ALBERT

Description: Many studies exist on magmatic volatiles (H, C, N, F, S, Cl) in and on the Moon, within the last several years, that have cast into question the post-Apollo view of lunar formation, the distribution and sources of volatiles in the Earth-Moon system, and the thermal and magmatic evolution of the Moon. However, these recent observations are not the first data on lunar volatiles. When Apollo samples were first returned, substantial efforts were made to understand volatile elements, and a wealth of data regarding volatile elements exists in this older literature. In this review paper, we approach volatiles in and on the Moon using new and old data derived from lunar samples and remote sensing. From combining these data sets, we identified many points of convergence, although numerous questions remain unanswered. The abundances of volatiles in the bulk silicate Moon (BSM), lunar mantle, and urKREEP [last ~1% of the lunar magma ocean (LMO)] were estimated and placed within the context of the LMO model. The lunar mantle is likely heterogeneous with respect to volatiles, and the relative abundances of F, Cl, and H 2 O in the lunar mantle (H 2 O 〉 F 〉〉 Cl) do not directly reflect those of BSM or urKREEP (Cl 〉 H 2 O F). In fact, the abundances of volatiles in the cumulate lunar mantle were likely controlled by partitioning of volatiles between LMO liquid and nominally anhydrous minerals instead of residual liquid trapped in the cumulate pile. An internally consistent model for lunar volatiles in BSM should reproduce the absolute and relative abundances of volatiles in urKREEP, the anorthositic primary crust, and the lunar mantle within the context of processes that occurred during the thermal and magmatic evolution of the Moon. Using this mass-balance constraint, we conducted LMO crystallization calculations with a specific focus on the distributions and abundances of F, Cl, and H 2 O to determine whether or not estimates of F, Cl, and H 2 O in urKREEP are consistent with those of the lunar mantle, estimated independently from the analysis of volatiles in mare volcanic materials. Our estimate of volatiles in the bulk lunar mantle are 0.54–4.5 ppm F, 0.15–5.3 ppm H 2 O, 0.26–2.9 ppm Cl, 0.014–0.57 ppm C, and 78.9 ppm S. Our estimates of H 2 O are depleted compared to independent estimates of H 2 O in the lunar mantle, which are largely biased toward the "wettest" samples. Although the lunar mantle is depleted in volatiles relative to Earth, unlike the Earth, the mantle is not the primary host for volatiles. The primary host of the Moon’s incompatible lithophile volatiles (F, Cl, H 2 O) is urKREEP, which we estimate to have 660 ppm F, 300–1250 ppm H 2 O, and 1100–1350 ppm Cl. This urKREEP composition implies a BSM with 7.1 ppm F, 3–13 ppm H 2 O, and 11–14 ppm Cl. An upper bound on the abundances of F, Cl, and H 2 O in urKREEP and the BSM, based on F abundances in CI carbonaceous chondrites, are reported to be 5500 ppm F, 0.26–1.09 wt% H 2 O, and 0.98–1.2 wt% Cl and 60 ppm F, 27–114 ppm H 2 O, and 100–123 ppm Cl, respectively. The role of volatiles in many lunar geologic processes was also determined and discussed. Specifically, analyses of volatiles from lunar glass beads as well as the phase assemblages present in coatings on those beads were used to infer that H 2 is likely the primary vapor component responsible for propelling the fire-fountain eruptions that produced the pyroclastic glass beads (as opposed to CO). The textural occurrences of some volatile-bearing minerals are used to identify hydrothermal alteration, which is manifested by sulfide veining and sulfide-replacement textures in silicates. Metasomatic alteration in lunar systems differs substantially from terrestrial alteration due to differences in oxygen fugacity between the two bodies that result in H 2 O as the primary solvent for alteration fluids on Earth and H 2 as the primary solvent for alteration fluids on the Moon (and other reduced planetary bodies). Additionally, volatile abundances in volatile-bearing materials are combined with isotopic data to determine possible secondary processes that have affected the primary magmatic volatile signatures of lunar rocks including degassing, assimilation, and terrestrial contamination; however, these processes prove difficult to untangle within individual data sets. Data from remote sensing and lunar soils are combined to understand the distribution, origin, and abundances of volatiles on the lunar surface, which can be explained largely by solar wind implantation and spallogenic processes, although some of the volatiles in the soils may also be either indigenous to the Moon or terrestrial contamination. We have also provided a complete inventory of volatile-bearing mineral phases indigenous to lunar samples and discuss some of the "unconfirmed" volatile-bearing minerals that have been reported. Finally, a compilation of unanswered questions and future avenues of research on the topic of lunar volatiles are presented, along with a critical analysis of approaches for answering these questions.

