¹Jesse Reimink,²Carolyn Crow,³Desmond Moser,⁴Benjamin Jacobsen,⁵Ann Bauer,⁶Thomas Chacko
Earth and Planetary Science Letters 604, 118007 Link to Article [https://doi.org/10.1016/j.epsl.2023.118007]
¹Department of Geosciences, Penn State University, PA, 16802, USA
²Department of Geological Sciences, CU Boulder, CO, 80309, USA
³Department of Earth Sciences, University of Western Ontario, Ontario, N6A 3K7, Canada
⁴Nuclear and Chemical Science Division, Lawrence Livermore National Laboratory, 94550, USA
⁵Department of Geoscience, University of Wisconsin, WI, 53706, USA
⁶Department of Earth and Atmospheric Science, University of Alberta, Alberta, T6G 2E3, Canada
Copyright Elsevier

The first 500 million years of Earth history is thought to be a period of intense planetary bombardment, but the timing and flux of this meteorite bombardment is poorly understood. In particular, on the basis of an inferred lunar impact history, some workers have hypothesized a ∼3.9 Ga terminal cataclysm (TC) in which there was marked increase in the impact flux affecting the Moon, the Earth and possibly other terrestrial planets. Minerals that survived this enigmatic period offer a way to test early planetary bombardment models as they may contain telltale micro- to nanoscale shock features. Here, we present results from a numerical modeling calculation that assesses the probability that a zircon residing in the crust would escape shock melting or shock deformation during a TC bombardment event. Even with conservative pressure estimates for zircon shock deformation and intermediate bombardment intensities, we find that only ∼6% of ≥4.0 Ga crust would be expected to survive a 3.9 Ga cataclysm without experiencing either complete melting or zircon shock metamorphism. We couple this modeling with a search for shock effects in the oldest zircons from the Acasta Gneiss Complex, which would have been present in the Earth’s crust during a putative 3.9 Ga TC. Spatially correlated electron and NanoSIMS ion microscopy of 4.02 Ga igneous zircons from Acasta reveals no evidence of ancient shock. These data, together with similar results from other Hadean zircon suites, confirm that a post-Hadean TC is unlikely to have occurred. We suggest that the dearth of pre-3.9 Ga terrestrial crust and zircons is instead best explained by endogenic processes related to the mechanisms of early crust formation. Our modeling allows us to evaluate bombardment scenarios from the terrestrial zircon record by applying probabilistic interpretations to zircon shock deformation data. This approach will be valuable for other planetary bodies, allowing broader conclusions to be drawn from geographically limited datasets.

¹Marina Martínez,^1,2Charles K.Shearer,¹Adrian J.Brearley
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.016]
¹Department of Earth & Planetary Sciences, MSC03-2040, 1University of New Mexico, Albuquerque, NM 87131, USA
²Institute of Meteoritics, MSC03-2040, University of New Mexico, Albuquerque, NM 87131, USA
Copyright Elsevier

Melt inclusions are of major significance because they can constrain the volatile abundances in magmas. Here, we report the discovery of the first melt inclusion in a martian apatite containing the first chloro-amphibole reported in Northwest Africa (NWA) 998, a sample that crystallized early from the nakhlite-source. The amphibole is also the first sodic-calcic amphibole in a nakhlite, identified as ferro-chloro-winchite (4.75 wt% Cl) by FIB-TEM. The melt inclusion is present in a euhedral, cumulus apatite grain (Cl/F = 2.11) and is surrounded by a shell of voids. Evidence indicates that the melt inclusion remained as a closed system although syn- and post-entrapment processes may have modified the chemical composition of the original trapped melt. The inclusion also contains Fe-rich, Ca-poor pyroxene and a residual silicate melt consisting of pyroxene and interstitial K-rich glass. Additionally, Cl-enriched apatite is present within the boundaries of the melt inclusion. This apatite could result from cracking of host-apatite during contraction of the melt inclusion glass or represent daughter apatite crystallizing on the walls of the inclusion. Given that Cl-enrichments are found in the host apatite outside the melt inclusion, it is inferred that a later, fluid alteration event locally modified the composition of the apatite in and/or around the melt inclusion. The calculated bulk composition of the melt inclusion is generally consistent with previous work in other nakhlites. Prior to this study, Cl-rich amphiboles have only been found within olivine- and pyroxene-hosted melt inclusions in the later-formed nakhlites. The present study thus demonstrates that (i) the nakhlites record magmatic mixing with a Cl-rich exogenous component that is absent within olivine-hosted melt inclusions in the chassignites, (ii) Cl-rich amphiboles were able to crystallize from the earliest nakhlite parent melt, and (iii) the presence of a Cl-rich fluid was not required to stabilize chloro-amphiboles. We also conclude that magmatic martian amphiboles likely stabilized at lower pressures (and temperatures) than terrestrial amphiboles due to their higher Cl contents.

