The volatile content of Vesta: Clues from apatite in eucrites

Apatite was analyzed by electron microprobe in 3 cumulate and 10 basaltic eucrites. Eucritic apatite is fluorine‐rich with minor chlorine and hydroxyl (calculated by difference). We confirmed the hydroxyl content by measuring hydroxyl directly in apatites from three representative eucrites using secondary ionization mass spectroscopy. Overall, most eucritic apatites resemble fluorine‐rich lunar mare apatites, but intriguing OH‐ and Cl‐rich apatites suggest a role for water and/or hydrothermal fluids in the Vestan interior or on other related differentiated asteroids. Most late‐stage apatite found in mesostasis has little hydroxyl or chlorine and is thought to have crystallized from a degassed magma; however, several apatites exhibit atypical compositions and/or textural characteristics. For example, the isotopically anomalous basaltic eucrite Pasamonte has apatite in the mesostasis with significant OH. Apatites in Juvinas also have significant OH and occur as veinlets crosscutting silicates. Euhedral apatites in the Moore County cumulate eucrite occur as inclusions in pyroxene and are also hydroxyl‐rich (0.62 wt% OH). The OH was confirmed by SIMS analysis and this apatite clearly points to the presence of water, at least locally, in the Vestan interior. Portions of Elephant Moraine (EET) 90020 have large and abundant apatites, which may be the product of apatite accumulation in a zone of melt‐rock reaction. Relatively chlorine‐rich apatites occur in basaltic eucrite Graves Nunataks (GRA) 98098 (approximately 1 wt% Cl). Particularly striking is the compositional similarity between apatite in GRA 98098 and apatites in lunar KREEP, which may indicate the presence of residual magmas from an asteroid‐wide magma ocean on Vesta.     

Ancient geologic events on Mars revealed by zircons and apatites from the Martian regolith breccia NWA 7034

Zircons and apatites in clasts and matrix from the Martian breccia NWA 7034 are well documented, timing ancient geologic events on Mars. Furthermore, in this study, zircon trace elemental content, apatite volatile content, and apatite volatile isotopic compositions measured in situ could constrain the evolution of those geologic events. The U‐Pb dates of zircons in basalt, basaltic andesite, trachyandesite igneous clasts, and the matrix are similar (4.4 Ga) suggesting intense volcanism on ancient Mars. However, two metamict zircon grains found in the matrix have an upper intercept date of ~4465 Ma in crystalline, whereas amorphous areas have a lower intercept date of 1634 ± 93 Ma. The younger date is consistent with the date of apatites (1530 ± 65 Ma), suggesting a metamorphic event that completely reset the U‐Pb system in both the amorphous areas of zircon and all apatites. δD values in all apatites negatively correlate with water content in a two‐endmember mixing trend. The D (δD up to 2459‰) and ³⁷Cl heavy core (3.8‰) of a large apatite grain suggest a D‐, ³⁷Cl‐rich fluid during the metamorphic event ~1.6 Ga ago, consistent with the trace elements Y, Hf and Ti and P in zircons. The fluid was also therefore P‐rich. The D‐, ³⁷Cl‐poor H₂O‐rich rim (<313‰) suggests the degassing of water from the Martian Cl‐poor interior at a later time. This D‐, ³⁷Cl‐poor Martian mantle reservoir could have derived from volcanic intrusions postdating the younger metamorphic event recorded in NWA 7034.     

Heterogeneous distribution of H2O in the Martian interior: Implications for the abundance of H2O in depleted and enriched mantle sources

We conducted a petrologic study of apatite within 12 Martian meteorites, including 11 shergottites and one basaltic regolith breccia. These data were combined with previously published data to gain a better understanding of the abundance and distribution of volatiles in the Martian interior. Apatites in individual Martian meteorites span a wide range of compositions, indicating they did not form by equilibrium crystallization. In fact, the intrasample variation in apatite is best described by either fractional crystallization or crustal contamination with a Cl‐rich crustal component. We determined that most Martian meteorites investigated here have been affected by crustal contamination and hence cannot be used to estimate volatile abundances of the Martian mantle. Using the subset of samples that did not exhibit crustal contamination, we determined that the enriched shergottite source has 36–73 ppm H₂O and the depleted source has 14–23 ppm H₂O. This result is consistent with other observed geochemical differences between enriched and depleted shergottites and supports the idea that there are at least two geochemically distinct reservoirs in the Martian mantle. We also estimated the H₂O, Cl, and F content of the Martian crust using known crust‐mantle distributions for incompatible lithophile elements. We determined that the bulk Martian crust has ~1410 ppm H₂O, 450 ppm Cl, and 106 ppm F, and Cl and H₂O are preferentially distributed toward the Martian surface. The estimate of crustal H₂O results in a global equivalent surface layer (GEL) of ~229 m, which can account for at least some of the surface features on Mars attributed to flowing water and may be sufficient to support the past presence of a shallow sea on Mars' surface.     

