 47% SiO₂, 6.3% Al₂O₃, 9.6% CaO, 1.8% K₂O, and 0.9% Na₂O, with K₂O/Na₂O = 2.0. We infer that the high K₂O content of PTL_oliv is not due to boundary layer effects and represents a real property of the melt from which the host olivine crystallized. This melt was cosaturated with olivine and augite. Its mg# is model‐dependent and is constrained only to be ≥19 (equilibrium Fo = 40). Based on analyses of 91 melt inclusions in augite cores, the PTL in augite, PTL_aug, contained (by wt) 53–54% SiO₂, 7–8% Al₂O₃, 0.8–1.1% K₂O, and 1.1–1.4% Na₂O, with K₂O/Na₂O = 0.7–0.8. This K₂O content and K₂O/Na₂O ratio are significantly higher than inferred in studies of melt inclusions in augite in Nakhla by experimental rehomogenization. PTL_aug was saturated only with augite, and in equilibrium with augite cores of mg# 62. PTL_aug represents the Nakhla parent magma, and does not evolve to PTL_oliv by fractional crystallization. We therefore conclude that olivine cores in Nakhla (and, by extension, other nakhlites) are xenocrystic. We propose that PTL_oliv and PTL_aug were generated from the same source region. PTL_oliv was generated first and emplaced to form olivine‐rich cumulate rocks. Shortly thereafter, PTL_aug was generated and ascended through these olivine‐rich cumulates, incorporating fragments of wallrock that became the xenocrystic olivine cores in Nakhla. The Nakhla (nakhlite) mantle source region was pyroxenitic with some olivine, and could have become enriched in K relative to Na via metasomatism. A high degree of melting of this source produced the silica‐poor, alkali‐rich magma PTL_oliv. Further ascension and decompression of the source led to generation of the silica‐rich, relatively alkali‐poor magma PTL_aug. Potassium‐rich magmas like those involved in the formation of the nakhlites represent an important part of the diversity of Martian igneous rocks.