Light element geochemistry of the Apollo 16 site

Pronounced variations in abundances and isotopic compositions of some light elements in soils from the Apollo 16 site are interpreted in terms of differing degrees of solar wind exposure for an originally, and approximately, homogeneous regolith. Carbon abundances in soils are compatible with a model in which equilibrium is established, after 10⁴-10⁵ yr, between solar wind input and loss by H stripping. However, this model does not explain the observed C isotopic distribution, suggesting that other sources of C or other processes, or both, are also important. Carbon abundances in rocks from Apollo 16 are higher (average 40 ppm) than at other landing sites although their isotopic compositions, ?35 < δ¹³C < ?16%. PDB, are normal. Abundances of N and, to a less extent, He and H in soils correlate with C as does a fraction of metallic Fe attributed to in situ reduction of indigenous Fe²⁺ by solar wind H.Fillet soil 67461 apparently contains solar wind C and N in a relatively unfractionated form, yielding an upper limit to solar wind (δ¹³C of ?16%., PDB and a value of 3.4 for $\text{C}\text{N}$ in the solar wind.Sulfur at the Apollo 16 site represents a paradox in that, although abundances in soils are apparently controlled by local rock S contents, they also correlate, for all but one sample, with δ³⁴S, which itself is apparently controlled by surface exposure age. A complex lunar S cycle is suggested.     

Do lunar and meteoritic archives record temporal variations in the composition of solar wind noble gases and nitrogen? A reassessment in the light of Genesis data

Since about half a century samples from the lunar and asteroidal regoliths been used to derive information about elemental and isotopic composition and other properties of the present and past solar wind, predominantly for the noble gases and nitrogen. Secular changes of several important compositional parameters in the solar wind were proposed, as was a likely secular decrease of the solar wind flux. In 2004 NASA’s Genesis mission returned samples which had been exposed to the solar wind for almost 2.5 years. Their analyses resulted in an unprecendented accuracy for the isotopic and elemental composition of several elements in the solar wind, including noble gases, O and N. The Genesis data therefore also allow to re-evaluate the lunar and meteorite data, which is done here. In particular, claims for long-term changes of solar wind composition are reviewed.Outermost grain layers from relatively recently irradiated lunar regolith samples conserve the true isotopic ratios of implanted solar wind species. This conclusion had been made before Genesis based on the agreement of He and Ne isotopic data measured in the aluminum foils exposed to the solar wind on the Moon during the Apollo missions with data obtained in the first gas release fractions of stepwise in-vacuo etch experiments. Genesis data allowed to strengthen this conclusion and to extend it to all five noble gases. Minor variations in the isotopic compositions of implanted solar noble gases between relatively recently irradiated samples (<100 Ma) and samples irradiated billions of years ago are very likely the result of isotopic fractionation processes that happened after trapping of the gases rather than indicative of true secular changes in the solar wind composition. This is particularly important for the ³He/⁴He ratio, whose constancy over billions of years indicates that hardly any ³He produced as transient product of the pp-chains has been mixed from the solar interior into its outer convective zone. The He isotopic composition measured in the present-day solar wind therefore is identical to the (D + ³He)/⁴He ratio at the start of the suns’s main sequence phase and hence can be used to determine the protosolar D/H ratio.Genesis settled the long-standing controversy on the isotopic composition of nitrogen in lunar regolith samples. The ¹⁵N/¹⁴N ratio in the solar wind as measured by Genesis is lower than in any lunar sample. This proves that nitrogen in regolith samples is dominated by non-solar sources. A postulated secular increase of ¹⁵N/¹⁴N by some 30% over the past few Ga is not tenable any longer. Genesis also provided accurate data on the isotopic composition of oxygen in the solar wind, invaluable for cosmochemisty. These data superseded but essentially confirmed one value – and disproved a second one – derived from lunar regolith samples shortly prior to Genesis.Genesis also confirmed prior conclusions that lunar regolith samples essentially conserve the true elemental ratios of the heavy noble gases in the solar wind (Ar/Kr, Kr/Xe). Several secular changes of elemental abundances of noble gases in the solar wind had been proposed based on lunar and meteoritic data. I argue here that lunar data – in concert with Genesis – provide convincing evidence only for a long-term decrease of the Kr/Xe ratio by almost a factor of two over the past several Ga. It appears that the enhancement of abundances of elements with a low first ionisation potential in the solar wind (FIP effect) changed with time.Finally, Genesis allows a somewhat improved comparison of the present-day flux of solar wind Kr and Xe with the total amount of heavy solar wind noble gases in the lunar regolith. It remains unclear whether the past solar wind flux has been several times higher on average than it is today.     