^1,2C.Deligny,¹E.Füri,¹E.Deloule,^3,4A.H.Peslier,¹F.Faure,¹Y.Marrocchi
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.017]
¹Université de Lorraine, CNRS, CRPG, F-54000 Nancy, France
²Department of Geosciences, Swedish Museum of Natural History, Stockholm, Sweden1
³Jacobs, NASA-Johnson Space Center, Mail Code X13, Houston, TX 77058, USA
⁴Dept. of Geological Sciences, New Mexico State University, Las Cruces, NM 88011, USA
Copyright Elsevier

Martian meteorites are key for assessing the isotopic characteristics of nitrogen in different martian reservoirs (i.e., mantle, crust, and atmosphere), and, ultimately, for constraining the source(s) of nitrogen trapped during the earliest stages of planetary accretion in the terrestrial planet-forming region. In this study, we analysed, for the first time, the nitrogen content and isotopic composition of glassy melt inclusions of Chassigny and of the mesostasis of five nakhlites (MIL 03346, Nakhla, NWA 6148, NWA 998, and Y 000593) by in situ secondary ion mass spectrometry. The nitrogen content of Chassigny melt inclusions, corrected for olivine overgrowth on the inclusion walls, varies from 4 ± 1 to 860 ± 45 ppm N, and the majority of δ15N values range from –35 ± 41 to +73 ± 36‰. The estimated nitrogen isotopic signature of the primitive melt, prior to degassing of N2 or NH3, is 0 ± 32‰. The mesostasis of nakhlites contains 2.7 ± 0.2 to 943 ± 156 ppm N, with δ15N values from –30 ± 37 to +348 ± 43‰. Whereas degassing of N2 or NH3 can explain the lowest nitrogen isotopic ratios measured in the nakhlite mesostasis, the 15N-enriched isotopic composition (δ15N > 150‰) of four nakhlites (MIL 03346, Nakhla, NWA 6148, and Y 000593) likely results from interaction of the mesostasis melt with the martian atmosphere during ejection. The δ15N values (+25 ± 42 and +77 ± 19‰) of two melt inclusions in Y 000593 are comparable to those of Chassigny, further confirming that these meteorites likely sample a common volatile reservoir in the martian interior. Overall, the new results indicate that the chassignite-nakhlite reservoir did not inherit nitrogen from the solar nebula but, instead, from chondritic-like materials. These findings further confirm that planetary bodies in the inner solar system accreted (isotopically) chondritic nitrogen during the first few million years of solar system history.

¹S.A.Singerling,^2,5L.R.Nittler,²J.Barosch,³E.Dobrică,⁴A.J.Brearley,^1,5R.M.Stroud
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.015]
¹U.S. Naval Research Laboratory, Code 6366, Washington, DC 20375, USA
²Carnegie Institution of Washington, Washington, DC 20015, USA
³University of Hawai’i at Mānoa, Honolulu, HI 96822, USA
⁴University of New Mexico, Albuquerque, NM 87131, USA
⁵Arizona State University, Tempe, AZ 85287, USA
Copyright Elsevier

We conducted a transmission electron microscopy (TEM) study of an unusual oxide-silicate composite presolar grain (F2-8) from the unequilibrated ordinary chondrite Semarkona (LL3.00). The presolar composite grain is relatively large (>1 µm), has an amoeboidal shape, and contains Mg-rich olivine (forsterite), Mg-Al spinel, and Ca-rich pyroxene. The shape and phase assemblage are reminiscent of amoeboid-olivine-aggregates (AOAs) and add to the growing number of TEM observations of presolar refractory inclusion-like (CAIs and AOAs) grains. In addition to the dominant components, F2-8 also contains multiple subgrains, including an alabandite-oldhamite composite grain within the olivine and several magnetite subgrains within the Mg-Al spinel. We argue that the olivine, Mg-Al spinel, and alabandite-oldhamite formed by equilibrium condensation, whereas the Ca-rich pyroxene formed by non-equilibrium condensation, all in an M-type AGB star envelope. On the other hand, the magnetite subgrains are likely the result of aqueous alteration on the Semarkona asteroidal parent body. Additional evidence of secondary processing includes Fe-enrichment in the Mg-Al spinel and olivine, elevated Al contents in the olivine, and beam sensitivity and a modulated structure for the olivine.