Constraints on the water,chlorine, and fluorine content of the Martian mantle

Previous estimates of the volatile contents of Martian basalts, and hence their source regions, ranged from nearly volatile‐free through estimates similar to those found in terrestrial subduction zones. Here, we use the bulk chemistry of Martian meteorites, along with Martian apatite and amphibole chemistry, to constrain the volatile contents of the Martian interior. Our estimates show that the volatile content of the source region for the Martian meteorites is similar to the terrestrial Mid‐Ocean‐Ridge Mantle source. Chlorine is enriched compared with the depleted terrestrial mantle but is similar to the terrestrial enriched source region; fluorine is similar to the terrestrial primitive mantle; and water is consistent with the terrestrial mantle. Our results show that Martian magmas were not volatile saturated; had water/chlorine and water/fluorine ratios ~0.4–18; and are most similar, in terms of volatiles, to terrestrial MORBs. Presumably, there are variations in volatile content in the Martian interior as suggested by apatite compositions, but more bulk chemical data, especially for fluorine and water, are required to investigate these variations. Finally, the Noachian Martian interior, as exemplified by surface basalts and NWA 7034, may have had higher volatile contents.     

Petrography,mineral chemistry,and crystallization history of olivine‐phyric shergottite NWA 6234: A new melt composition

Knowledge of Martian igneous and mantle compositions is crucial for understanding Mars' mantle evolution, including early differentiation, mantle convection, and the chemical alteration at the surface. Primitive magmas provide the most direct information about their mantle source regions, but most Martian meteorites either contain cumulate olivine or crystallized from fractionated melts. The new Martian meteorite Northwest Africa (NWA) 6234 is an olivine‐phyric shergottite. Its most magnesian olivine cores (Fo₇₈) are in Mg‐Fe equilibrium with a magma of the bulk rock composition, suggesting that it represents a melt composition. Thermochemical calculations show that NWA 6234 not only represents a melt composition but is a primitive melt derived from an approximately Fo₈₀ mantle. Thus, NWA 6234 is similar to NWA 5789 and Y 980459 in the sense that all three are olivine‐phyric shergottites and represent primitive magma compositions. However, NWA 6234 is of special significance because it represents the first olivine‐phyric shergottite from a primitive ferroan magma. On the basis of Al/Ti ratio of pyroxenes in NWA 6234, the minor components in olivine and merrillite, and phosphorus zoning of olivine, we infer that the rock crystallized completely at pressures consistent with conditions in Mars' upper crust. The textural intergrowths of the two phosphates (merrillite and apatite) indicate that at a very last stage of crystallization, merrillite reacted with an OH‐Cl‐F‐rich melt to form apatite. As this meteorite crystallized completely at depth and never erupted, it is likely that its apatite compositions represent snapshots of the volatile ratios of the source region without being affected by degassing processes, which contain high OH‐F content.     

Magmatic history and parental melt composition of olivine‐phyric shergottite LAR 06319: Importance of magmatic degassing and olivine antecrysts in Martian magmatism

Several olivine‐phyric shergottites contain enough olivine that they could conceivably represent the products of closed‐system crystallization of primary melts derived from partial melting of the Martian mantle. Larkman Nunatak (LAR) 06319 has been suggested to represent a close approach to a Martian primary liquid composition based on approximate equilibrium between its olivine and groundmass. To better understand the olivine–melt relationship and the evolution of this meteorite, we report the results of new petrographic and chemical analyses. We find that olivine megacryst cores are generally not in equilibrium with the groundmass, but rather have been homogenized by diffusion to Mg# 72. We have identified two unique grain types: an olivine glomerocryst and an olivine grain preserving a primary magmatic boundary that constrains the time scale of eruption to be on the order of hours. We also report the presence of trace oxide phases and phosphate compositions that suggest that the melt contained approximately 1.1% H₂O and lost volatiles during cooling, also associated with an increase in oxygen fugacity upon degassing. We additionally report in situ rare earth element measurements of the various mineral phases in LAR 06319. Based on these reported trace element abundances, we estimate the oxygen fugacity in the LAR 06319 parent melt early in its crystallization sequence (i.e., at the time of crystallization of the low‐Ca and high‐Ca pyroxenes), the rare earth element composition of the parent melt, and those of melts in equilibrium with later formed phases. We suggest that LAR 06319 represents the product of closed‐system crystallization within a shallow magma chamber, with additional olivine accumulated from a cumulate pile. We infer that the olivine megacrysts are antecrysts, derived from a single magma chamber, but not directly related to the host magma, and suggest that mixing of antecrysts within magma chambers may be a common process in Martian magmatic systems.     