Re-examination of the formation ages of the Apollo 16 regolith breccias

The lunar regolith is exposed to irradiation from the solar wind and to bombardment by asteroids, comets and inter-planetary dust. Fragments of projectiles in the lunar regolith can potentially provide a direct measure of the sources of exogenous material being delivered to the Moon. Constraining the temporal flux of their delivery helps to address key questions about the bombardment history of the inner Solar System.Here, we use a revised antiquity calibration (after Eugster et al., 2001) that utilises the ratio of trapped ⁴⁰Ar/³⁶Ar (‘parentless’ ⁴⁰Ar derived from radioactive decay of ⁴⁰K, against solar wind derived ³⁶Ar) to semi-quantitatively calculate the timing of the assembly of the Apollo 16 regolith breccias. We use the trapped ⁴⁰Ar/³⁶Ar ratios reported by McKay et al. (1986). Our model indicates that the Apollo 16 ancient regolith breccia population was formed between ∼3.8 and 3.4 Ga, consistent with regoliths developed and assembled after the Imbrium basin-forming event at ∼3.85 Ga, and during a time of declining basin-forming impacts. The material contained within the ancient samples potentially provides evidence of impactors delivered to the Moon in the Late-Imbrian epoch. We also find that a young regolith population was assembled, probably by local impacts in the Apollo 16 area, in the Eratosthenian period between ∼2.5 and 2.2 Ga, providing insights to the sources of post-basin bombardment. The ‘soil-like’ regolith breccia population, and the majority of local Apollo 16 soils, were likely closed in the last 2 Ga and, therefore, potentially provide an archive of projectile types in the Eratosthenian and Copernican periods.     

Total nitrogen in lunar soils,breccias and rocks

The total nitrogen contents of a number of lunar samples from Apollo 16 and 17 missions are reported. Solar wind is the main source for the observed excess nitrogen in most fines. Total nitrogen in the soils is found to be proportional to the solar wind rare gases Ar³⁶ and Xe¹³². Linear correlations are also noted between the agglutinate contents of the soils and their carbon and nitrogen contents. Seventeen soils (Apollo 15, 16 and 17) have been sieved and nitrogen has been measured in various grain size fractions. An inverse correlation between the mean grain diameter and the nitrogen contents is seen, showing that a large fraction of the solar wind nitrogen is surface correlated. An apparent volume component, due to the presence of agglutinates, is found in most soils.     

Irradiation records in regolith materials. I: isotopic compositions of solar-wind neon and argon in single lunar mineral grains

We have applied a stepwise pyrolytic extraction technique to eleven individual lunar regolith grains to investigate the compositions of light noble gases embedded in grain surfaces by solar wind irradiation, with emphasis on the rather poorly known isotopic composition of solar-wind argon. Results are intriguing: average ²⁰Ne/²²Ne ratios observed in early pyrolytic releases from ilmenite grains separated from lunar soils 71501, 79035 and 10084 agree very well with both direct measures of the solar wind neon composition in the Apollo foils and with values obtained in first releases from acid-etched ilmenites by the Zürich laboratory, whereas these same pyrolytic and acid-etch fractions carry argon isotopic signatures that significantly disagree—average ³⁶Ar/³⁸Ar ratios near 5.8 for thermal extraction compared to 5.4–5.5 for chemical etching at Zürich. Consideration of the isotopic and elemental data from these grains in the context of first-order diffusive modeling calculations points to gas release at low temperatures, without significant isotopic or elemental fractionation, from isolated grain-surface reservoirs of solar wind composition. The physical nature of these reservoirs is presently unknown. In this interpretation the preferred solar wind ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios deduced from this study are respectively 13.81 ± 0.08 and 0.0333 ± 0.0003, both within error of the Zürich acid-etch values, and ³⁶Ar/³⁸Ar = 5.77 ± 0.08. It may be possible to reconcile the discrepancy between the acid-etch and pyrolytic estimates for the solar wind ³⁶Ar/³⁸Ar ratio in the context of arguments originally advanced by Benkert et al. (1993) to account for their He and Ne isotopic compositions. At the other, high-temperature end of the release profile from one of these grains there are clear isotopic indications of the presence of a Ne constituent with ²⁰Ne/²²Ne close to the 11.2 ratio found at Zürich and attributed by these workers to a deeply-sited component implanted by solar energetic particles.     