Description: Tridymite, a low-pressure, high-temperature (〉870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.%...

Description: Apatite grains in lunar mare basalts contain hydrogen that ranges in D/H ratio by more than a factor of two. For most of these basalts, the D/H ratios in their apatite grains decrease with measures of the host basalts’ time spent at elevated temperature, specifically the Fe-Mg homogenization of their pyroxenes. Most basalts with homogeneous pyroxenes (i.e., with constant Fe/Mg ratio) have apatite grains with low D/H (D –100), whereas most basalts with heterogeneous pyroxenes (i.e., varying or zoned Fe/Mg) have apatite with high D/H (D up to ~ +1100). This relationship suggests that low D/H values were acquired during thermal processing, i.e., during Fe-Mg chemical equilibration, during or after emplacement. This light hydrogen is likely derived from solar wind implanted into the lunar regolith (with D from –125 to –800), and could enter basalts either by assimilation of regolith or by vapor transport from regolith heated by the flow. If a basalt could not interact with regolith rich in solar wind (e.g., it was emplaced onto other fresh basalts), its apatite could retain a magmatic D/H signature. The high D/H component (in the apatites of unequilibrated basalts) is most reasonably that indigenous magmatic hydrogen, i.e., representing hydrogen in the basalt’s source mantles, or magmatic hydrogen that was residual after partial degassing of H 2 .

Description: Among the lunar samples that were returned by the Apollo missions are many cumulate plutonic rocks with high Mg# [molar Mg/(Mg+Fe) in %] and abundances of KREEP elements (potassium, rare earth elements, phosphorus, U, Th, etc.) that imply KREEP-rich parental magmas. These rocks, collectively called the magnesian suite, are nearly absent from sampling sites distant from Imbrium basin ejecta, including those of lunar highlands meteorites. This absence has significant implications for the early differentiation of the Moon and its distribution of heat-producing elements (K, Th, U). Here, we analyze a unique fragment of basalt with the mineralogy and mineral chemistry of a magnesian suite rock, in the lunar highlands meteorite Allan Hills (ALH) A81005. In thin section, the fragment is 700 x 300 μm, and has a sub-ophitic texture with olivine phenocrysts, euhedral plagioclase grains (An 97-70 ),and interstitial pyroxenes. Its minerals are chemically equilibrated. Olivine has Fe/Mn ~ 70 (consistent with a lunar origin), and Mg# ~80, which is consistent with rocks of the magnesian suite and far higher than in mare basalts. It has a rich suite of minor minerals: fluorapatite, ilmenite, Zr-armalcolite, chromite, troilite, silica, and Fe metal (Ni = 3.8%, Co = 0.17%). The metal is comparable to that in chondrite meteorites, which suggests that the fragment is from an impact melt. The fragment itself is not a piece of magnesian suite rock (which are plutonic), but its mineralogy and mineral chemistry suggest that its protolith (which was melted by impact) was related to the magnesian suite. However, the fragment’s mineral chemistry and minor minerals are not identical to those of known magnesian suite rocks, suggesting that the suite may be more varied than apparent in the Apollo samples. Although ALHA81005 is from the lunar highlands (and likely from the farside), Clast U need not have formed in the highlands. It could have formed in an impact melt pool on the nearside and been transported by meteoroid impact. Lunar highlands meteorites should be searched for rock fragments related to the magnesian-suite rocks, but the fragments are rare and may have mineral compositions similar to some meteoritic (impactor) materials.

Description: The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free ("dry") Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because 37 Cl/ 35 Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, 37 Cl/ 35 Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high 37 Cl/ 35 Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon’s history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets.

