A number of distinct methodologies are available for determining the oxygen isotope composition of minerals and rocks, these include laser-assisted fluorination, secondary ion mass spectrometry ...(SIMS) and UV laser ablation. In this review we focus on laser-assisted fluorination, which currently achieves the highest levels of precision available for oxygen isotope analysis. In particular, we examine how results using this method have furthered our understanding of early-formed differentiated meteorites. Due to its rapid reaction times and low blank levels, laser-assisted fluorination has now largely superseded the conventional externally-heated Ni “bomb” technique for bulk analysis. Unlike UV laser ablation and SIMS analysis, laser-assisted fluorination is not capable of focused spot analysis. While laser fluorination is now a mature technology, further analytical improvements are possible via refinements to the construction of sample chambers, clean-up lines and the use of ultra-high resolution mass spectrometers.
High-precision oxygen isotope analysis has proved to be a particularly powerful technique for investigating the formation and evolution of early-formed differentiated asteroids and has provided unique insights into the interrelationships between various groups of achondrites. A clear example of this is seen in samples that lie close to the terrestrial fractionation line (TFL). Based on the data from conventional oxygen isotope analysis, it was suggested that the main-group pallasites, the howardite eucrite diogenite suite (HEDs) and mesosiderites could all be derived from a single common parent body. However, high precision analysis demonstrates that main-group pallasites have a Δ17O composition that is fully resolvable from that of the HEDs and mesosiderites, indicating the involvement of at least two parent bodies. The range of Δ17O values exhibited by an achondrite group provides a useful means of assessing the extent to which their parent body underwent melting and isotopic homogenization. Oxygen isotope analysis can also highlight relationships between ungrouped achondrites and the more well-populated groups. A clear example of this is the proposed link between the evolved GRA 06128/9 meteorites and the brachinites.
The evidence from oxygen isotopes, in conjunction with that from other techniques, indicates that we have samples from approximately 110 asteroidal parent bodies (∼60 irons, ∼35 achondrites and stony-iron, and ∼15 chondrites) in our global meteorite collection. However, compared to the likely size of the original protoplanetary asteroid population, this is an extremely low value. In addition, almost all of the differentiated samples (achondrites, stony-iron and irons) are derived from parent bodies that were highly disrupted early in their evolution.
High-precision oxygen isotope analysis of achondrites provides some important insights into the origin of mass-independent variation in the early Solar System. In particular, the evidence from various primitive achondrite groups indicates that both the slope 1 (Y&R) and CCAM lines are of primordial significance. Δ17O differences between water ice and silicate-rich solids were probably the initial source of the slope 1 anomaly. These phases most likely acquired their isotopic composition as a result of UV photo-dissociation of CO that took place either in the early solar nebula or precursor giant molecular cloud. Such small-scale isotopic heterogeneities were propagated into larger-sized bodies, such as asteroids and planets, as a result of early Solar System processes, including dehydration, aqueous alteration, melting and collisional interactions.
There is increasing evidence that chondritic parent bodies accreted relatively late compared to achondritic asteroids. This may account for the fact that apart from a few notable exceptions’ such as the aubrite-enstatite chondrite association, known chondrite groups could not have been the parents to the main achondrite groups.