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.     

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.     

Petrology and trace element geochemistry of Tissint,the newest shergottite fall

The fall and recovery of the Tissint meteorite in 2011 created a rare opportunity to examine a Martian sample with a known, short residence time on Earth. Tissint is an olivine‐phyric shergottite that accumulated olivine antecrysts within a single magmatic system. Coarse olivine grains with nearly homogeneous cores of Mg# >80 suggest slow re‐equilibration. Many macroscopic features of this sample resemble those of LAR 06319, including the olivine crystal size distribution and the presence of evolved oxide and olivine compositions. Unlike LAR 06319, however, no magmatic hydrous phases were found in the analyzed samples of Tissint. Minor and trace element compositions indicate that the meteorite is the product of closed‐system crystallization from a parent melt derived from a depleted source, with no obvious addition of a LREE‐rich (crustal?) component prior to or during crystallization. The whole‐rock REE pattern is similar to that of intermediate olivine‐phyric shergottite EETA 79001 lithology A, and could also be approximated by a more olivine‐rich version of depleted basaltic shergottite QUE 94201. Magmatic oxygen fugacities are at the low end of the shergottite range, with log fO₂ of QFM‐3.5 to ‐4.0 estimated based on early‐crystallized minerals and QFM‐2.4 estimated based on the Eu in pyroxene oxybarometer. These values are similarly comparable to other depleted shergottites, including SaU 005 and QUE 94201. Tissint occupies a previously unsampled niche in shergottite chemistry: containing olivines with Mg# >80, resembling the enriched olivine‐phyric shergottite LAR 06319 in its crystallization path, and comparable to intermediate olivine‐phyric shergottite EETA 79001A, depleted olivine‐phyric shergottite DaG 476, and depleted basaltic shergottite QUE 94201 in its trace element abundances and oxygen fugacity. The apparent absence of evidence for terrestrial alteration in Tissint (particularly in trace element abundances in the whole‐rock and individual minerals) confirms that exposure to the arid desert environment results in only minimal weathering of samples, provided the exposure times are brief.     

Fluids on differentiated asteroids: Evidence from phosphates in differentiated meteorites GRA 06128 and GRA 06129

Abstract– Paired meteorites Graves Nunatak 06128 and 06129 (GRA) represent an ancient cumulate lithology (4565.9 Ma ± 0.3) containing high abundances of sodic plagioclase. Textures and stable isotope compositions of GRA indicate that superimposed on the igneous lithology is a complex history of subsolidus reequilibration and low‐temperature alteration that may have extended over a period of 150 Myr. In GRA, apatite is halogen‐rich with Cl between 4.5 and 5.5 wt% and F between 0.3 and 0.9 wt%. The Cl/(Cl+F+OH) ratio of the apatite is between 0.65 and 0.82. The Cl and F are negatively correlated and are heterogeneously distributed in the apatite. Merrillite is low in halogens with substantial Na in the 6‐fold coordinated Na‐site (≈2.5%) and Mg in the smaller octahedral site. The merrillite has a negative Eu anomaly, whereas the apatite has a positive Eu anomaly. The chlorine isotope composition of the bulk GRA leachate is +1.2‰ relative to standard mean ocean chloride (SMOC). Ion microprobe chlorine isotope analyses of the apatite range between ?0.5 and +1.2‰. Textural relationships between the merrillite and apatite, and the high‐Cl content of the apatite, suggest that the merrillite is magmatic in origin, whereas the apatite is a product of the interaction between merrillite and a Cl‐rich fluid. If the replacement of merrillite by apatite occurred at approximately 800 °C, the fluid composition is f(HCl)/f(H₂O) = 0.0383 and a HCl molality of 2.13 and f(HCl)/f(HF) = 50–100. It is anticipated that the calculated f(HCl)/f(H₂O) and a HCl molality are minimum values due to assumptions made on the OH component in apatite and basing the calculations on the apatite with the lowest X_Cl. The bulk δ³⁷Cl of GRA is a >2σ outlier from chondritic meteorites and suggests that parent body processes resulted in fractionation of the Cl isotopes.     