18O16O ratios in Luna 16 fines

Partial fluorination experiments developed on a 26 mg sample of Luna 16 fines show a big ¹⁸O enrichment in the first oxygen evolved similar to those observed by Epstein and Taylor on Apollo samples and probably related to the high solar wind content of this sample.     

On the origin of impact glass in the Apollo 16 regolith

This study addresses the issue of what fraction of the impact glass in the regolith of a lunar landing site derives from local impacts (those within a few kilometers of the site) as opposed to distant impacts (10 or more kilometers away). Among 10,323 fragments from the 64-210-μm grain-size fraction of three Apollo 16 regolith samples, 14% are impact glasses, that is, fragments consisting wholly or largely of glass produced in a crater-forming impact. Another 16% are agglutinates formed by impacts of micrometeorites into regolith. We analyzed the glass in 1559 fragments for major- and minor-element concentrations by electron probe microanalysis and a subset of 112 of the fragments that are homogeneous impact glasses for trace elements by secondary ion mass spectrometry. Of the impact glasses, 75% are substantially different in composition from either the Apollo 16 regolith or any mixture of rocks of which the regolith is mainly composed. About 40% of the impact glasses are richer in Fe, Mg, and Ti, as well as K, P, and Sm, than are common rocks of the feldspathic highlands. These glasses must originate from craters in maria or the Procellarum KREEP Terrane. Of the feldspathic impact glasses, some are substantially more magnesian (greater MgO/FeO) or have substantially lower concentrations of incompatible elements than the regolith of the Apollo 16 site. Many of these, however, are in the range of feldspathic lunar meteorites, most of which derive from points in the feldspathic highlands distant from the Procellarum KREEP Terrane. These observations indicate that a significant proportion of the impact glass in the Apollo 16 regolith is from craters occurring 100 km or more from the landing site. In contrast, the composition of glass in agglutinates, on average, is similar to the composition of the Apollo 16 regolith, consistent with local origin.     

Apollo 12 revisited

We present compositional data for 358 lithic fragments (2-4-mm size range) and 15 soils (<1-mm fines) from regolith samples collected at the Apollo 12 site. The regolith is dominated by mare basalt, KREEP impact-melt breccias (crystalline and glassy), and regolith breccias. Minor components include alkali anorthosite, alkali norite, granite, quartz monzogabbro, and anorthositic rocks from the feldspathic highlands. The typical KREEP impact-melt breccia of Apollo 12 (mean Th: 16 μg/g) is similar to that of the Apollo 14 site (16 μg/g), 180 km away. Both contain a minor component (0.3% at Apollo 12, 0.6% at Apollo 14) of FeNi metal that is dissimilar to metal in ordinary chondrites but is similar to metal found in Apollo 16 impact-melt breccias. The Apollo 12 regolith contains another variety of KREEP impact-melt breccia that differs from any type of breccia described from the Apollo sites in being substantially richer in Th (30 μg/g) but with only moderate concentrations of K. It is, however, similar in composition to the melt breccia lithology in lunar meteorite Sayh al Uhaymir 169. The average composition of typical mature soil corresponds to a mixture of 65% mare basalt, 20% typical KREEP impact-melt breccia, 7% high-Th impact-melt breccia, 6% feldspathic material, 2.6% alkali noritic anorthosite, and 0.9% CM chondrite. Thus, although the site was resurfaced by basaltic volcanism 3.1-3.3 Ga ago, a third of the material in the present regolith is of nonmare origin, mainly in the form of KREEP impact-melt breccias and glass. These materials occur in the Apollo 12 regolith mainly as a result of moderate-sized impacts into surrounding Fra Mauro and Alpes Formations that formed craters Copernicus (93 km diameter, 406 km distance), Reinhold (48 km diameter, 196 km distance), and possibly Lansberg (39 km diameter, 108 km distance), aided by excavation of basalt interlayers and mixing of regolith by small, local impacts. Anomalous immature soil samples 12024, 12032, and 12033 contain a lesser proportion of mare basalt and a correspondingly greater proportion of KREEP lithologies. These samples consist mainly of fossil or paleoregolith, likely ejecta from Copernicus, that was buried beneath the mixing zone of micrometeorite gardening, and then brought to the near surface by local craters such as Head, Bench, and Sharp Craters.     

