Hexamethylenetetramine as precursor of prebiotic chemistry in the Inner Solar System.

The presence of organic molecules in extraterrestrial environments has been widely accepted thanks to recent successes in the in situ detection of cometary molecules toward 67P/ Churyumov-Gerasimenko, as well as long-standing astronomical observations and analyses of carbonaceous meteorites in laboratories. However, despite extensive studies on the formation of organic molecules in various extraterrestrial environments such as molecular clouds, protosolar nebula, and asteroids, it still remains under debate when, where, and how such extraterrestrial molecules were abiotically formed.

A key molecule to solve the problems is hexamethylenetetramine, which is a polyheterocyclic organic molecule. Based on laboratory experiments simulating photochemical and thermal reactions of interstellar and cometary ice analogues (at about 10 degrees Kelvin) initially made of observed molecules, such as water, ammonia, and methanol, hexamethylenetetramine is in general a significant product (up to 60% by weight) in the total organic products. Although the composition of products varies depending on the experimental conditions, hexamethylenetetramine is generally abundant especially when methanol is used as an initial reactant. Since methanol is abundant in interstellar ices, the hexamethylenetetramine formation is likely to take place in the interstellar medium and become incorporated into solar system ices similar to other interstellar molecules. 

Yet hexamethylenetetramine has not been observed toward any extraterrestrial environments. Owing to its symmetric tetrahedral structure, hexamethylenetetramine does not possess a permanent dipole moment, which precludes its remote observational detection by rotational spectroscopy. Though hexamethylenetetramine is an infrared active molecule, its detection in the presence of deep nitrogen–hydrogen, carbon–hydrogen, and carbon–nitrogen bands in ices, as well as the presence of a strong silicate band at 10 μm, would complicate its definitive identification, so it is also not surprising that it has not yet been observed in interstellar or planetary ices. However, hexamethylenetetramine has been postulated to be one of the extended sources of ammonia and hydrogen cyanide in comets. Besides the lack of astronomical detection, there has also been no report on the detection of hexamethylenetetramine in any extraterrestrial materials including carbonaceous meteorites, interstellar dust particles, and cometary return samples.

Since hexamethylenetetramine is susceptible to degradation by 100°C water and acid hydrolysis methods traditionally used in meteoritic soluble organic analyses; a different method to extract hexamethylenetetramine from meteorites was developed. In a paper published in the journal Nature Communications on 7 December 2020, Yasuhiro Oba of the Institute of Low Temperature Science at Hokkaido University, Yoshinori Takano of the Biogeochemistry Research Center at the Japan Agency for Marine-Earth Science and Technology, Hiroshi Naraoka of the Department of Earth and Planetary Sciences and Research Center for Planetary Trace Organic Compounds at Kyushu University, Yoshihiro Furukawa of the Department of Earth Science at Tohoku University, Daniel Glavin and Jason Dworkin of the Solar System Exploration Division at NASA's Goddard Space Flight Center, and Shogo Tachibana of the University of Tokyo Organization for Planetary and Space Science and the Institute of Space and Astronautical Science at the Japan Aerospace Exploration Agency, present the results of a study in which they extracted relatively large portions (masses ranging from 0.5 to 2 g) of interior samples of three carbonaceous chondrites, Murchison, Murray, and Tagish Lake, under mild conditions which utilised neither concentrated acidic solutions nor high temperatures for the extraction processes. The aqueous extracts were purified using cation-exchange chromatography and were then analysed using a high-resolution mass spectrometer coupled with a high-performance liquid chromatograph. Hexamethylenetetramine was successfully detected from Murchison, Tagish Lake, and Murray meteorite extracts at parts-per-billion levels.

 

Molecular structure and exact mass information of hexamethylenetetramine (HMT) and some representative derivatives showing methyl-hexamethylenetetramine, amino-hexamethylenetetramine, hydroxyl-hexamethylenetetramine, hydroxymethyl-hexamethylenetetramine, methoxy-hexamethylenetetramine, and monohydroxy-monomethyl-hexamethylenetetramine discussed in this study. Note that monohydroxy-monomethyl-hexamethylenetetramine possesses three structural isomers depending on the positions of the two functional groups. Oba et al. (2020).

Oba et al. produced mass chromatograms of the Murchison, Murray, and Tagish Lake meteorites at the mass-to-charge ratio of 141.1135 ± 0.0004, which corresponds to the protonated ion of hexamethylenetetramine formed by electrospray ionisation, analysed by a high-performance liquid chromatograph equipped with an InertSustain PFP analytical column. One sharp peak was observed for each chromatogram at about 20.5 min, which was consistent with hexamethylenetetramine standard reagent and far above the blank detection level. The similar consistency was also observed when the sample was analysed under different analytical conditions where Hypercarb or InertSustain Amide was used as a separation column for high-performance liquid chromatograph analysis. Based on the retention time and mass accuracy (within 3 parts per million of the theoretical mass-to-charge ratio), even under the different analytical conditions, the observed peak can be confidently assigned to hexamethylenetetramine. The observed consistency in the fragmentation pattern of hexamethylenetetramine by tandem mass spectrometry experiments  between the Murchison extract and the standard reagent further supports this conclusion. The concentrations of hexamethylenetetramine in the three meteorites were 846 ± 37, 29 ± 9, and 671 ± 9 parts per billion for Murchison, Murray, and Tagish Lake, respectively. Mass peaks attributable to the deuterium, carbon¹³, and nitrogen¹⁵-substituted isotopologues of hexamethylenetetramine were also identified in the mass spectra of the Murchison extract. Oba et al. have confirmed that the loss of hexamethylenetetramine is negligible and that there is no hydrogen isotopic fractionation of hexamethylenetetramine during their analytical procedure.

 

The symmetric chemical structure of hexamethylenetetramine and the equivalent electrostatic potential in the ground state condition. Oba et al. (2020).

Oba et al. also observed several peaks with the mass-to-charge ratio values well consistent with the hexamethylenetetramine derivatives methyl-hexamethylenetetramine, amino-hexamethylenetetramine, hydroxy-hexamethylenetetramine, and hydroxymethyl-hexamethylenetetramine, in the mass chromatograms at the mass-to-charge ratios of 155.1291, 156.1244, 157.1084, and 171.1240, respectively, as each protonated ion formula in Murchison. The mass-to-charge ratio 171.1240 trace shows at least three peaks, which might be derived from hydroxymethyl-hexamethylenetetramine and its structural isomers methoxy-hexamethylenetetramine and monohydroxy-monomethyl-hexamethylenetetramine. No authentic standards were available, so these assignments are the most likely but other isomers (e.g. ethyl-pentamethylene tetramine instead of methyl-hexamethylenetetramine) cannot be excluded. The absence of these species on the mass chromatograms for the hexamethylenetetramine standard reagent indicates that these are likely not formed during workup or clusters or N-functionalisations formed by electrospray ionisation and so should be indigenous to the meteorite samples. Without authentic standards, an estimate of their possible abundances assumed the same ionization efficiency as hexamethylenetetramine; the most abundant derivative was methyl-hexamethylenetetramine (2% of hexamethylenetetramine), followed by hydroxymethyl-hexamethylenetetramine or its isomers (less than 0.6%), hydroxy-hexamethylenetetramine (0.2%), and amino-hexamethylenetetramine (0.03%).