Cover

The papers in this special issue are based on the Workshop on Volatiles in the Martian Interior, which was held at the Lunar and Planetary Institute in November 2014. The top panel shows the topography of the equatorial region of Mars, based on NASA Mars Global Surveyor data. The second panel is from Figure 1 within Breuer et al. (pp. 1959–1958). The top half of the second panel shows schematic diagrams of the initial water distribution after accretion and magma ocean crystallization for three different formation scenarios and the bottom half of the second panel shows possible present‐day water confi gurations on Mars. The bottom panel comes from Howarth et al. (pp. 2061–2072) and shows X‐ray compositional maps for apatites from the enriched, olivine‐phyric shergottite LAR 12011. Panel (a) shows a Ca X‐ray map of apatite, and panel (b) shows a Cl X‐ray map of the same apatite.     

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.     

The chlorine isotope composition of Martian meteorites 2. Implications for the early solar system and the formation of Mars

We determined the chlorine isotope composition of 16 Martian meteorites using gas source mass spectrometry on bulk samples and in situ secondary ion microprobe analysis on apatite grains. Measured δ³⁷Cl values range from ?3.8 to +8.6‰. The olivine‐phyric shergottites are the isotopically lightest samples, with δ³⁷Cl mostly ranging from ?4 to ?2‰. Samples with evidence for a crustal component have positive δ³⁷Cl values, with an extreme value of 8.6‰. Most of the basaltic shergottites have intermediate δ³⁷Cl values of ?1 to 0‰, except for Shergotty, which is similar to the olivine‐phyric shergottites. We interpret these data as due to mixing of a two‐component system. The first component is the mantle value of ?4 to ?3‰. This most likely represents the original bulk Martian Cl isotope value. The other endmember is a ³⁷Cl‐enriched crustal component. We speculate that preferential loss of ³⁵Cl to space has resulted in a high δ³⁷Cl value for the Martian surface, similar to what is seen in other volatile systems. The basaltic shergottites are a mixture of the other two endmembers. The low δ³⁷Cl value of primitive Mars is different from Earth and most chondrites, both of which are close to 0‰. We are not aware of any parent‐body process that could lower the δ³⁷Cl value of the Martian mantle to ?4 to ?3‰. Instead, we propose that this low δ³⁷Cl value represents the primordial bulk composition of Mars inherited during accretion. The higher δ³⁷Cl values seen in many chondrites are explained by later incorporation of ³⁷Cl‐enriched HCl‐hydrate.     

The chlorine isotopic composition of Martian meteorites 1: Chlorine isotope composition of Martian mantle and crustal reservoirs and their interactions

The Martian meteorites record a wide diversity of environments, processes, and ages. Much work has been done to decipher potential mantle sources for Martian magmas and their interactions with crustal and surface environments. Chlorine isotopes provide a unique opportunity to assess interactions between Martian mantle‐derived magmas and the crust. We have measured the Cl‐isotopic composition of 17 samples that span the range of known ages, Martian environments, and mantle reservoirs. The ³⁷Cl of the Martian mantle, as represented by the olivine‐phyric shergottites, NWA 2737 (chassignite), and Shergotty (basaltic shergottite), has a low value of approximately ?3.8‰. This value is lower than that of all other planetary bodies measured thus far. The Martian crust, as represented by regolith breccia NWA 7034, is variably enriched in the heavy isotope of Cl. This enrichment is reflective of preferential loss of ³⁵Cl to space. Most basaltic shergottites (less Shergotty), nakhlites, Chassigny, and Allan Hills 84001 lie on a continuum between the Martian mantle and crust. This intermediate range is explained by mechanical mixing through impact, fluid interaction, and assimilation‐fractional crystallization.     