Evidence from Ar/Ar ages of lunar impact glasses for an increase in the impact rate ∼800 Ma ago

Geochemical and ⁴⁰Ar/³⁹Ar data on nine impact glasses from the Apollo 14, 16, and 17 landing sites indicate at least seven distinct impact events with ages ∼800 Ma. Rock fragments analyzed by Barra et al. [Barra F., Swindle T. D., Korotev R. L., Jolliff B. L., Zeigler R. A., and Olsen E. (2006) ⁴⁰Ar-³⁹Ar dating of Apollo 12 regolith: implications for the age of Copernicus and the source of nonmare materials, Geochim. Cosmochim. Acta,70, 6016-6031] from the Apollo 12 landing site and some Apollo 12 spherules reported by Levine et al. [Levine J., Becker T. A., Muller R. A., Renne P. R. (2005) ⁴⁰Ar/³⁹Ar dating of Apollo 12 impact spherules, Geophys. Res. Let., 32, L15201, doi: 10.1029/2005GL022874.] show ∼800 Ma ages, close to the accepted age of the Copernicus event, 800 ± 15 Ma [Bogard D. D., Garrison D. H., Shih C. Y., and Nyquist L. E. (1994) ³⁹Ar-⁴⁰Ar dating of two lunar granites: The age of Copernicus, Geochim. Cosmochim. Acta, 58, 3093-3100]. These Apollo 12 samples are thought to have been affected by material from the Copernicus event since there is a Copernicus ray going through the Apollo 12 landing site. When all of these data are viewed collectively, including an Apollo 16 glass bomb [Borchardt R., Stöffler D., Spettel B., Palme H. and Wänke H. (1986) Composition, structure, and age of the Apollo 16 subregolith basement as deduced from the chemistry of post-Imbrium melt bombs. In Proceedings, 17th Lunar and Planetary Science Conference, pp. E43-E54], and in the context of diverse compositional range and sample location, there is a suggestion that there may have been a transient increase in the global lunar impact flux at ∼800 Ma. Therefore, the Copernicus impact event could have been one of many. If correct, there should be evidence for this increased impact flux around 800 Ma ago in the age statistics of terrestrial impact samples.     

Two oxygen isotopic components with extra-selenial origins observed among lunar metallic grains - In search for the solar wind component

Oxygen isotopic analyses were performed in the surface layers of lunar metallic grains from lunar regolith samples 71501 and 79035, presumably exposed at the Moon surface at different times. We were able to reproduce the two extreme O components previously found [Hashizume K. and Chaussidon M. (2005) A non-terrestrial ¹⁶O-rich isotopic composition for the protosolar nebula. Nature434, 619-622; Ireland T. R., Holden P., Norman M. D. and Clarke J. (2006) Isotopic enhancements of ¹⁷O and ¹⁸O from solar wind particles in the lunar regolith. Nature440, 776-778], with a range observed of −12 ± 5 < Δ¹⁷O < +33 ± 3‰ (1σ). The relatively minor ¹⁶O-rich component corresponding to an end-member Δ¹⁷O value lower than −20‰ is likely the solar component. This comes from the fact that its concentration roughly agrees with the maximum solar wind abundance expected among the grains from the two samples. At variance the ¹⁶O-poor component is 5-10 times more abundant and thus likely non-solar. The δ¹⁸O range found for the ¹⁶O-poor component may reflect various processes such as isotope exchange reaction during oxidation of metallic iron and/or isotope fractionation by evaporation/condensation at the surface of the Moon or during implantation at depth in the lunar metallic grains. The present study suggests that planetary solid materials in bulk are systematically depleted in ¹⁶O relative to the solar isotopic composition, suggesting the existence of non-mass-dependent isotopic fractionations associated to the formation of solids in the accretion disk.     