 

Identification of hexamethylenetetramine in meteorites. Mass chromatograms at the mass-to-charge ratio of 141.1135 within (a) 3 parts per million exact mass window at each monoisotopic mass for a hexamethylenetetramine standard reagent, (b) hexamethylenetetramine in Murchison, (c) Tagish Lake, and (d) Murray meteorites, measured using the InertSustain PFP column. The numbers in parenthesis represent the absolute scale in ion intensities for each chromatogram. The numbers near the peak represent the retention time. Here that a retention time difference between the standard reagent and the target molecule sometimes occurs in a chromatographic separation for complex organic matter. To compensate this issue, the measured mass within 3-parts per million window was monitored for the data quality assurance. Also, small levels of fluctuation in the retention time are caused by variations in daily conditions of the liquid chromatograph. The Tagish Lake and Murray extracts were analysed in a different day (the retention time for the hexamethylenetetramine standard reagent was 21.07 min) with the Murchison extract. Oba et al. (2020).

The negligible amounts of hexamethylenetetramine in the blank and control samples compared to the elevated concentrations of hexamethylenetetramine measured in the meteorite extracts argue that hexamethylenetetramine is indigenous to the meteorites. In addition, the likely detection of several hexamethylenetetramine-derivatives also bolsters this conclusion; unlike hexamethylenetetramine itself, to Oba et al.'s best knowledge, these hexamethylenetetramine-derivatives are commercially unavailable and their presence in terrestrial environments has not been reported. However, these hexamethylenetetramine-derivatives have been identified in organic residues produced by photolysis of interstellar ice analogues followed by warming to room temperatures, which mimics the processes of molecular evolution toward star formation. Furthermore, the estimated relative abundances of these hexamethylenetetramine-derivatives in the organic residues (orders of magnitudes less abundant than hexamethylenetetramine) are in reasonable agreement with those of the meteoritic hexamethylenetetramine-derivatives.

 

Results of tandem mass spectrometry experiments. Mass fragmentation patterns of hexamethylenetetramine (HMT) in (a) the standard reagent and (b) the Murchison extract measured by andem mass spectrometry experiments. A schematic image of hexamethylenetetramine fragmentation is shown alongside the panel (a). The 6–7 digit numbers in the mass spectra indicate the exact masses of the parent molecule. The fragmentation patterns are consistent with each other except the presence of peaks with a red asterisk in the Murchison extract, which are derived from other species coexisting with hexamethylenetetramine. Note: the mass peak at the mass-to-charge ratio (m/z) of 68.9352 in the Murchison extract could not be successfully assigned to any ions under the assumption that the ion is composed of carbon, hydrogen, nitrogen, and oxygen. The mass peak assigned to C7H11 (m/z = 95.0856) is a background signal on the LC condition. Oba et al.

The concentration of hexamethylenetetramine in Murchison (846 ± 37 parts per billion) is within the range of individual water-extractable and acid-produced amino acids (200–5000 parts per billion) and higher than that of sugars (below 180 parts per billion) and nucleobases (less than about 70 parts per billion) in the Murchison Meteorite. In the Tagish Lake Meteorite, the concentration of hexamethylenetetramine (671 ± 9 parts per billion) is also in the range of individual amino acid concentrations identified in acid hydrolysed water extracts of the Tagish Lake Meteorite (less than 14 parts per billion: Tagish Lake 11i, less than 1000 parts per billion: Tagish Lake 11 h). While in Murray, the concentration of hexamethylenetetramine (29 ± 9 parts per billion) is lower than individual amino acid concentrations (51–2834 parts per billion) in the same meteorite. It is possible that differences in the Murchison/Tagish Lake and Murray parent body conditions (e.g. temperature, water/rock ratio, etc.) led to lower abundances or higher loss rates of hexamethylenetetramine, which may partly be related to the formation of soluble organics. A mass chromatogram of the hexamethylenetetramine concentrations normalized with glycine concentrations in the same meteorite showed no obvious trend in the concentrations of hexamethylenetetramine with glycine, suggesting no obvious correlation in terms of their formation history in each meteorite. Mass chromatograms of each meteorite extract at the mass-to-charge ratio values corresponding to imidazole and its alkylsubstituted homologues (up to seven carbon chains), which are proposed as the products after the hydrothermal degradation of hexamethylenetetramine, showed that for Murchison and Murray, the presence of alkylimidazoles was strongly expected in their extracts; while, they were significantly depleted in Tagish Lake. These results do not contradict the assumption that Tagish Lake, at least the specimen used in the present study, could have experienced less extensive hydrothermal alteration than Murchison and Murray on their parent bodies.

 

Detection of hexamethylenetetramine isotopologues. Mass chromatograms extracted at the mass-to-charge ratio of (a) 141.1135, (b) 142.1105, (c) 142.1168, and (d) 142.1197, which correspond to the protonated ions of hexamethylenetetramine (HMT), nitrogen¹⁵-hexamethylenetetramine, carbon¹³-hexamethylenetetramine, and deuterium-hexamethylenetetramine, respectively (3-parts per million window at each monoisotopic mass) in the Murchison meteorite extract. The numbers on the upper right in each panel represent the absolute scale for each chromatogram. Oba et al. (2020).