In this study we have measured the OH contents and D/H ratios in apatite grains in lunar basalts. These new data considerably expand the limited dataset published so far. The data presented in this ...study also show that there is a major difference between high- and low-Ti mare basalts in terms of their OH and D/H systematics. Apatites in high-Ti basaltic samples display a relatively restricted range in OH contents (∼1500–3000ppm) with large δD variations (∼600–1000 ‰) whereas apatites in low-Ti Apollo basalts and lunar meteorites display a comparatively larger range in OH contents (∼500–15000ppm), each sample displaying relatively restricted variations in their D/H ratios. Analyses of apatites in basaltic meteorites Miller Range 05035 and LaPaz Icefield 04841 substantially expand the lower bound for δD values measured in apatites from Apollo mare basalts, down to δD values of ∼100‰. In these meteorites, high resolution mapping of the distribution of secondary ions of H and C was used to avoid cracks and hotspots. Together with mixing calculations for terrestrial contamination, this analytical protocol ensured that most of the values reported for MIL 05035 and LAP 04841 correspond to their actual lunar signatures. We interpret the large variations of apatite δD values in mare basalts between ∼200‰ and 1000‰ as a result of different amounts of degassing of H-bearing species initially dissolved in the basaltic parental melts. Indeed, the average δD values measured in different low-Ti basalts are consistent with ∼85–99% degassing of H as H2, starting from a δD value of 100‰. Degassing of H-bearing species essentially as H2 was favoured by the reduced nature of lunar magmas. In low-Ti mare basalts, apatite crystallisation occurred after degassing of the H-bearing species and the OH variations reflect different degrees of fractional crystallisation. In high-Ti mare basalts, large δD variations with relatively restricted range in OH contents imply that apatite crystallisation and degassing of H-bearing species were mostly coeval. Geochemical modelling integrating corrections for degassing and fractional crystallisation suggests that the mantle source regions of the different low-Ti mare basalts could have contained ∼5–50ppm H (equivalent to ∼45–450ppm H2O), which are similar to the estimated range of ∼60–350ppm water for the Earth’s upper mantle. Finally, the H isotopic composition of pre-degassed lunar hydrogen in mare basalts is consistent with a CI-chondrite-type value of ∼100‰, which is consistent with the increasing evidence suggesting that the Earth, Mars and the Moon might have accreted similar water of chondritic origin.
The Moon exhibits a heavier chlorine (Cl) isotopic composition compared to the Earth. Several hypotheses have been put forward to explain this difference, based mostly on analyses of apatite in lunar ...samples complemented by bulk-rock data. The earliest hypothesis argued for Cl isotope fractionation during the degassing of anhydrous basaltic magmas on the Moon. Subsequently, other hypotheses emerged linking Cl isotope fractionation on the Moon with the degassing during the crystallization of the Lunar Magma Ocean (LMO). Currently, a variant of the LMO degassing model involving mixing between two end-member components, defined by early-formed cumulates, from which mare magmas were subsequently derived, and a KREEP component, which formed towards the end of the LMO crystallization, seems to reconcile some existing Cl isotope data on lunar samples. To further ascertain the history of Cl in the Moon and to investigate any evolution of Cl during magma crystallization and emplacement events, which could help resolve the chlorine isotopic variation between the Earth and the Moon, we analysed the Cl abundance and its isotopic composition in 36 olivine- and pyroxene-hosted melt inclusions (MI) in five Apollo basalts (10020, 12004, 12040, 14072 and 15016). Olivine-hosted MI have an average of 3.3±1.4ppm Cl. Higher Cl abundances (11.9 ppm on average) are measured for pyroxene-hosted MI, consistent with their formation at later stages in the crystallization of their parental melt compared to olivines. Chlorine isotopic composition (δ37Cl) of MI in the five Apollo basalts have weighted averages of +12.8±2.4‰ and +10.1±3.2‰ for olivine- and pyroxene-hosted MI, respectively, which are statistically indistinguishable. These isotopic compositions are also similar to those measured in apatite in these lunar basalts, with the exception of sample 14072, which is known to have a distinct petrogenetic history compared to other mare basalts. Based on our dataset, we conclude that, post-MI-entrapment, no significant Cl isotopic fractionation occurred during the crystallization and subsequent eruption of the parent magma and that Cl isotopic composition of MI and apatite primarily reflect the signature of the source region of these lunar basalts. Our findings are compatible with the hypothesis that in the majority of the cases the heavy Cl isotopic signature of the Moon was acquired during the earliest stages of LMO evolution. Interestingly, MI data from 14072 suggests that Apollo 14 lunar basalts might be an exception and may have experienced post-crystallization processes, possibly metasomatism, resulting in additional Cl isotopic fractionation recorded by apatite but not melt inclusions.