Compound presolar grains, in particular oxide-silicate AOA-like grains such as F2-8, record condensation conditions over a wide range of temperatures. Additionally, the presence of several different presolar phases in a composite grain can impart information on the relative rates and effects of post-condensation processing in a range of environments, including the interstellar medium, solar nebula, and the host asteroid parent body. For example, the olivine and spinel in F2-8 show evidence of fluid infiltration, but each component reacted in different ways and to different extents. The TEM observations of F2-8 provide insights across the lifetime of the grain from its formation by condensation in an M-type AGB star envelope, its transit through the interstellar medium, and aqueous alteration during its residence on Semarkona’s asteroidal parent body.

¹E. Clavé et al. (>10)
Journal of Geophysical research (Planets) Link to Article [https://doi.org/10.1029/2022JE007463]
¹CELIA, Université de Bordeaux, CNRS, CEA, Bordeaux, France
Published by arrangement with John Wiley & Sons

Perseverance explored two geological units on the floor of Jezero Crater over the first 420 Martian days of the Mars2020 mission. These units, the Máaz and Séítah formations, are interpreted to be igneous in origin, with traces of alteration. We report the detection of carbonate phases along the rover traverse based on laser-induced breakdown spectroscopy (LIBS), infrared reflectance spectroscopy (IRS), and time-resolved Raman (TRR) spectroscopy by the SuperCam instrument. Carbonates are identified through direct detection of vibrational modes of CO3 functional groups (IRS and TRR), major oxides content, and ratios of C and O signal intensities (LIBS). In Séítah, the carbonates are consistent with magnesite-siderite solid solutions (Mg# of 0.42-0.70) with low calcium contents (<5 wt.% CaO). They are detected together with olivine in IRS and TRR spectra. LIBS and IRS also indicate a spatial association of the carbonates with clays. Carbonates in Máaz are detected in fewer points, as: (i) siderite (Mg# as low as 0.03); (ii) carbonate-containing coatings, enriched in Mg (Mg# ∼0.82) and spatially associated with different salts. Overall, using conservative criteria, carbonate detections are rare in LIBS (∼30/2000 points), IRS (∼15/2000 points), and TRR (1 /150 points) data. This is best explained by (i) a low carbonate content overall, (ii) small carbonate grains mixed with other phases, (iii) intrinsic complexity of in situ measurements. This is consistent with orbital observations of Jezero crater, and similar to compositions of carbonates previously reported in Martian meteorites. This suggests a limited carbonation of Jezero rocks by locally equilibrated fluids.

¹L.Mandon et al. (>10)
Journal of Geophysical research (Planets) Link to Article [https://doi.org/10.1029/2022JE007450]
¹LESIA, Observatoire de Paris, Université PSL, CNRS, Sorbonne Université, Université de Paris, Meudon, France
Published by arrangement with John Wiley & Sons

The Perseverance rover landed in the ancient lakebed of Jezero crater, Mars on February 2021. Here we assess the mineralogy of the rocks, regolith, and dust measured during the first year of the mission on the crater floor, using the visible and near-infrared spectrometer of SuperCam onboard the Perseverance rover. Most of the minerals detected from orbit are present in the bedrock, with olivine-bearing rocks at the bottom of the stratigraphy and high-Ca pyroxene-bearing rocks at the top. This is distinct from the overall low-Ca pyroxene-bearing composition of the watershed of Jezero, and points towards an igneous origin. Alteration mineral phases were detected in most of the rocks analyzed in low proportions, suggesting that aqueous alteration of the crater floor has been spatially widespread, but limited in intensity and/or time. The diverse aqueous mineralogy suggests that the aqueous alteration history of the crater floor consists of at least two stages, to form phyllosilicates and oxyhydroxides, and later sulfates. We interpret their formation in a lake or under deeper serpentinization conditions, and in an evaporative environment, respectively. Spectral similarities of dust with some rock coatings suggest widespread past processes of dust induration under liquid water activity late in the history of Jezero. Analysis of the regolith revealed some local inputs from the surrounding rocks. Relevant to the Mars Sample Return mission, the spectral features exhibited by the rocks sampled on the crater floor are representative of the diversity of spectra measured on the geological units investigated by the rover.