Given the harsh extraction conditions of amino acid analyses, one possibility is that some of the hexamethylenetetramine and its derivatives can form amino acids during routine amino acid extraction and workup. In fact, acid hydrolysis of hexamethylenetetramine-containing organic mixtures yielded amino acids, and the role of hexamethylenetetramine for amino acid formation has been investigated well in recent studies. However, the argument that hexamethylenetetramine is the origin of amino acids during workup is weakened by Murray, which has a similar abundance of amino acids to Murchison, yet the hexamethylenetetramine concentration was lower by about an order of magnitude than Murchison. Moreover, sample heterogeneity between different specimens of the same meteorite, which has been often invoked for explaining different quantitative results of some molecules including their different enantiomeric distributions in the same meteorites, can also be invoked. On the other hand, it is likely that hexamethylenetetramine is formed during our laboratory workup if both ammonia and formaldehyde are present in the aqueous extract. Previous studies detected both molecules from carbonaceous meteorites after hydrothermal treatment and/or acid hydrolysis of meteorite powders at about 100°C or above, implying that both free ammonia and formaldehyde are released from their acidlabile precursors after these treatments. Although it is not clear whether such precursors can contribute to the formation of hexamethylenetetramine in aqueous solutions without acid and high-temperature treatment at room temperature, Oba et al. expect that hexamethylenetetramine formed as such does not constitute a significant fraction in the detected hexamethylenetetramine abundance. Nevertheless, there are still a number of uncertainties on the origin of the difference in hexamethylenetetramine abundance between three meteorites analysed in the present study (e.g. hexamethylenetetramine abundance when each parent body is formed by accretion).

 

Evaluation of artifact for the formation of hexamethylenetetramine derivatives. Mass chromatograms at the mass-to-charge ratio of (a) 141.1135, (b) 155.1291, (c) 156.1244, (d) 157.1084, and (e) 171.1240, which correspond to hexamethylenetetramine (HMT), methyl-hexamethylenetetramine, amino-hexamethylenetetramine, hydroxy-hexamethylenetetramine, and hydroxymethyl-hexamethylenetetramine, respectively, for the hexamethylenetetramine standard reagent (3-parts per million window at each monoisotopic mass). Hexamethylenetetramine derivatives were not identified on the mass chromatograms, indicating that the hexamethylenetetramine-derivatives detected in the Murchison extract are not artifacts but are indigenous to the meteorite. Oba et al. (2020).

It is reasonable that interstellar medium-derived hexamethylenetetramine would be highly deuterium-enriched. Though the typical interstellar values (i.e. a deuterium/hydrogen ration of less than 0.01) are far higher than seen in any meteoritic compound. No levels of this extreme deuteration of hexamethylenetetramine were visible. Yet, it is still possible that the hexamethylenetetramine detected has an interstellar provenance and the interstellar medium deuterium was lost to exchange with comparatively deuterium-poor parent body fluids. Oba et al. tested the deuterium/hydrogen exchange in hexamethylenetetramine upon heating with water and silicates to simulate possible variations in the deuteration level of meteoritic hexamethylenetetramine through hydrothermal processes in asteroids. When fully deuterated hexamethylenetetramine was heated with water under alkaline conditions (pH 10) at 100°C, deuterium atoms in hexamethylenetetramine were gradually replaced with hydrogen atoms in water, resulting in the formation of partly hydrogenated hexamethylenetetramine after several days. These results suggest that even if hexamethylenetetramine was enriched in deuterium upon the formation in the interstellar medium, it might get depleted in deuterium through interactions with relatively deuterium-depleted water on the parent bodies of CM chondrite meteorites (the most common type of carbonaceous chondrite).

 

Variations in the relative abundance of hexamethylenetetramine with glycine in each meteorite. The error bars represent the standard deviation from the mean value of hexamethylenetetramine to glycine for each meteorite. Oba et al. (2020).

Once hexamethylenetetramine is incorporated into planetary systems and into a meteorite parent body, it has three likely fates: (1) physicochemical desorption from the surface of asteroids into the gas phase of the solar system, (2) decomposition, and (3) preservation. It is likely that desorption of HMT from asteroids could be induced either or both by external excitation energies (e.g. cosmic rays and ultraviolet photons) and by thermal processes, although these processes have not been studied experimentally so far. Laboratory studies strongly suggest that aqueous or thermal degradation of hexamethylenetetramine on meteorite parent bodies has a potential to yield various kinds of molecules, such as formaldehyde, ammonia, amines, amino acids, and nitrogen heterocycles, many of which have been identified in carbonaceous meteorites after hydrothermal treatment at around 100°C or acid hydrolysis. Hexamethylenetetramine that survived these desorption and degradation processes might be delivered to the Earth via meteorites and possibly interplanetary dust particles.

 

Alkyl imidazoles in Murchison. Mass chromatograms at the mass-to-charge ratio values corresponding to the protonated ions of alkylated imidazole series in the Murchison extract (3-parts per million window at each monoisotopic mass). The values in parentheses are the theoretical masses of the alkylated imidazoles. The uppermost panel corresponds to the protonated ion of imidazole. The values on the right side represent each absolute intensity. Oba et al. (2020).

Among the various kinds of molecules which can form via hydrothermal degradation of hexamethylenetetramine, both formaldehyde and ammonia are considered particularly important for the formation of soluble organic molecules, such as amino acids and sugars, and insoluble organic matter in meteorites through various reactions such as formose and Mannich reactions or Strecker-cyanohydrin synthesis. Although formaldehyde and ammonia are two significant components in interstellar ices, which are mainly formed by the hydrogenation of carbon, oxygen and nitrogen atoms, respectively, due to their low desorption temperatures from interstellar grains (less than 100 K), unless transformed into other (non-volatile) species by chemical reactions, both molecules are likely to be lost from grains during warming up phases toward star formation if the temperature of the grains exceeds the desorption temperature of both molecules. In contrast, since solid hexamethylenetetramine does not desorb from grains even at 330 K, it should have more opportunity to be incorporated into inner solar system bodies. Naturally, since hexamethylenetetramine is in equilibrium with formaldehyde and ammonia, it could also have been formed on meteorite parent bodies from both molecules if they are really present, which could keep the hexamethylenetetramine concentration relatively constant. However, formaldehyde and ammonia have been identified in carbonaceous meteorites upon hydrothermal treatment at around 100°C or acid hydrolysis, conversely these species may be from the decomposition of hexamethylenetetramine on the parent body or during laboratory workup. As such, it will be challenging to constrain the location of hexamethylenetetramine formation but its presence in the processed interstellar ice analogues can be a good indicator to explain its presence in meteorites. Hence, the presence of hexamethylenetetramine in carbonaceous meteorites promises its pivotal role to carry interstellar prebiotic precursors to the inner solar system, which should contribute to the chemical evolution in the primordial stage on Earth.

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Carbonaceous chondrite meteorite recovered from England after February fireball.

Scientists from the Natural History Museum in London have confirmed the discovery of a meteorite within twelve hours of a fireball meteor (defined as a meteor brighter than the planet Venus) being seen over England. The fireball was seen over the West Midlands region of England slightly before 10.00 pm GMT on Sunday 28 February 2021, and within a few hours a resident of the village of Winchcombe in Gloucestershire had reported finding a chunk of meteorite on their driveway.