•Cl isotopic composition of lunar MIs are similar to apatite for most mare basalts.•Cl isotopic composition of MIs and apatites in 14072 are distinct.•The heavy Cl isotopic signature of the Moon was acquired during the LMO evolution.•Apollo 14 lunar basalts may have experienced post-crystallization processes.
Current models for the Moon's formation have yet to fully account for the thermal evolution of the Moon in the presence of H2O and other volatiles. Of particular importance is chlorine, since most ...lunar samples are characterised by unique heavy δ37Cl values, significantly deviating from those of other planetary materials, including Earth, for which δ37Cl values cluster around ∼0‰. In order to unravel the cause(s) of the Moon's unique chlorine isotope signature, we performed a comprehensive study of high-precision in situ Cl isotope measurements of apatite from a suite of Apollo samples with a range of geochemical characteristics and petrologic types. The Cl-isotopic compositions measured in lunar apatite in the studied samples display a wide range of δ37Cl values (reaching a maximum value of +36‰), which are positively correlated with the amount of potassium (K), Rare Earth Element (REE) and phosphorous (P) (KREEP) component in each sample. Using these new data, integrated with existing H-isotope data obtained for the same samples, we are able to place these findings in the context of the canonical lunar magma ocean (LMO) model. The results are consistent with the urKREEP reservoir being characterised by a δ37Cl ∼+30‰. Such a heavy Cl isotope signature requires metal-chloride degassing from a Cl-enriched urKREEP LMO residue, a process likely to have been triggered by at least one large crust-breaching impact event that facilitated the transport and exposure of urKREEP liquid to the lunar surface.
•We have analysed apatite in a diverse range of lunar samples.•Cl-isotopic compositions of lunar apatite range from ∼+2 to ∼+36‰.•Lunar samples acquired heavy δ37Cl values from variable interaction with urKREEP.•Differentiation of the Moon via the LMO results in an urKREEP layer rich in Cl.•urKREEP degassed following enrichment by a crust-puncturing impact event(s).
A few eucrites have anomalous oxygen isotopic compositions. To help understand their origin and identify additional samples, we have analyzed the oxygen isotopic compositions of 18 eucrites and four ...diogenites. Except for five eucrites, these meteorites have Δ
17O values that lie within 2σ of their mean value viz., −0.242
±
0.016‰, consistent with igneous isotopic homogenization of Vesta. The five exceptional eucrites—NWA 1240, Pasamonte (both clast and matrix samples), PCA 91007, A-881394, and Ibitira—have Δ
17O values that lie, respectively, 4σ, 5σ, 5σ, 15σ, and 21σ away from this mean value. NWA 1240 has a δ
18O value that is 5σ below the mean eucrite value. Four of the five outliers are unbrecciated and unshocked basaltic eucrites, like NWA 011, the first eucrite found to have an anomalous oxygen isotopic composition. The fifth outlier, Pasamonte, is composed almost entirely of unequilibrated basaltic clasts. Published chemical data for the six eucrites with anomalous oxygen isotopic compositions (including NWA 011) exclude contamination by chondritic projectiles as a source of the oxygen anomalies. Only NWA 011 has an anomalous Fe/Mn ratio, but several anomalous eucrites have exceptional Na, Ti, or Cr concentrations. We infer that the six anomalous eucrites are probably derived from five distinct Vesta-like parent bodies (Pasamonte and PCA 91007 could come from one body). These anomalous eucrites, like the isotopically normal, unbrecciated eucrites with 4.48 Gyr Ar-Ar ages, are probably deficient in brecciation and shock effects because they were sequestered in small asteroids (∼10
km diameter) during the Late Heavy Bombardment following ejection from Vesta-like bodies. The preservation of Vesta’s crust and the lack of deeply buried samples from the hypothesized Vesta-like bodies are consistent with the removal of these bodies from the asteroid belt by gravitational perturbations from planets and protoplanets, rather than by collisional grinding.