Solar and cosmogenic argon in dated lunar impact spherules

We have studied lunar impact spherules from the Apollo 12 and Apollo 14 landing sites, examining the isotopic composition of argon released by stepwise heating. Elsewhere, we reported the formation ages of these spherules, determined by the ⁴⁰Ar/³⁹Ar isochron method. Here, we discuss solar and cosmogenic argon from the same spherules, separating these two components by correlating their partial releases with the releases of calcium-derived ³⁷Ar on a “cosmochron” diagram. We use the abundances of cosmogenic argon to derive a cosmic ray exposure age for each spherule, and demonstrate that single scoops of lunar soil contain spherules which have experienced very different histories of exposure and burial. The solar argon is seen to be separated into isotopically lighter and heavier fractions, which presumably were implanted to different depths in the spherules. The abundance of the isotopically heavy solar argon is too great to explain as a minor constituent of the solar particle flux, such as the suprathermal tail of the solar wind. The fact that the spherules have been individually dated allows us to look for possible variations in the solar wind as a function of time, over the history of the Solar System. However, the isotopic composition and fluence of solar argon preserved in the lunar spherules appear to be independent of formation age. We believe that most of the spherules are saturated with solar argon, having reached a condition in which implantation by the solar wind is offset by losses from solar-wind sputtering and diffusion.     

Solar wind helium, neon, and argon isotopic and elemental composition: Data from the metallic glass flown on NASA’s Genesis mission

Solar wind (SW) helium, neon, and argon trapped in a bulk metallic glass (BMG) target flown on NASA’s Genesis mission were analyzed for their bulk composition and depth-dependent distribution. The bulk isotopic and elemental composition for all three elements is in good agreement with the mean values observed in the Apollo Solar Wind Composition (SWC) experiment. Conversely, the He fluence derived from the BMG is up to 30% lower than values reported from other Genesis bulk targets or in-situ measurements during the exposure period. SRIM implantation simulations using a uniform isotopic composition and the observed bulk velocity histogram during exposure reproduces the Ne and Ar isotopic variations with depth within the BMG in a way which is generally consistent with observations. The similarity of the BMG release patterns with the depth-dependent distributions of trapped solar He, Ne, and Ar found in lunar and asteroidal regolith samples shows that also the solar noble gas record of extraterrestrial samples can be explained by mass separation of implanted SW ions with depth. Consequently, we conclude that a second solar noble gas component in lunar samples, referred to as the “SEP” component, is not needed. On the other hand, a small fraction of the total solar gas in the BMG released from shallow depths is markedly enriched in the light isotopes relative to predictions from implantation simulations with a uniform isotopic composition. Contributions from a neutral solar or interstellar component are too small to explain this shallow sited gas. We tentatively attribute this superficially implanted gas to low-speed, current-sheet related SW, which was fractionated in the corona due to inefficient Coulomb drag. This fractionation process could also explain relatively high Ne/Ar elemental ratios in the same initial gas fraction.     

Trapped solar wind noble gases and exposure age of Luna 16 lunar fines

He, Ne, Ar, Kr and Xe concentrations and isotopic abundances were measured in three bulk grain size fractions prepared from sample L-16-19, No. 120 (C level, 20–22 cm depth) returned by the Luna 16 mission. The expected anticorrelation between the concentrations of trapped solar wind noble gases and grain size is observed. Elemental abundances of solar wind trapped noble gases are similar to those previously found in corresponding grain size fractions of the Apollo 11 and 12 fines. The trapped ratio ${}^4\text{He}{}^{20}\text{Ne}$ varies in the soils from different lunar maria due to diffusion losses. A rough correlation of ${}^4\text{He}{}^{20}\text{Ne}$ with the proportion of ilmenite in these samples is apparent. The elemental and isotopic ratios of the surface correlated noble gases in Luna 16 resemble those previously found in Apollo fines. Based on ²¹Ne, ⁷⁸Kr and ¹²⁶Xe a cosmic ray exposure age of 360 my was determined. This age is similar to those obtained for the soils from other lunar maria.     

Argon, krypton, and xenon in the bulk solar wind as collected by the Genesis mission