 

A chunk of meteorite found on a driveway in the village of Winchcombe in Gloucestershire following observations of a fireball meteor over the West Midlands region of England on 28 February 2021. Natural History Museum.

The meteorite is described as soft to the touch, and is of a type known as a carbonaceous chondrite. Such meteorites are rich in clay minerals (implying the freezing of water within the rock at some point in their history), and are much rarer than stoney (generally basaltic) or iron meteorites, largely because they tend not to survive the journey through the Earth's atmosphere, however similar material has been recovered from asteroid 162173 Ryugu by the Hayabusa2 space probe, and from asteroid 101955 Bennu by the OSIRIS-REx space probe, implying that carbonaceous chondrite material may be more common in the Solar System than on Earth.

 

Fireball meteor seen over England on Sunday 28 February 2021. UK Meteor Network.

The fact that the Winchcombe Meteorite made it to the ground at all implies that the body which produced it was travelling relatively slowly compared to the Earth; most meteors hit the atmosphere at about 70 km per second, which means that material, particularly soft material, from them has little chance of reaching the ground intact. However, if a body is travelling on a trajectory similar to that of the Earth, it may intersect the atmosphere at a much lower speed, making it much more likely that some of it will reach the ground. 

This makes the Winchcombe Meteorite special for several reasons. Carbonaceous chondrites are rare, and yield much more information about the early Solar System than iron or basaltic meteorites, as they frequently contain organic molecules, important for our understanding of the emergence of life. Such meteorites seldom make it through the atmosphere intact, and those that do need to be recovered quickly, as their soft nature means that they are quickly altered and eroded by Earth's atmosphere and moisture. Moreover, meteorites connected to observed meteors are also rare, and can tell us more about their origin than a meteorite found, for example, on top of an Antarctic glacier, which might have sat there for hundreds of years before being discovered. About 90 000 meteorites are known in museum collections around the world only 51 are carbonaceous chondrites that can be linked to meteor observations. Because the Winchcombe Meteorite was observed not only by a large number of Human observers, but by a large number of fixed cameras, it is highly likely that scientists will be able to reconstruct its original trajectory, and determine where abouts in the Solar System it came from.

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The Bench Crater Carbonaceous Chondrite, a meteorite from the Apollo 12 Landing Site.

A key driver of future lunar scientific exploration is to deter-mine the source(s) of water ice and volatiles found on the Moon’s surface at the present day, and to understand past origins of water and volatiles in the Earth-Moon system. Potential caches of water and other volatiles at the lunar surface are being targeted by spacecraft missions for both scientific and exploration objectives. Such volatile reservoirs at the lunar surface are of key astrobiological interest and may also prove to be useful for in situresource utilisation for the next generation of lunar surface exploration. Over the past decade, laboratory measurements of hydroxyl and water locked in volcanic picritic glass beads and melt inclusions they host, in the phosphate mineral apatite, and in nominally anhydrous minerals have also allowed investigation of the diver-sity and budgets of volatile reservoirs in the lunar interior. Lunar surface volatile budgets have been constrained by spectral identifications of hydroxide ions bound in regolith soils, concentrations of volatiles within the regolith of permanently shadowed polar craters, and in Apollo regolith glasses and impact breccias. However, the origin of these dif-ferent reservoirs is poorly constrained: they are likely a mixture of both indigenous and exogenous sources. Unravelling the geochemical and isotopic records of volatiles at the lunar surface is complicated by (i) limited direct measurements of end-member compositions (i.e.impactor types, so-lar wind-derived volatiles, and interior sources), (ii) few com-plete volatile inventory analyses of lunar soil and regolith samples, and (iii) complications with calculating isotopic con-tributions from spallogenically-derived components.

To address the first of these challenges, Katherine Joy of the Department of Earth and Environmental Sciences of the University of Manchester, and the Center for Lunar Science and Exploration at the Lunar and Planetary Institute, Romain Tartèse, also of the Department of Earth and Environmental Sciences of the University of Manchester, Scott Messenger of the Robert M Walker Laboratory for Space Science at NASA's Johnson Space Center, Michael Zolensky, also of the Center for Lunar Science and Exploration at the Lunar and Planetary Institute, and of Astromaterials Research and Exploration Science at NASA's Johnson Space Center, Yves Marrocchi of the Université de Lorraine, David Frank, also of  Astromaterials Research and Exploration Science at NASA's Johnson Space Center, and the Institute of Geophysics and Planetology at the University of Hawai’i at Manoa, and David Kring, again of Astromaterials Research and Exploration Science at NASA's Johnson Space Center, and of the NASA Solar System Exploration Research Virtual Institute, have determined the isotopic composition of the volatile elements hydrogen, carbon, nitrogen and oxygen in a carbonaceous chondrite meteorite fragment from the Moon. This study, published in the journal Earth and Planetary Science Letters on 22 April 2020, therefore, provides the first ground-truth for the composi-tion of asteroid-derived volatiles hosted by the lunar regolith.

The types of meteoritic material that are recovered today on the Earth might also be rep-resentative of the sources of material striking the Moon, contribut-ing to the addition of volatiles to the lunar regolith. There are, however, two significant knowledge gaps preventing us from mak-ing this assessment. Firstly, weakly consolidated, and likely the most volatile-rich, meteorites (and micrometeorites) are largely contaminated (especially volatile elements) or destroyed during descent through the Earth’s atmosphere and are poorly sampled, or unavailable in the Earth’s meteorite collection. Thus, knowledge of their con-tribution to the meteoritic volatile inventory is incomplete. Sec-ondly, the flux and nature of meteoritic debris maybe variable as the dynamical evolution of small bodies in the Solar System has changed through time. Thus, meteoritic fragments found in the lu-nar regolith may provide us with a complementary and often older record compared to meteorites found on Earth. To address both of those existing shortcomings we need to examine the Moon’s surficial regolith for volatile-rich meteoritic relics. Retention of such projectile material at the lunar surface depends upon impact velocity, impact angle, and impactor and target material properties including strength and porosity. Theoretical calculations indicate that aster-oids deliver the majority of lunar near-surface volatiles compared with cometary dust particles. To date, all impactor debris found on the Moon have been very small, rang-ing from a few microns to only a few mm in size, yet provide a vital ground-truth for characteri-sation of volatile resources by future in situmission analysis of the lunar regolith, and samples returned to the Earth.

Joy et al. characterised the petrography, mineralogy and geochemistry of a fragment of the Bench Crater carbonaceous chondrite meteorite. The meteorite was identified from a range of small (0.6 to 3 mm) rock particles ex-tracted from soil sample 12037, collected from the rim of a 75 m impact crater on the nearside of the Moon at the Apollo 12 landing site (3.01°S 23.4°W).