Experimental petrology,crystallization history,and parental magma characteristics of olivine‐phyric shergottite NWA 1068: Implications for the petrogenesis of “enriched” olivine‐phyric shergottites

Abstract– Northwest Africa (NWA) 1068 is one of the few olivine‐phyric shergottites (e.g., NWA 1068, Larkman Nunatak [LAR] 06319, and Roberts Massif [RBT] 04262) that is not depleted in light rare earth elements (LREE). Its REE pattern is similar to that of the basaltic shergottite Shergotty, suggesting a possible connection between the olivine‐phyric and the basaltic shergottites. To test this possible link, we have investigated the high‐pressure near‐liquidus phase equilibria for the NWA 1068 meteorite bulk composition. Our results show that the NWA 1068 bulk composition does not represent an unmodified mantle‐derived melt; the olivine and pyroxene in our near‐liquidus experiments are more magnesian than in the rock itself, which suggests that NWA 1068 contains cumulate minerals (extra olivine). We have then used these experimental results combined with the pyroxene compositions in NWA 1068 to constrain the possible high‐pressure crystallization history of the parental magma. These results suggest that NWA 1068 had a complex polybaric history. Finally, we have calculated a model parental magma composition for the NWA 1068 meteorite. The calculated parental magma is an evolved basaltic composition which is too ferroan to be a primitive melt directly derived from the mantle. We suggest that it ponded and crystallized at approximately the base of the crust. This provided an opportunity for the magma to become contaminated by an “enriched” crustal component prior to crystallization. The results and modeling from these experiments are applicable not only to the NWA 1068 meteorite, but also to LAR 06319 and possibly any other enriched olivine‐phyric shergottite.     

The chlorine isotope composition of iron meteorites: Evidence for the Cl isotope composition of the solar nebula and implications for extensive devolatilization during planet formation

The bulk chlorine concentrations and isotopic compositions of a suite of non‐carbonaceous (NC) and carbonaceous (CC) iron meteorites were measured using gas source mass spectrometry. The δ³⁷Cl values of magmatic irons range from ?7.2 to 18.0‰ versus standard mean ocean chloride and are unrelated to their chlorine concentrations, which range from 0.3 to 161 ppm. Nonmagmatic IAB irons are comparatively Cl‐rich containing >161 ppm with δ³⁷Cl values ranging from ?6.1 to ?3.2‰. The anomalously high and low δ³⁷Cl values are inconsistent with a terrestrial source, and as Cl contents in magmatic irons are largely consistent with derivation from a chondrite‐like silicate complement, we suggest that Cl is indigenous to iron meteorites. Two NC irons, Cape York and Gibeon, have high cooling rates with anomalously high δ³⁷Cl values of 13.4 and 18.0‰. We interpret these high isotopic compositions to result from Cl degassing during the disruption of their parent bodies, consistent with their low volatile contents (Ga, Ge, Ag). As no relevant mechanisms in iron meteorite parent bodies are expected to decrease δ³⁷Cl values, whereas volatilization is known to increase δ³⁷Cl values by the preferential loss of light isotopes, we interpret the low isotope values of <?5‰ and down to ?7.2‰ to most closely represent the primordial isotopic composition of Cl in the solar nebula. Similar conclusions have been derived from low δ³⁷Cl values down to ?6, and ?3.8‰ measured in Martian and Vestan meteorites, respectively. These low δ³⁷Cl values are in contrast to those of chondrites which average around 0‰ previously explained by the incorporation of isotopically heavy HCl clathrate into chondrite parent bodies. The poor retention of low δ³⁷Cl values in many differentiated planetary materials suggest that extensive devolatilization occurred during planet formation, which can explain Earth's high δ³⁷Cl value by the loss of approximately 60% of the initial Cl content.     

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.     

A petrogenetic model for the comagmatic origin of chassignites and nakhlites: Inferences from chlorine‐rich minerals,petrology, and geochemistry

Twelve samples belonging to the chassignite and nakhlite subgroups of Martian meteorites were investigated using a variety of micro‐beam analytical techniques to gain insight into the petrogenesis of these two meteorite classes. There are a striking number of geochemical similarities between the chassignites and nakhlites, including mineralogy and petrology, crystallization age, cosmic‐ray exposure age, and radiogenic isotopic compositions. However, there are also geochemical differences, namely in trace element systematics of pyroxenes, that have led some authors to conclude that the nakhlites are comagmatic with each other, but not comagmatic with the chassignites. On the basis of data presented here, we propose a model in which these differences can be reconciled by the addition of an exogenous Cl‐rich fluid to the chassignite‐nakhlite magma body shortly after the formation of the cumulate horizon that was sampled by the Chassigny meteorite. This model is supported by the textural and chemical associations of the volatile‐bearing minerals apatite, amphibole, and biotite, which record a history starting with the addition of a Cl‐ and LREE‐enriched fluid to the magma body. As the magma continued to crystallize, it eventually reached chloride saturation and degassed a Cl‐rich fluid phase. Depending on the provenance of the Cl‐rich fluid, this model could explain how the chassignites and nakhlites originated from an LREE‐depleted source, yet all exhibit LREE‐enriched bulk‐rock patterns. Additionally, the model explains the range in oxygen fugacity that is recorded by the chassignites and nakhlites because eventual exsolution and loss of Cl‐rich fluid phases near the end of crystallization of the nakhlite sequence leads to auto‐oxidation of the magma body due to the preferential partitioning of Fe²⁺ into the fluid phase.     