We present bulk solar wind isotopic and elemental ratios for Ar, Kr, and Xe averaged from up to 14 individual analyses on silicon targets exposed to the solar wind for ∼2.3 years during NASA’s Genesis mission. All averages are given with 1σ standard errors of the means and include the uncertainties of our absolute calibrations. The isotopic ratios ⁸⁶Kr/⁸⁴Kr and ¹²⁹Xe/¹³²Xe are 0.303 ± 0.001 and 1.06 ± 0.01, respectively. The elemental ratios ³⁶Ar/⁸⁴Kr and ⁸⁴Kr/¹³²Xe are 2390 ± 120 and 9.9 ± 0.3, respectively. Average fluxes of ⁸⁴Kr and ¹³²Xe in the bulk solar wind in atoms/(cm² s) are 0.166 ± 0.009 and 0.017 ± 0.001, respectively. The flux uncertainties also include a 2% uncertainty for the determination of the extracted areas. The bulk solar wind ³⁶Ar/³⁸Ar ratio of 5.50 ± 0.01 and the ³⁶Ar flux of 397 ± 11 atoms/(cm² s) determined from silicon targets agree well with the ³⁶Ar/³⁸Ar ratio and the ³⁶Ar flux determined earlier on a different type of target by Heber et al. (2009). A comparison of the solar wind noble gas/oxygen abundance ratios with those in the solar photosphere revealed a slight enrichment of Xe and, within uncertainties a roughly uniform depletion of Kr-He in the solar wind, possibly related to the first ionization potentials of the studied elements. Thus, the solar wind elemental abundances He-Kr display within uncertainties roughly photospheric compositions relative to each other. A comparison of the Genesis data with solar wind heavy noble gas data deduced from lunar regolith samples irradiated with solar wind at different times in the past reveals uniform ³⁶Ar/⁸⁴Kr ratios over the last 1-2 Ga but an increase of the ⁸⁴Kr/¹³²Xe ratio of about a factor of 2 during the same time span. The reason for this change in the solar wind composition remains unknown.     

Irradiation records in regolith materials, II: Solar wind and solar energetic particle components in helium, neon, and argon extracted from single lunar mineral grains and from the Kapoeta howardite by stepwise pulse heating

High-resolution stepped heating has been used to extract light noble gases implanted in a suite of 13 individual lunar ilmenite and iron grains and in the Kapoeta howardite by solar wind (SW) and solar energetic particle (SEP) irradiation. Isotopic analyses of gases evolved at low temperatures from the lunar grains confirm the neon and argon compositions obtained by Pepin et al. (Pepin R. O., Becker R. H., and Schlutter D. J., “Irradiation records in regolith materials, I: Isotopic compositions of solar-wind neon and argon in single lunar regolith grains”, Geochim. Cosmochim. Acta63, 2145-2162, 1999) in an initial study of 11 regolith grains, primarily ilmenites. Combination of the data sets from both investigations yields ²⁰Ne/²²Ne = 13.85 ± 0.04, ²¹Ne/²²Ne = 0.0334 ± 0.0003, and ³⁶Ar/³⁸Ar = 5.80 ± 0.06 for the lunar samples; the corresponding ³⁶Ar/³⁸Ar ratio in Kapoeta is 5.74 ± 0.06. The neon ratios agree well with those measured by Benkert et al. (Benkert J.-P., Baur H., Signer P., and Wieler R., “He, Ne, and Ar from the solar wind and solar energetic particles in lunar ilmenites and pyroxenes”, J. Geophys. Res. (Planets)98, 13147-13162, 1993) in gases extracted from bulk lunar ilmenite samples by stepped acid etching and attributed by them to the SW. The ³⁶Ar/³⁸Ar ratios, however, are significantly above both Benkert et al.’s (1993) proposed SW value of 5.48 ± 0.05 and a later estimate of 5.58 ± 0.03 from an acid-etch analysis of Kapoeta (Becker R. H., Schlutter D. J., Rider P. E., and Pepin R. O., “An acid-etch study of the Kapoeta achondrite: Implications for the argon-36/argon-38 ratio in the solar wind”, Meteorit. Planet. Sci.33, 109-113, 1998). We believe, for reasons discussed here and in our earlier report, that 5.80 ± 0.06 ratio most nearly represents the wind composition. The ³He/⁴He ratio in low-temperature gas releases, not measured in the first particle suite, is found in several grains to be indistinguishable from Benkert et al.’s (1993) SW estimate. Elemental ratios of He, Ne, and Ar initially released from grain-surface SW implantation zones are solar-like, as found earlier by Pepin et al. (1999). Gases evolved from these reservoirs at higher temperatures show evidence for perturbations from solar elemental compositions by prior He loss, thermal mobilization of excess Ne from fractionated SW components, or both.Attention in this second investigation was focused on estimating the isotopic compositions of both the SW and the more deeply sited SEP components in regolith grains. Several high-temperature “isotopic plateaus”—approximately constant isotopic ratios in gas fractions released over a number of consecutive heating steps—were observed in the close vicinities of the SEP ratios for He, Ne, and Ar reported by Benkert et al. (1993). Arguments presented in the text suggest that these plateaus are relatively free of interferences from multicomponent mixing artifacts that can mimic pure component signatures. Average SEP compositions derived from the stepped-heating plateau measurements are in remarkable agreement with the Zürich acid-etch values for all three gases.     