The Bench Crater meteorite. (a) Transmitted light optical image of Bench Crater meteorite showing a dark matrix and brown-coloured ferromagnesian silicate aggre-gates. (b) Backscattered electron microscope  image; the white arrow indicates the location where some matrix was extracted for Nanoscale secondary ion mass spectrometry analysis. (c) False colour X-ray element composite map showing the mineralogical composition of the meteorite. Colour scheme indicated on the figure, where ferromagnesian silicate aggregates are cyan; matrix material is blue; apatite, calcite and dolomite are yellow; pyrrhotite, pentlandite and magnetite are red; ilmenite is pink; and the feldspathic agglutinate rim is white. (d) False colour X-ray element composite map. Colour scheme indicated on the figure, where apatite is cyan; calcite and dolomite are blue; pyrrhotite and pentlandite (Sulphur-bearing phases) are yellow; and magnetite is red. Joy et al. (2020).

The 12037 bulk soil is sub-mature, meaning that it underwent medium levels of solar wind exposure at the lunar surface com-pared with other Apollo soil samples. The dura-tion of exposure of this 12037 soil to the space environment has been estimated to be 10-20 million years based upon the density of cos-mic ray tracks and nitrogen spallation ages. his exposure age is younger than the proposed Apollo 12 landing site Bench Impact Crater formation episode, thought to be less than about 99 million years, and probably less than 55 million years. It may be that the Bench Crater me-teorite represents part of the impactor that made this crater, but it may also have been delivered after this event. In any case, the Bench Crater meteorite likely impacted the Moon’s surface in the last 100 million years.

Optical image of grain mount 12037,188. The Bench Crater meteorite is indicated with the arrow. Other small regolith rock fragments in the mount are a collection of impact melt breccias with varying textures. Joy et al. (2020).

Small pieces of the Bench Crater meteorite in section 12037,188 were removed with a needle. Microtomed sec-tions were prepared and analysed using the NASA Johnson Space Center JEOL 2200FS field emission gun transmission electron microscope coupled to an Oxford energy-dispersive X-ray spectroscopy system to check the presence of hydrated phases and determine the composition of matrix materials. Two 15 × 15 μm areas (Area 1 and Area 2) of fragments pressed into gold foil were spatially mapped for hydrogen, carbon, and nitrogen isotope compositions and two 10 × 10 μm areas (Area 3 and 4) were spatially mapped for their hydrogen isotope composition in separate sessions using the NASA Johnson Space Center Nanoscale secondary ion mass spectrometry 50L ion microprobe.

Collection context of the 12037 soil sample at the Apollo 12 landing site from the rim of Bench crater. Astronaut traverses and sample selection sites are overlain on LROC Narrow Angle Camera image. Image is courtesy of NASA/Goddard Spaceflight Center/Arizona State University and taken from the LROC website using their Apollo sites viewing webtool and overlay feature function. Joy et al. (2020).

After removing a small sub-split of the sample for nanoscale secondary ion mass spectrometry work, we also analysed the whole polished grain mount of Bench Crater using the NASA Johnson Space Center JEOL 7600f FEG scanning electron microscope to collect backscatter electron images and X-ray element maps. Normalised phase modal proportions were estimated by combining these element maps and using Adobe Photoshop to count the number of pixels in each assigned phase type. Further backscatter electron imaging was carried out using a FEI Quanta 650 FEG scanning electron microscope at the University of Manchester, and mineral compositions were acquired using a Cameca SX 100 electron microprobe at the University of Manchester.

Collection site location of soil sample 12037 on the edge of Bench Crater at the Apollo 12 landing site showing astronaut’s shadow. Image is courtesy of NASA (image catalogue AS12-48-7064). Joy et al. (2020).

Finally, Joy et al. measured the oxygen isotopic compositions of silicates, magnetite and carbonate in situ in the Bench Crater meteorite thin section using a CAMECA IMS 1270 E7 at the Centre de Recherches Pétrographiques et Géochimiques in Nancy, France. After the analyses, all the SIMS spots were carefully checked by back-scattered electron-scanning electron microscope to estimate poten-tial contribution by adjacent minerals. 

Location of the roughly 15 μm SIMS spots within (a) silicate phases in the largest aqueously altered chondrule, and (b) within magnetite phases. Joy et al. (2020).

The Bench Crater meteorite is 3.00 × 1.75 mm in size. Transmitted light optical microscope observations show that the meteorite appears very well preserved with a low-level petrofabric (preferred matrix cross-cutting fracture orienta-tion), sub-rounded magnetite grains, and fractured sulphides. It is composed of brown-coloured aggregates of ferromagnesian minerals that are possibly aqueously altered chondrules (olivine + pyroxene, roughly 10% by area) of the meteorite; embedded within a fine-grained matrix (roughly 68% by area). Many ferromagnesian phases in the matrix have been replaced by the hydrated mineral saponite that retained structural water even after delivery to the lunar surface. This is consistent with low electron-probe microanalysis analytical totals of 91-93 percent by weight obtained on matrix areas, since water/hydroxide is not measured by electron-probe microanalysis. Lath shaped sulphides (about 5.3% by area) comprise pyrrhotite, pentlandite, and rare chalcopyrite, including the large rectangular sulphide crystal in the middle of the sample. Manganese-rich ilmenite occurs at trace levels (roughly 0.3% by area). Low-temperature aqueous alteration minerals in-clude framboidal and plaquet magnetite (roughly 12.4% by area). The Bench Crater meteorite also contains calcium-rich minerals includ-ing calcite and dolomite (roughly2.4% by area) and apatite (roughly 2.3% by area). Apatite is typically found within the aqueously altered chondrules, is chlorine-poor, and is characterised by low fluorine abundance (0.8-1.1% by weight) compared to apatite in indigenous lunar samples, which typically contains at least 3% fluorine by weight.

Backscattered electron images of Bench Crater meteorite fabric showing a representative matrix region of the meteorite (a), and close up views of different ferro-magnesian aggregates (F-M Agg) (aqueously altered chondrule) comprised of intermediate phases (I-M phase), amorphous phases, ilmenite, apatite and pyrrhotite (Pyrr). Black linear features are fractures. Joy et al. (2020).