Description: A suite of Hawaiian basalts that were variably altered in the presence of SO 2 -rich gases during the current summit eruptive episode at Halemaumau crater, Kilauea, were studied to determine their alteration phase assemblage and reactive pathways using electron microscopy, Mössbauer spectroscopy, and X-ray diffraction. The alteration conditions represent an acid fog environment. Alteration rinds on the basalts vary in thickness from tens of micrometers to the entirety of the rock and are composed of amorphous silica rims (85–95 wt% SiO 2 ) overlain by sulfates. Sulfate mineralogy consisted of gypsum, anhydrite, and natroalunite-jarosite. No phyllosilicates were observed in any alteration assemblages. Phenocrysts and glass were both observed to be extensively reacted during alteration. The Halemaumau samples may provide good analogs for basalt alteration on other rocky planetary bodies, i.e., Mars, Venus, and Mercury, where S is ubiquitous and low fluid/rock ratios are common.

Description: The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ~20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H 2 O inside the CheMin instrument (relative humidity 〈1%). Smectite interlayers in John Klein collapsed sometime between clay mineral formation and the time of analysis to a basal spacing of 10 Å, but largely remain open in the Cumberland sample with a basal spacing of ~13.2 Å. Partial intercalation of Cumberland smectites by metal-hydroxyl groups, a common process in certain pedogenic and lacustrine settings on Earth, is our favored explanation for these differences. The relatively low abundances of olivine and enriched levels of magnetite in the Sheepbed mudstone, when compared with regional basalt compositions derived from orbital data, suggest that clay minerals formed with magnetite in situ via aqueous alteration of olivine. Mass-balance calculations are permissive of such a reaction. Moreover, the Sheepbed mudstone mineral assemblage is consistent with minimal inputs of detrital clay minerals from the crater walls and rim. Early diagenetic fabrics suggest clay mineral formation prior to lithification. Thermodynamic modeling indicates that the production of authigenic magnetite and saponite at surficial temperatures requires a moderate supply of oxidants, allowing circum-neutral pH. The kinetics of olivine alteration suggest the presence of fluids for thousands to hundreds of thousands of years. Mineralogical evidence of the persistence of benign aqueous conditions at YKB for extended periods indicates a potentially habitable environment where life could establish itself. Mediated oxidation of Fe 2+ in olivine to Fe 3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

Description: Mg-Al spinel is rare in lunar rocks (Apollo and meteorite collections), and occurs mostly in troctolites and troctolitic cataclastites. Recently, a new lunar lithology, rich in spinel and plagioclase, and lacking abundant olivine and pyroxene, was recognized in visible to near-infrared (VNIR) reflectance spectra by the Moon Mineralogy Mapper (M 3 ) instrument on the Chandrayaan-1 spacecraft at the Moscoviense basin. These outcrop-scale areas are inferred to contain 20–30% Mg-Al spinel. Possible explanations for the petrogenesis of spinel-bearing and spinel-rich lithology(s) range from low-pressure near-surface crystallization to a deep-seated origin in the lower lunar crust or upper mantle. Here, we describe 1-bar crystallization experiments conducted on rock compositions rich in olivine and plagioclase that crystallize spinel. This would be equivalent to impact-melting, which is moderately common among lunar plutonic rocks and granulites. To explore possible precursor materials and the maximum amount of spinel that could be crystallized, a lunar troctolitic composition similar to Apollo pink spinel troctolite 65785, and a composition similar to ALHA81005 as analog to the source region of this meteorite have been chosen. The crystallization experiments on the composition of AHLA 81005 did not yield any spinel; experiments on the composition similar to Apollo 65785 crystallized a maximum of ~8 wt% spinel, much less than the suggested 20–30% spinel of the new lithology detected by M 3 . However, our VNIR spectral reflectance analyses of the experimental run products indicate that the spinel composition of the experimental run products not only appears to be similar to the composition of the spinel lithology detected by M 3 (characteristics of the spinel absorption), but also that the modal abundances of coexisting phases (e.g., mafic glass) influence the spectral reflectance properties. Thus, the spinel-rich deposits detected by M 3 might not be as spinel-rich as previously thought and could contain as little as 4–5 wt% spinel. However, the effect of space weathering on spinel is unknown and could significantly weaken its 2 μm absorptions. If this occurs, weathered lunar rocks could contain more spinel than a comparison with our unweathered experimental charges would suggest.