^1,2Wen-Ping Liu,^1,2Wei Yin,³Bin-Long Ye,^1,2Tian-Lei Zhao,⁴Qi-Zhi Yao,^1,3Yi-Liang Li,⁵Sheng-Quan Fu,^1,2,6Gen-Tao Zhou
Icarus (in Press) Link to Article [https://doi.org/10.1016/j.icarus.2023.115440]
¹Deep Space Exploration Laboratory, School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026, China
²CAS Key Laboratory of Crust-Mantle Materials and Environments, University of Science and Technology of China, Hefei 230026, China
³Department of Earth Sciences and Laboratory for Space Research, University of Hong Kong, Hong Kong 999077, China
⁴School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
⁵Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
⁶CAS Center for Excellence in Comparative Planetology, Hefei 230026, China
Copyright Elsevier

Mars has become the preeminent target of astrobiology due to its many Earth-like features. Serpentinized environments on Mars are increasingly of astrobiological interest because they imply the presence of several of the “key elements” for life. The Mars 2020 rover carries a compelling set of spectral instruments with the intent to characterize past habitable serpentinized environments, search for potential biosignatures, and collect samples for potential return to Earth. Reliable spectroscopic identification of serpentinization minerals is, of course, a prerequisite for mission accomplishment. The current assignment of spectroscopic features is based on the databases derived from pure minerals. However, many studies have confirmed that mineral assemblage can complicate spectrum identification, often leading to misinterpretation of the data. Therefore, a rock-based library should be built, which will increase our capability to interpret the Martian spectroscopic data. As such, we performed a comprehensive mineralogical and spectroscopic survey of several rocks sampled from an ophiolite complex in Qaidam Basin, one of the largest Mars analogs on Earth, to build an ophiolite spectral database. X-ray fluorescence (XRF), visible and near-infrared (VNIR), Raman spectroscopy, and XRD were used to identify minerals in the rocks. The results show that serpentine in the rocks with talc could be misinterpreted as sepiolite only relying on the Raman vibrations, while the VNIR spectra can identify serpentine well in all rocks. In addition, the camera and Raman spectrometer on the Mars rover should work together to identify different polymorphs of serpentine, i.e., antigorite, lizardite, and chrysotile. Raman and/or VNIR spectroscopy is effective for other minerals associated with serpentinization, including brucite, dolomite, magnesite, magnetite, talc, and quartz. Our study provides a framework for detecting serpentinization minerals on Mars with spectrometers and can be used for data interpretation by the Mars 2020 mission. All the spectral data presented in the supplementary material facilitate further comparison with future in situ and orbital measurements on Mars.

¹Damanveer S.Grewal,¹Paul D.Asimow
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.012]
¹Division of Geological and Planetary Sciences, California Institute of Technology, 1200 E California Blvd, Pasadena, CA 91125, USA
Copyright Elsevier