The meteorite fragment has a patchy thin (less than 100 μm) vesicular crust, coating about 10% of its exterior. This crust is more feldspathic (12.8% by weight aluminium oxide) and enriched in titanium dioxide (2.2% by weight titanium dioxide) compared to carbonaceous chondrite meteorites (less than 5% by weight aluminium oxide, and less than 0.3% % by weight titanium dioxide) and instead is more similar to Apollo 12 bulk regolith compositions (13.9% by weight aluminium oxide, 3.1% by weight titanium dioxide). As the Moon has no atmosphere, this crust is not a fusion crust (formed on Earth during breakup of bolides as they are frictionally heated during atmospheric entry), but is more akin to agglutinitic or splash coat crusts found on rocks in the lunar regolith formed from flash impact melting. The lunar-like composition of the vesicular rim suggests interaction between the impactor and melted local basaltic lunar regolith either during or after its delivery. Temperatures of about 1100°C are required to melt lunar regolith. Therefore, some areas of the outer 10-30 μm of Bench Crater have likely been affected by flash heating, provoking dehydration of the matrix to form fibrous material. How-ever, the occurrence of hydrated saponite-bearing matrix just over 50 μm away from the glassy coat suggests that heat was quickly dissipated, and that the internal part of the sample was not baked and extensively degassed during the agglutination process.

Backscattered electron images of Bench Crater meteorite. (a)–(d) Close up of the thin (less than 100μm) irregular vesicular glassy agglutinitic rim that partially coats about 10% of the exterior of Bench Crater meteorite. Chemical analysis of the coat shows it to be feldspathic. Abbreviations: Ap, apatite; Mag, magnetite; F-M Agg, ferro-magnesian aggregate; Pyrr, pyrrhotite. Joy et al. (2020).

To try to classify Bench Crater’s parent meteorite group, Joy et al. measured in situ the oxygen isotope composition of magnetite, carbonate and the groundmass of the aqueously altered chondrules (within both intermediate phase and amorphous material). In matrix areas, the proportions of oxygen¹⁸ and oxygen¹⁷ values range from about 9.9 to 16.8 parts per thousand and 5.2 to 8.3 parts per thousand, respectively, generally falling along the terrestrial fractionation line, between the oxygen isotope compositions of the matrices of CM and CI carbonaceous chondrite falls (i.e. members of the Mighei and Ivuna carbonaceous chondrite meteorite families). The magnetite proportions of oxygen¹⁸ and oxygen¹⁷ values range from about 5.7 to 8.5 parts per thousand and 4.8 to 6.1 parts per thousand, respectively, and fall above the terrestrial fractionation line, on the same mass dependent fractionation line than the one defined by oxygen isotope compositions of magnetite in CI and CM carbonaceous chondrite falls. The two carbonate analyses yielded oxygen isotope compositions roughly similar to those measured in the aqueously altered chondrules, plotting at the oxygen¹⁶-rich end of the trend defined by carbonate analysis in CM chondrite falls.

Joy et al. removed a small portion of the matrix of the Bench Crater meteorite and analysed its hydrogen, carbon and nitrogen isotope compositions in situin two different 15 × 15 μm areas These two areas yielded comparative bulk deuterium proportion values of −36 and +200 parts per thousand, and a comparative bulk average proportion of −13 parts per thousand.

Nanoscale secondary ion mass spectrometry imaging did not show any micron-size hydrogen-, carbon-or nitrogen-isotopically anomalous regions, con-trary to what is observed in interplanetary dust particles, ultracarbonaceous Antarctic micrometeorites, and the most prim-itive chondrites like Murchison, in which hotspots with elevated isotope ratios are common. There was also no isotopic distinction between carbon-rich and carbon-poor areas of the Bench Crater samples.

Comparison of the deuterium/hydrogen distribution in Murchison (a) and Bench Crater (b) Murchison is characterised by a bulk matrix relative proportional value of -117  with deuterium-rich hotspots with relative proportional value ranging from 2300 to 4800 parta per thousand, which is consistent with organic globules observed previously in the matrix of other primitive carbonaceous chondrites. The Bench Crater matrix does not display these deuterium-rich hotspots that are common among the most primitive chondrites and interplanetary dust particles. Joy et al. (2020).

The Bench Crater meteorite provides the first direct evidence of surviving hydrated carbonaceous chondrite material delivered to the lunar regolith. It is, thus, currently the only direct ground-truth of the planetary end-member for all hydrogen, nitrogen and carbon light-element isotopic analysis of lunar soils. These findings pro-vide important benchmarks for models of volatile processing and transport across the lunar surface.

The Bench Crater meteorite is mineralogically and composition-ally unusual compared with other carbonaceous chondrite groups. It is mineralogically distinct from CV types (Vigarano carbonaceous chondrite meteorites), which are lacking in calcite and dolomite and have comparatively lower abundances of phyllosilicates (1.9–4.2%) and magnetite (6%). than Bench Crater. Affinities have previously been made with C-ungrouped types (carbonaceous chondrites not placed in any family) and CM2 carbonaceous chondrites (Type 2 Mighei carbonaceous chondrites). For instance, the high abundance of acicular sulphides and the presence of aqueously altered chondrules are similar to the CM1/2 Boriskino Meteorite, and thermally metamorphosed CI, CM and CY chondrites (e.g. Ikeda). However, the high modal abundance of magnetite bears more resemblance to CI chondrites and matrix-rich (altered) CR chondrites such as Al Rais and Grove Mountains (GRO) 95577. Notably the me-teorite matrix is magnesian and is compositionally more similar to CI-meteorite groups than CM or CR types, suggesting a higher state of parent body aqueous alter-ation. It should be noted that minor dehydration due thermal pro-cessing is unlikely to have changed the magnesium oxide/iron oxide ratio; this ratio being constant in CM chondrites having experienced dehydration. Bench Crater also share similarities with the Lonewolf Nunataks (LON) 94101 meteorite, which has been described as a CM chondrite with coarse acicular sulphides and a wide variety of CM-and magnetite-rich CI-like clasts. Bench Crater might be akin a clast-rich CM chondrite, but its limited size and hence representativeness precludes defini-tive assessment of this possibility. All these observations indicate that the Bench Crater meteorite cannot be directly related to any known carbonaceous chondrite groups present in our current me-teorite collections.

Bench Crater meteorite also shows oxygen isotope character-istics that connect it to the hydrated CI and CM carbonaceous chondrites. For example, the Bench Crater magnetite grains have oxygen isotope compositions that are on the same mass fractionation line as magnetite in CI and CM chondrite groups. Furthermore, Bench Crater carbonates are characterised by oxygen isotope compositions plotting at the oxygen¹⁶-rich end of the trend defined by carbonates from CM2 chondrite falls and some CM1 chondrites from the Antarctic meteorite collection (Allan Hills 83100, Allan Hills 84034 and Meteorite Hills 01070). The oxygen isotope com-position of silicates in Bench Crater aqueously altered chondrules plots along the terrestrial fractionation line, similarly to the oxygen isotope compositions measured in bulk CI chondrites and in their matrix and most olivine grains. The oxygen isotope compositions of silicates in aqueously altered chondrules yield an average relative proportion of oxygen¹⁷ of −0.12 parts per thousand . Such a oxygen¹⁷ proportion value is, within errors, intermediate between the oxygen¹⁷ proportion of CI chondrite matrix (0.37 parts per thousand) and to that of CM chondrite matrix ( oxygen¹⁷ proportion −1.76  parts per thousand ). Finally, the relative oxygen¹⁷ and oxygen¹⁸ isotope ratios in Bench Crater component are significantly lower than the oxygen¹⁷ and oxygen¹⁸ isotope ratio values of bulk CY chondrites.