Description: Ferrian saponite from the eastern Santa Monica Mountain, near Griffith Park (Los Angeles, California), was investigated as a mineralogical analog to smectites discovered on Mars by the CheMin X-ray diffraction instrument onboard the Mars Science Laboratory (MSL) rover. The martian clay minerals occur in sediment of basaltic composition and have 02 l diffraction bands peaking at 4.59 Å, consistent with tri-octahedral smectites. The Griffith saponite occurs in basalts as pseudomorphs after olivine and mesostasis glass and as fillings of vesicles and cracks and has 02 l diffraction bands at that same position. We obtained chemical compositions (by electron microprobe), X-ray diffraction patterns with a lab version of the CheMin instrument, Mössbauer spectra, and visible and near-IR reflectance (VNIR) spectra on several samples from that locality. The Griffith saponite is magnesian, Mg/(Mg+Fe) = 65–70%, lacks tetrahedral Fe 3+ and octahedral Al 3+ , and has Fe 3+ /Fe from 64 to 93%. Its chemical composition is consistent with a fully tri-octahedral smectite, but the abundance of Fe 3+ gives a nominal excess charge of +1 to +2 per formula unit. The excess charge is likely compensated by substitution of O 2– for OH – , causing distortion of octahedral sites as inferred from Mössbauer spectra. We hypothesize that the Griffith saponite was initially deposited with all its iron as Fe 2+ and was oxidized later. X-ray diffraction shows a sharp 001 peak at 15 Å, 00 l peaks, and a 02 l diffraction band at the same position (4.59 Å) and shape as those of the martian samples, indicating that the martian saponite is not fully oxidized. VNIR spectra of the Griffith saponite show distinct absorptions at 1.40, 1.90, 2.30–2.32, and 2.40 μm, arising from H 2 O and hydroxyl groups in various settings. The position of the ~2.31 μm spectral feature varies systematically with the redox state of the octahedrally coordinated Fe. This correlation may permit surface oxidation state to be inferred (in some cases) from VNIR spectra of Mars obtained from orbit, and, in any case, ferrian saponite is a viable assignment for spectral detections in the range 2.30–2.32 μm.

Description: In the last decade, it has been recognized that the Moon contains significant proportions of volatile elements (H, F, Cl), and that they are transported through the lunar crust and across its surface. Here, we document a significant segment of that volatile cycle in lunar granulite breccia 79215: impact-induced remobilization of volatiles, and vapor-phase transport with extreme elemental fractionation. 79215 contains ~1% volume of fluorapatite, Ca 5 (PO 4 ) 3 (F,Cl,OH), in crystals to 1 mm long, which is reflected in its analyzed abundances of F, Cl, and P. The apatite has a molar F/Cl ratio of ~10, and contains only 25 ppm OH and low abundances of the rare earth elements (REE). The chlorine in the apatite is isotopically heavy, at 37 Cl = +32.7 ± 1.6. Hydrogen in the apatite is heavy at D = +1060 ± 180; much of that D came from spallogenic nuclear reactions, and the original D was lower, between +350 and +700. Unlike other P-rich lunar rocks (e.g., 65015), 79215 lacks abundant K and REE, and other igneous incompatible elements characteristic of the lunar KREEP component. Here, we show that the P and halogens in 79215 were added to an otherwise "normal" granulite by vapor-phase metasomatism, similar to rock alteration by fumarolic exhalations as observed on Earth. The ultimate source of the P and halogens was most likely KREEP, it being the richest reservoir of P on the Moon, and 79215 having H and Cl isotopic compositions consistent with KREEP. A KREEP-rich rock was heated and devolatilized by an impact event. This vapor was fractionated by interaction with solid phases, including merrillite (a volatile-free phosphate mineral), a Fe-Ti oxide, and a Zr-bearing phase. These solids removed REE, Th, Zr, Hf, etc., from the vapor, and allowed the vapor to transport primarily P, F, and Cl, with lesser proportions of Ba and U into 79215. Vapor-deposited crystals of apatite (to 30 μm) are known in some lunar regolith samples, but lunar vapor has not (before this) been implicated in significant mass transfer. It seems unlikely, however, that phosphate-halogen metasomatism is related to the high-Th/Sm abundance ratios of this and other lunar magnesian granulites. The metasomatism of 79215 emphasizes the importance of impact heating in the lunar volatile cycle, both in mobilizing volatile components into vapor and in generating strong elemental fractionations.