Disagreement regarding the origin of the bulk silicate Earth’s (BSE) superchondritic carbon/nitrogen (C/N) ratio is due, in part, to the unknown C/N ratios of differentiated planetesimals − the building blocks of Earth-like rocky planets. In this study we report solid-liquid metal partitioning experiments for C and N that allow us to reconstruct, from the C and N contents of iron meteorites, the C/N ratios of the cores of the earliest formed planetesimals. Due to their siderophile character, most of the C and N retained in these bodies after differentiation resides in their cores. Therefore, estimates of the bulk C and N contents and C/N ratios of the cores yield confident estimates of these quantities in the complete parent bodies of iron meteorites. Our experimental data, at 1 GPa and 1200-1400 °C, show that C and N are incompatible in solid metal relative to S-poor liquids but compatible in solid metal relative to S-rich liquids. Crucially, N is approximately an order of magnitude more compatible than C in S-rich systems. S itself is incompatible in solid metal and so the late-crystallizing liquids persisting at the end of core freezing were S-rich for most cores. Although these late-crystallizing liquids are unsampled by iron meteorites, we infer that their N contents and C/N ratios were generally lower and higher, respectively, than those in iron meteorites. Depending upon the fraction of unsampled late-crystallizing liquids as well as their S contents, the C/N ratios of the bulk cores and complete parent bodies are either similar to or higher than those measured in iron meteorites. The reconstructed C/N ratios of most of the parent bodies of iron meteorites are chondritic, except that the volatile-rich IC and IIC groups have superchondritic C/N ratios. Importantly, the C/N ratio of the parent body of the IC iron meteorite group lies within the estimated range of the BSE, whereas the C/N ratios of all other groups are distinctly lower. Correlated depletion of moderately volatile elements like Ge and Ga with C and N, variations in metallographic cooling rates, and Pd-Ag isotope systematics suggest that the parent cores of the volatile-depleted iron meteorite groups were likely affected by volatile degassing. If volatile-rich iron meteorites like the IC group better capture the C and N inventories of the parent cores of the earliest formed planetesimals, then delivery of C and N via such planetesimals makes the superchondritic C/N ratio of the BSE a natural consequence of the Earth’s accretion history. Otherwise, poorly constrained processes like atmospheric erosion or C and N delivery by exotic materials are required to explain the superchondritic C/N ratio of the BSE.

^1,2Alessandro Bragagni,¹Frank Wombacher,^1,3Maria Kirchenbaur,^1,4Ninja Braukmüller,¹Carsten Münker
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2023.01.014]
¹Institut für Geologie und Mineralogie, Universität zu Köln, Zülpicher Str. 49b, 50674 Köln, Germany
²Dipartimento di Scienze della Terra, Università degli studi di Firenze, via La Pira 4, 50121 Firenze, Italy
³Institut für Mineralogie, Leibniz Universität Hannover, Callinstraße 3, 30167 Hannover, Germany
⁴Institut für Geologische Wissenschaften, Freie Universität, Malteserstr. 74-100, 12249, Berlin, Germany
Copyright Elsevier

Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In.

Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures.

Most chondrites show a deficit in 115Sn/120Sn (typically -150 to -200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 115Sn/120Sn data correlate with In/Sn, being consistent with the β- decay of 115In over the age of the solar system. This represents the first evidence of the 115In-115Sn decay system in natural samples. The radiogenic 115Sn signature of the BSE derives from a suprachondritic In/SnBSE, which reflects preferential partitioning of Sn into the Earth’s core.

¹Nina Kopacz et al. (>10)
Icarus (in Press) Link to Article [https://doi.org/10.1016/j.icarus.2023.115437]
¹Department of Earth Sciences, Utrecht University, Utrecht, The Netherlands
Copyright Elsevier

The photochemical evolution of polycyclic aromatic hydrocarbons (PAHs), an abundant form of meteoritic organic carbon, is of great interest to early Earth and Mars origin-of-life studies and current organic molecule detection efforts on Mars. Fe-rich clay environments were abundant on early Earth and Mars, and may have played a role in prebiotic chemistry, catalyzing the breakdown of PAHs and freeing up carbon for subsequent chemical complexification. Current Mars is abundant in clay-rich environments, which are most promising for harboring organic molecules and have comprised the main studied features by the Curiosity rover in search of them. In this work we studied the photocatalytic effects of the Fe-rich clay nontronite on adsorbed PAHs. We tested the effect of ultraviolet radiation on pyrene, fluoranthene, perylene, triphenylene, and coronene adsorbed to nontronite using the spike technique, and in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in a Mars simulation chamber. We studied the infrared vibrational PAH bands with first order reaction kinetics and observed an extensive decrease of bands of pyrene, fluoranthene, and perylene, accompanied by the formation of PAH cations, while triphenylene and coronene remained preserved. We further analyzed our irradiated samples with nuclear magnetic resonance (NMR). Our study showed certain PAHs to be degraded via the (photo)Fenton mechanism, even under a dry, hypoxic atmosphere. Using solar spectra representative of early Earth, early Mars, and current Mars surface illumination up to 400 nm, the processes occurring in our set up are indicative of the UV-induced photochemistry taking place in Fe-rich clay environments on early Earth and Mars.