The evolution of the relative oxygen¹⁷ values in Bench Crater meteorite components implies that the oxygen isotope compositions of sec-ondary phases (magnetite, carbonates) did not result from fluid circulation along a temperature gradient, which would produce a trend with a slope of 0.52. Instead, variations of relative oxygen¹⁷ values imply that the main process controlling the oxygen isotope compo-sitions of the Bench Crater secondary phases is related to iso-topic equilibrium between oxygen¹⁶-rich anhydrous silicates and oxygen¹⁷-and oxygen¹⁸-rich fluids as commonly reported in CM chondrites. In this sce-nario, magnetite would correspond to early precipitates whereas carbonates formed after significant hydrothermal alteration. Fur-thermore, the carbonate oxygen isotope compositions show similarity with those reported in CM chondrites whose precipitation temper-atures were estimated to be less than 200°C. This suggests that Bench Crater did not experience significant heating. and dehydration processes, although the lack of tochilinite would suggest a temperature higher than 320°C. However, we note that the stability field of tochilinite is strongly affected by magnesium-iron substitutions and is not well constrained.

Taken together, the oxygen isotope composition of Bench Crater mineral phases, along with its modal mineralogy and matrix composition, do not exactly match that of a known carbonaceous chondrite group. It might represent a rare type of carbonaceous asteroid parent body that is currently unsam-pled in the Earth’s meteorite collection. However, Bench Crater has important similarities with carbon-rich hydrated CI and CM chon-drites; the differences could be related to greater amounts of water ice grains originally accreted by the Bench Crater parent body. Such a hypothesis could be tested thanks to several assumptions, and following the methodology applied to CM, CO, CR and CV carbona-ceous chondrites. Bench Crater carbonates show relative oxygen¹⁷ and oxygen¹⁸ values plotting on the CM calcium-carbonate trend, suggesting they precipitated from water with a similar oxygen isotope evolution than that of CM chondrites. Assuming that the bulk oxygen isotope composition of Bench Crater is similar to the most altered CM chondrites (i.e. relative oxygen¹⁸ values of ten parts per thousand), and considering the oxygen isotope composition of anhydrous CM sil-icates as plausible Bench Crater protolith (i.e. relative oxygen¹⁸ values of -4.2 parts per thousand), Joy et al. calculated the water/rock ratio at different temperature ranging from 25 to 150°C. This gives a water/rock ratio for Bench Crater in the range 0.35 to 0.55, which is slightly higher than for most CM chondrites that are characterised by a narrow range of water/rock ratio of 0.3-0.4 irrespective of their petrological type. Although speculative, these results suggest thatthe Bench Crater asteroidal parent-body was more water-rich than the source location(s) of other CM chondrites. In addition, the physio-chemical conditions of hydrothermal alteration in the Bench Crater parent-body might have been different than in other CM chondrite original parent body(ies), as indicated by the higher abundance of magnetite in Bench Crater compared to most CM chondrites (i.e. 12.4% by area vs. 1.1-2.4 % by volume), and the lack of tochilinite.

The agglutinitic rim of Bench Crater indicates that it has been affected by flash heating on the lunar surface, but that such effects only affected the outer about 10-30 μm of the fragment. Matrix mineralogy and chemical composition also allows assessing the thermal history of the Bench Crater fragment as a whole. Low analytical totals obtained through electron microprobe analyses in the matrix of Bench Crater (91-93 %; by weight) may be related to the presence of micro-porosity, and/or species not accounted for during electron microprobe analysis such as water/hydroxide and/or carbon. Transmission electron microscopy observation of saponite in the matrix suggests that the missing 7-9 wt% are likely related to the presence of water and/or hydroxide. However, low electron microprobe totals obtained in Bench Crater matrix are higher than those typically recorded in unmodified CI and CM meteorite matrix and more similar to carbonaceous chondrite types that have undergone a small degree of dehydration from thermal processing at around 500-600°C.

Location of the approximately 15 μm secondary ion mass spectrometry spots locations in (a) dolomite and (b) predominantly calcite with minor dolomite phase. Joy et al. (2020).

Peak temperatures experienced by the bulk Bench Crater mete-orite can be constrained by petrographic observations. The preser-vation of saponite indicates that the bulk meteorite did not experience heating over about 700-900°C, as saponite has been shown to fully decompose above these temperatures. Moreover, temperatures cannot have exceeded about 600-700°C as carbonates are not decomposed and no vesicles can be seen in calcite phases (from carbon dioxide loss). As no serpentine is observed in the Bench Crater sample matrix, heating may have occurred at temperatures between about 400 and 800°C as serpentine breaks down by about 400°C. Boundaries of the aque-ously altered chondrules are generally well preserved, analogous to those observed in carbonaceous chondrite heating experiments below 600°C. Interestingly, about 600°C also corresponds to the temperature where hydrogen isotope anomaly hotspots have been shown to disappear in Murchison organics, which may account for the ab-sence of hydrogen hotspots in Bench Crater. Therefore, we estimate that the bulk Bench Crater meteorite underwent heating between about 400-600°C, which was enough to partially, but not totally, dehydrate the fine-grained matrix.

It is challenging to determine if heating of Bench Crater was caused by asteroidal parent body processes (for example, internal heating from aluminium²⁶ decay, impact metamorphism, flash heating from solar irradiation during an orbital transfer close to the Sun, during the impact event that delivered Bench Crater to the Moon, or during lunar surface res-idence (e.g., repeated diurnal thermal cycling, flash heating from other impact events). It is generally thought that thermal meta-morphism that has affected the dozens of heated CM chondrites was short lived and took place billions of years after the forma-tion of the Solar System, ruling out internal heating from aluminium²⁶ decay as a possible cause. If heating of Bench Crater took place on its parent body the remaining options then include short-lived impact-related meta-morphism or solar irradiation. The Bench Crater meteorite does not have a strong petrofabric, unlike some of the shocked CM chondrite types, suggesting that it has not been highly shocked. How-ever, intermediate phase (i.e., decomposed phyllosilicates) similar to that observed in Bench Crater was observed during less than 21-30 gigapascal peak pressure impact experiments on the Murchison (CM2) meteorite. Thus, it is difficult to further discrim-inate whether shock metamorphism or solar irradiation were responsible for heating of Bench Crater if metamorphism took place on its parent body.