The Apollo-derived tenet of an anhydrous Moon has been contested following measurement of water in several lunar samples that require water to be present in the lunar interior. However, significant ...uncertainties exist regarding the flux, sources and timing of water delivery to the Moon. Here we address those fundamental issues by constraining the mass of water accreted to the Moon and modelling the relative proportions of asteroidal and cometary sources for water that are consistent with measured isotopic compositions of lunar samples. We determine that a combination of carbonaceous chondrite-type materials were responsible for the majority of water (and nitrogen) delivered to the Earth-Moon system. Crucially, we conclude that comets containing water enriched in deuterium contributed significantly <20% of the water in the Moon. Therefore, our work places important constraints on the types of objects impacting the Moon ∼4.5-4.3 billion years ago and on the origin of water in the inner Solar System.
The Paris chondrite provides an excellent opportunity to study CM chondrules and refractory inclusions in a more pristine state than currently possible from other CMs, and to investigate the earliest ...stages of aqueous alteration captured within a single CM bulk composition. It was found in the effects of a former colonial mining engineer and may have been an observed fall. The texture, mineralogy, petrography, magnetic properties and chemical and isotopic compositions are consistent with classification as a CM2 chondrite. There are ∼45vol.% high-temperature components mainly Type I chondrules (with olivine mostly Fa0–2, mean Fa0.9) with granular textures because of low mesostasis abundances. Type II chondrules contain olivine Fa7 to Fa76. These are dominantly of Type IIA, but there are IIAB and IIB chondrules, II(A)B chondrules with minor highly ferroan olivine, and IIA(C) with augite as the only pyroxene. The refractory inclusions in Paris are amoeboid olivine aggregates (AOAs) and fine-grained spinel-rich Ca–Al-rich inclusions (CAIs). The CAI phases formed in the sequence hibonite, perovskite, grossite, spinel, gehlenite, anorthite, diopside/fassaite and forsterite. The most refractory phases are embedded in spinel, which also occurs as massive nodules. Refractory metal nuggets are found in many CAI and refractory platinum group element abundances (PGE) decrease following the observed condensation sequences of their host phases. Mn–Cr isotope measurements of mineral separates from Paris define a regression line with a slope of 53Mn/55Mn=(5.76±0.76)×106. If we interpret Cr isotopic systematics as dating Paris components, particularly the chondrules, the age is 4566.44±0.66Myr, which is close to the age of CAI and puts new constraints on the early evolution of the solar system. Eleven individual Paris samples define an O isotope mixing line that passes through CM2 and CO3 falls and indicates that Paris is a very fresh sample, with variation explained by local differences in the extent of alteration. The anhydrous precursor to the CM2s was CO3-like, but the two groups differed in that the CMs accreted a higherproportion of water. Paris has little matrix (∼47%, plus 8% fine grained rims) and is less altered than other CM chondrites. Chondrule silicates (except mesostasis), CAI phases, submicron forsterite and amorphous silicate in the matrix are all well preserved in the freshest domains, and there is abundant metal preserved (metal alteration stage 1 of Palmer and Lauretta (2011)). Metal and sulfide compositions and textures correspond to the least heated or equilibrated CM chondrites, Category A of Kimura et al. (2011). The composition of tochilinite–cronstedtite intergrowths gives a PCP index of ∼2.9. Cronstedtite is more abundant in the more altered zones whereas in normal highly altered CM chondrites, with petrologic subtype 2.6–2.0 based on the S/SiO2 and ∑FeO/SiO2 ratios in PCP or tochilinite–cronstedtite intergrowths (Rubin et al., 2007), cronstedtite is destroyed by alteration. The matrix in fresh zones has CI chondritic volatile element abundances, but interactions between matrix and chondrules occurred during alteration, modifying the volatile element abundances in the altered zones. Paris has higher trapped Ne contents, more primitive organic compounds, and more primitive organic material than other CMs. There are gradational contacts between domains of different degree of alteration, on the scale of ∼1cm, but also highly altered clasts, suggesting mainly a water-limited style of alteration, with no significant metamorphic reheating.