Hydrogen isotopic composition of the Martian mantle inferred from the newest Martian meteorite fall,Tissint

The hydrogen isotopic composition of planetary reservoirs can provide key constraints on the origin and history of water on planets. The sources of water and the hydrological evolution of Mars may be inferred from the hydrogen isotopic compositions of mineral phases in Martian meteorites, which are currently the only samples of Mars available for Earth‐based laboratory investigations. Previous studies have shown that δD values in minerals in the Martian meteorites span a large range of ?250 to +6000‰. The highest hydrogen isotope ratios likely represent a Martian atmospheric component: either interaction with a reservoir in equilibrium with the Martian atmosphere (such as crustal water), or direct incorporation of the Martian atmosphere due to shock processes. The lowest δD values may represent those of the Martian mantle, but it has also been suggested that these values may represent terrestrial contamination in Martian meteorites. Here we report the hydrogen isotopic compositions and water contents of a variety of phases (merrillites, maskelynites, olivines, and an olivine‐hosted melt inclusion) in Tissint, the latest Martian meteorite fall that was minimally exposed to the terrestrial environment. We compared traditional sample preparation techniques with anhydrous sample preparation methods, to evaluate their effects on hydrogen isotopes, and find that for severely shocked meteorites like Tissint, the traditional sample preparation techniques increase water content and alter the D/H ratios toward more terrestrial‐like values. In the anhydrously prepared Tissint sample, we see a large range of δD values, most likely resulting from a combination of processes including magmatic degassing, secondary alteration by crustal fluids, shock‐related fractionation, and implantation of Martian atmosphere. Based on these data, our best estimate of the δD value for the Martian depleted mantle is ?116 ± 94‰, which is the lowest value measured in a phase in the anhydrously prepared section of Tissint. This value is similar to that of the terrestrial upper mantle, suggesting that water on Mars and Earth was derived from similar sources. The water contents of phases in Tissint are highly variable, and have been affected by secondary processes. Considering the H₂O abundances reported here in the driest phases (most likely representing primary igneous compositions) and appropriate partition coefficients, we estimate the H₂O content of the Tissint parent magma to be ≤0.2 wt%.     

H and Cl isotope systematics of apatite in brecciated lunar meteorites Northwest Africa 4472, Northwest Africa 773, Sayh al Uhaymir 169, and Kalahari 009

We have investigated the H and Cl systematics in apatite from four brecciated lunar meteorites. In Northwest Africa (NWA) 4472, most of the apatites contain ～2000–6000 ppm H₂O with δD between ?200 and 0‰, except for one grain isolated in the matrix, which contains ～6000 ppm H₂O with δD of ～500–900‰. This low‐δD apatite contains ～2500–7500 ppm Cl associated with δ³⁷Cl of ～15–20‰, while the high‐δD grain contains ～2500 ppm Cl with δ³⁷Cl of ～7–15‰. In NWA 773, apatites in a first group contain ～700–2500 ppm H₂O with δD values averaging around ～0 ± 100‰, while apatites in a second group contain ～5500–16500 ppm H₂O with δD ～250 ± 50‰. In Sayh al Uhaymir (SaU) 169 and Kalahari (Kal) 009, apatites are similar in terms of their H₂O contents (～600–3000 ppm) and δD values (?100 to 200‰). In SaU 169, apatites contain ～6000–10,000 ppm Cl, characterized by δ³⁷Cl of ～5–12‰. Overall, most of the analyzed apatite grains have δD within the range reported for carbonaceous chondrites, similar to apatite analyzed in ancient (>3.9 Ga) lunar magmatic. One grain in NWA 4472 has H and Cl isotope compositions similar to apatite from mare basalts. With an age of 4.35 Ga, this grain could be a representative of the oldest known lunar volcanic activity. Finally, since numerous evolved clasts in NWA 773 formed through silicate liquid immiscibility, the apatite grains with extremely high H₂O contents, reaching pure hydroxylapatite composition, could provide insights into the effects of such process on the evolution of volatiles in lunar magmas.