Hydrogen in carbonaceous chondrites is hosted within both phyllosilicate and organic phases, whereas carbon and nitrogen are mostly hosted within organic components, and to a lesser extent within carbonates for carbon. The hydrogen and carbon isotope compositions obtained on two areas of Bench Crater are similar to those obtained on bulk CI and CM chondrite meteorites. The hydrogen isotope compositions measured in Bench Crater is also consistent with the hydrogen isotope compositions measured in CI-and CM-like clasts found in Howardite-Eucrite-Diogenite meteorites. On the other hand, the nitrogen isotope com-position of Bench Crater is intermediate between the bulk proportion of nitrogen¹⁵ values of CI-CM chondrites and the bulk proportion of nitrogen¹⁵ value of the 12037 soil. There may be some slight bulk deuteriun, carbon¹³ and nitrogen¹⁵ variability between the two area analysed that may relate to sample heterogeneity on the scale of a few microns. Alternatively, the observed bulk deuteriun, carbon¹³ and nitrogen¹⁵ variations may be related to localised impact shock-induced volatile element isotopic fractionation. It is easier to ‘lose’ the isotopes carbon¹³, nitrogen¹⁵ and hydrogen mostly bound in inorganic phyllosilicate components in CI-CM type chondrites than carbon¹², nitrogen¹⁴ and deuterium that are mostly bound in insoluble organic matter, as has been shown for CM chondrites during 30-40 gigapascal peak shock pressure impact events (i.e.less than 1.5 km per second velocities). Starting from CM chondrite-like hydrogen, carbon and nitrogen isotope characteristics, such a process could qualitatively explain the concomitant proportionate deuterium increase and carbon¹³ and nitrogen¹⁵ decrease observed for the two areas analysed in the Bench Crater meteorite.

The wide range of isotope signatures observed for nitrogen trapped in the lunar regolith is consistent with varying mixing proportions between isotopically light solar wind nitrogen (nitrogen¹⁵ proportion around −400 ) and a more nitrogen¹⁵-rich ‘planetary’ component. The Bench Crater nitrogen¹⁵ proportion of −40 is lower than bulk nitrogen isotope compositions of CI-CM carbonaceous chondrite meteorites. This may indicate that Bench Crater sampled an asteroidal parent-body not repre-sented in the meteorite collection. However, the original nitrogen isotope composition of Bench Crater may have also been modified on the lunar surface. Its nitrogen¹⁵ proportion value is intermediate between that of the bulk 12037 soil and bulk CI-CM chondrite nitrogen¹⁵ proportion values, which may indicate that the original nitrogen isotope composition of Bench Crater has been lowered due to isotopic exchange with nitrogen in the target mare basaltic Apollo 12 soil, possibly during the flash-heating event that formed the meteorite’s agglutinitic rim. However, this latter scenario seems unlikely since CM-like chon-drites contain more than one order of magnitude more nitrogen (about 600 to 1000 parts per million) com-pared to the 12037 bulk soil (about 40 parts per million).

In situanalyses of Apollo soil and agglutinate particles have yielded a large range of deuterium/hydrogen ratios, suggesting mixing between nearly deuterium-free implanted solar wind and hydrogen-bearing sources with higher deuterium/hydrogen ratios that may include re-worked (melted) material from vaporisation of impacting deuterium-rich organics or water-bearing asteroids, interplanetary dust particles and comets, volcanic gases, or caused by a spallogenic component. Bench Crater has deuterium proportion values ranging between −36 and 200 parts per thousand. It is unlikely that the deuterium/hydrogen ratio of Bench Crater hydrogen-bearing species could have been significantly altered by interacting with low deuterium/hydrogen hydrogen derived from the lunar target soil since CM-like chondrites contain more than two orders of magnitude more hydrogen (1-1.5 % by weight) than Apollo 12 bulk soils (about 10-100 parts per million). Instead we inter-pret that this range of δD values of 0-200 likely corresponds to the bulk original hydrogen isotope composition of the Bench Crater parent body, which is consistent with bulk hydrogen isotope compositions measured in CI and CM chondrites.

The survivability of hydrated asteroidal material in Apollo 12 soil 12037 indicates that (i) delivered volatiles are stable against small meteoritic impact events at the Moon’s surface, and (ii) ag-glutination of impactor particles either during the impact event, or subsequently during lunar regolith gardening, does not neces-sarily cause complete degassing and dehydration or light stable isotope fractionation of delivered hydrated material. These find-ings provide important constraints to ground-truth future lunar prospecting missions that will investigate the volatile concentra-tion and isotopic composition of the lunar regolith at, and below, the surface. Bench Crater provides critical constraints for these exploration activities that aim to identify the sources of different volatile species with depth and time.

Bench Crater bears some resemblance with highly aqueously al-tered and/or brecciated CM chondrites such as Boriskino and LON 94101. However, fully evaluating the possibility that Bench Crater is a CI-like clast-rich brecciated CM chondrite is hindered by its limited size and thus representativeness. With this caveat in mind, detailed mineralogical, geochemical, and isotopic data obtained on Bench Crater might also suggest that it is unique compared with known carbonaceous meteorite groups present in our meteorite collection, providing evidence for delivery of a sample from a previously unknown type of mildly thermally processed carbonaceous asteroid parent body. Other types of potentially unique partially thermally heated carbonaceous chondrite clasts have also been observed in other planetary regolith samples, including those from the howardite and ureilite parent bodies. These ther-mally processed carbonaceous meteorites can provide important constraints for interpreting spectral observations of the surface of carbonaceous asteroids that likely host a mixture of hydrated and dehydrated phases. In addition, they may provide a close match to samples that will be brought back from asteroid 162173 Ryugu by the Hayabusa2 spacecraft in 2020, since spectral characteristics of its surface are consistent with those of thermally metamorphosed CI-CM-CY carbonaceous chondrites.

Altogether, Bench Crater mineralogical, geochemical and iso-topic characteristics do not match any other types of carbonaceous chondrite present in our collections. Given that Bench Crater may have been delivered to the Moon anytime in the last 100 million years, this may indicate a recent change in sources of materials impacting the Earth-Moon system. Identifying such changes would help to better understand the sources and causes of impact bombardment, providing better constraints to refine theoretical Solar System models and track the migration of volatile-rich planetary bodies into the inner Solar System through time.

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