Ar/Ar dating of Apollo 12 regolith: Implications for the age of Copernicus and the source of nonmare materials

Twenty-one 2–4 mm rock samples from the Apollo 12 regolith were analyzed by the ⁴⁰Ar/³⁹Ar geochronological technique in order to further constrain the age and source of nonmare materials at the Apollo 12 site. Among the samples analyzed are: 2 felsites, 11 KREEP breccias, 4 mare-basalt-bearing KREEP breccias, 2 alkali anorthosites, 1 olivine-bearing impact-melt breccia, and 1 high-Th mare basalt. Most samples show some degree of degassing at 700–800 Ma, with minimum formation ages that range from 1.0 to 3.1 Ga. We estimate that this degassing event occurred at 782 ± 21 Ma and may have been caused by the Copernicus impact event, either by providing degassed material or by causing heating at the Apollo 12 site. ⁴⁰Ar/³⁹Ar dating of two alkali anorthosite clasts yielded ages of 3.256 ± 0.022 Ga and 3.107 ± 0.058 Ga. We interpret these ages as the crystallization age of the rock and they represent the youngest age so far determined for a lunar anorthosite. The origin of these alkali anorthosite fragments is probably related to differentiation of shallow intrusives. Later impacts could have dispersed this material by lateral mixing or vertical mixing.     

Lunar materials: Their mineralogy,petrology and chemistry

The manned Apollo 11, 12, 14 and 15 and the automated Luna 16 lunar missions have provided us with lunar rock and regolith (soil) samples from a number of geologically distinct sites. The mare regions were sampled by Apollo 11, 12 and Luna 16, whereas Apollo 14 landed on a terrain with more relief, the Fra Mauro Formation which represents an ejecta blanket from the Imbrian Basin, and Apollo 15 touched down near the lunar highlands. The samples collected consist of a mixture, mainly of basalt, breccia and regolith (soil-particulate matter, generally < 1 cm in size). The basalts show considerable variation in texture, mineralogy and chemistry and probably represent fragments from various parts of relatively thin and extensive lava flows in the maria. The breccias represent regolith material which was indurated to varying degrees by impact events. The regolith is a product of the breakdown, again by impact, of coherent rock masses of basalt and breccia.     

History and origin of aubrites

The cosmic ray exposure (CRE) ages of aubrites are among the longest of stone meteorites. New aubrites have been recovered in Antarctica, and these meteorites permit a substantial extension of the database on CRE ages, compositional characteristics, and regolith histories. We report He, Ne, and Ar isotopic abundances of nine aubrites and discuss the compositional data, the CRE ages, and regolith histories of this class of achondrites. A Ne three-isotope correlation reveals a solar-type ratio of ²⁰Ne/²²Ne = 12.1, which is distinct from the present solar wind composition and lower than most ratios observed on the lunar surface. For some aubrites, the cosmic ray-produced noble gas abundances include components produced on the surface of the parent object. The Kr isotopic systematics reveal significant neutron-capture-produced excesses in four aubrites, which is consistent with Sm and Gd isotopic anomalies previously documented in some aubrites. The nominal CRE ages confirm a non-uniform distribution of exposure times, but the evidence for a CRE age cluster appears doubtful. Six meteorites are regolith breccias with solar-type noble gases, and the observed neutron effects indicate a regolith history. ALH aubrites, which were recovered from the same location and are considered to represent a multiple fall, yield differing nominal CRE ages and, if paired, document distinct precompaction histories.     