The recent discoveries of hydrogen (H) bearing species on the lunar surface and in samples derived from the lunar interior have necessitated a paradigm shift in our understanding of the water ...inventory of the Moon, which was previously considered to be a ‘bone-dry’ planetary body. Most sample-based studies have focused on assessing the water contents of the younger mare basalts and pyroclastic glasses, which are partial-melting products of the lunar mantle. In contrast, little attention has been paid to the inventory and source(s) of water in the lunar highlands rocks which are some of the oldest and most pristine materials available for laboratory investigations, and that have the potential to reveal the original history of water in the Earth–Moon system. Here, we report in-situ measurements of hydroxyl (OH) content and H isotopic composition of the mineral apatite from four lunar highlands samples (two norites, a troctolite, and a granite clast) collected during the Apollo missions. Apart from troctolite in which the measured OH contents in apatite are close to our analytical detection limit and its H isotopic composition appears to be severely compromised by secondary processes, we have measured up to ∼2200 ppm OH in the granite clast with a weighted average δD of ∼−105±130‰, and up to ∼3400 ppm OH in the two norites (77215 and 78235) with weighted average δD values of −281±49‰ and −27±98‰, respectively. The apatites in the granite clast and the norites are characterised by higher OH contents than have been reported so far for highlands samples, and have H isotopic compositions similar to those of terrestrial materials and some carbonaceous chondrites, providing one of the strongest pieces of evidence yet for a common origin for water in the Earth–Moon system. In addition, the presence of water, of terrestrial affinity, in some samples of the earliest-formed lunar crust suggests that either primordial terrestrial water survived the aftermath of the putative impact-origin of the Moon or water was added to the Earth–Moon system by a common source immediately after the accretion of the Moon.
•We carried out OH–δD measurements in apatites from lunar highlands samples.•Significant amounts of indigenous lunar water were measured in these samples.•The average δD of water in apatites is similar to terrestrial and chondritic water.•A common origin for water in the Earth–Moon system is proposed.
The isotopes of chlorine (37Cl and 35Cl) are highly fractionated in lunar samples compared to most other Solar System materials. Recently, the chlorine isotope signatures of lunar rocks have been ...attributed to large-scale degassing processes that occurred during the existence of a magma ocean. In this study we investigated how well a suite of lunar basalts, most of which have not previously been analyzed, conform to previous models. The Cl isotope compositions (δ37Cl (‰) = (37Cl/35Clsample/37Cl/35ClSMOC) − 1 × 1000, where SMOC refers to standard mean ocean chloride) recorded range from ∼+7 to +14‰ (Apollo 15), +10 to +19‰ (Apollo 12), +9 to +15‰ (70017), +4 to +8‰ (MIL 05035), and +15 to +22‰ (Kalahari 009). The Cl isotopic data from the present study support the mixing trends previously reported by Boyce et al. (2015) and Barnes et al. (2016), as the Cl isotopic composition of apatites are positively correlated with bulk-rock incompatible trace element abundances in the low-Ti basalts, inclusive of low-Ti and KREEP basalts. This trend has been interpreted as evidence that incompatible trace elements, including Cl, were concentrated in the urKREEP residual liquid of the lunar magma ocean, rather than the mantle cumulates, and that urKREEP Cl had a highly fractionated isotopic composition. The source regions for the basalts were thus created by variable mixing between the mantle (Cl-poor and relatively unfractionated) and urKREEP. The high-Ti basalts show much more variability in measured Cl isotope ratios and scatter around the trend formed by the low-Ti basalts. Most of the data for lunar meteorites also fits the mixing of volatiles in their sources, but Kalahari 009, which is highly depleted in incompatible trace elements, contains apatites with heavily fractionated Cl isotopic compositions. Given that Kalahari 009 is one of the oldest lunar basalts and ought to have been derived from very early-formed mantle cumulates, a heavy Cl isotopic signature is likely not related to its mantle source, but more likely to magmatic or secondary alteration processes, perhaps via impact-driven vapor metasomatism of the lunar crust.
PDF