The geochemistry and provenance of Apollo 16 mafic glasses

The regolith of the Apollo 16 lunar landing site is composed mainly of feldspathic lithologies but mafic lithologies are also present. A large proportion of the mafic material occurs as glass. We determined the major element composition of 280 mafic glasses (>10 wt% FeO) from six different Apollo 16 soil samples. A small proportion (5%) of the glasses are of volcanic origin with picritic compositions. Most, however, are of impact origin. Approximately half of the mafic impact glasses are of basaltic composition and half are of noritic composition with high concentrations of incompatible elements. A small fraction have compositions consistent with impact mixtures of mare material and material of the feldspathic highlands. On the basis of major-element chemistry, we identified six mafic glass groups: VLT picritic glass, low-Ti basaltic glass, high-Ti basaltic glass, high-Al basaltic glass, KREEPy glass, and basaltic-andesite glass. These glass groups encompass 60% of the total mafic glasses studied. Trace-element analyses by secondary ion mass spectroscopy for representative examples of each glass group (31 total analyses) support the major-element classifications and groupings. The lack of basaltic glass in Apollo 16 ancient regolith breccias, which provide snapshots of the Apollo 16 soil just after the infall of Imbrium ejecta, leads us to infer that most (if not all) of the basaltic glass was emplaced as ejecta from small- or moderate-sized impacts into the maria surrounding the Apollo 16 site after the Imbrium impact. The high-Ti basaltic glasses likely represent a new type of basalt from Mare Tranquillitatis, whereas the low-Ti and high-Al basaltic glasses possibly represent the composition of the basalts in Mare Nectaris. Both the low-Ti and high-Al basaltic glasses are enriched in light-REEs, which hints at the presence of a KREEP-bearing source region beneath Mare Nectaris. The basaltic andesite glasses have compositions that are siliceous, ferroan, alkali-rich, and moderately titaniferous; they are unlike any previously recognized lunar lithology or glass group. Their likely provenance is within the Procellarum KREEP Terrane, but they are not found within the Apollo 16 ancient regolith breccias and therefore were likely deposited at the Apollo 16 site post-Imbrium. The basaltic-andesite glasses are the most ferroan variety of KREEP yet discovered.     

Ages of lunar impact breccias: Limits for timing of the Imbrium impact

Since the Apollo 14 mission delivered samples of the Fra Mauro formation, interpreted as ejecta of the Imbrium impact, defining the age of this impact has emerged as one of the critical tasks required for the complete understanding of the asteroid bombardment history of the Moon and, by extension, the inner Solar System. Significant effort dedicated to this task has resulted in a substantial set of ages centered around 3.9 Ga and obtained for the samples from most Apollo landing sites using a variety of chronological methods. However, the available age data are scattered over a range of a few tens of millions of years, which hinders the ability to distinguish between the samples that are truly representative of the Imbrium impact and those formed/reset by other, broadly contemporaneous impact events. This study presents a new set of U-Pb ages obtained for the VHK (very high K) basalt clasts found in the Apollo 14 breccia sample 14305 and phosphates from (i) several fragments of impact-melt breccia extracted from Apollo 14 soil sample 14161, and (ii) two Apollo 15 breccias 15455 and 15445. The new data obtained for the Apollo 14 samples increase the number of independently dated samples from this landing site to ten. These Apollo 14 samples represent the Fra Mauro formation, which is traditionally viewed as Imbrium ejecta, and therefore should record the age of the Imbrium impact. Using the variance of ten ages, we propose an age of 3922 ± 12 Ma for this event. Samples that yield ages within these limits can be considered as possible products of the Imbrium impact, while those that fall significantly outside this range should be treated as representing different impact events. Comparison of this age for Imbrium (determined from Apollo 14 samples) with the ages of another eleven impact-melt breccia samples collected at four other landing sites and a related lunar meteorite suggests that they can be viewed as part of Imbrium ejecta. Comprehensive review of ⁴⁰Ar/³⁹Ar ages available for impact melt samples from different landing sites and obtained using the step-heating technique, suggests that the majority of the samples that gave robust plateau ages are indistinguishable within uncertainties and altogether yield a weighted average age of 3916 ± 7 Ma (95 % conf., MSWD = 1.1; P = 0.13) and a median average age of 3919 + 14/-12 Ma, both of which agree with the confidence interval obtained using the U-Pb system. These samples, dated by ⁴⁰Ar/³⁹Ar method, can be also viewed as representing the Imbrium impact. In total 36 out of 41 breccia samples from five landing sites can be interpreted to represent formation of the Imbrium basin, supporting the conclusion that Imbrium material was distributed widely across the near side of the Moon. Establishing temporal limits for the Imbrium impact allows discrimination of ten samples with Rb-Sr and ⁴⁰Ar/³⁹Ar ages about 50 Ma younger than 3922 ± 12 Ma. This group may represent a separate single impact on the Moon and needs to be investigated further to improve our understanding of lunar impact history.