Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly ...debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of +1.2‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe–δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons.
Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite–hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time.
The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼+6‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.
•We performed UV photo-oxidation experiments and measured Fe and O isotopes.•Fe isotopes follow a Rayleigh distillation (ΔFe(III)precipitate–Fe(II)56/54=+1.2‰).•The slope in a 3-isotope diagram for Fe follows the high-T equilibrium limit.•Photo-oxidation can explain the precipitation of BIFs.•Photo-oxidation is a viable process to form Fe(III)-minerals on Mars.
Venus is Earth’s closest planetary neighbour and both bodies are of similar size and mass. As a consequence, Venus is often described as Earth’s sister planet. But the two worlds have followed very ...different evolutionary paths, with Earth having benign surface conditions, whereas Venus has a surface temperature of 464 °C and a surface pressure of 92 bar. These inhospitable surface conditions may partially explain why there has been such a dearth of space missions to Venus in recent years.
The oxygen isotope composition of Venus is currently unknown. However, this single measurement (
Δ
17
O
) would have first order implications for our understanding of how large terrestrial planets are built. Recent isotopic studies indicate that the Solar System is bimodal in composition, divided into a carbonaceous chondrite (CC) group and a non-carbonaceous (NC) group. The CC group probably originated in the outer Solar System and the NC group in the inner Solar System. Venus comprises 41% by mass of the inner Solar System compared to 50% for Earth and only 5% for Mars. Models for building large terrestrial planets, such as Earth and Venus, would be significantly improved by a determination of the
Δ
17
O
composition of a returned sample from Venus. This measurement would help constrain the extent of early inner Solar System isotopic homogenisation and help to identify whether the feeding zones of the terrestrial planets were narrow or wide.
Determining the
Δ
17
O
composition of Venus would also have significant implications for our understanding of how the Moon formed. Recent lunar formation models invoke a high energy impact between the proto-Earth and an inner Solar System-derived impactor body, Theia. The close isotopic similarity between the Earth and Moon is explained by these models as being a consequence of high-temperature, post-impact mixing. However, if Earth and Venus proved to be isotopic clones with respect to
Δ
17
O
, this would favour the classic, lower energy, giant impact scenario.
We review the surface geology of Venus with the aim of identifying potential terrains that could be targeted by a robotic sample return mission. While the potentially ancient tessera terrains would be of great scientific interest, the need to minimise the influence of venusian weathering favours the sampling of young basaltic plains. In terms of a nominal sample mass, 10 g would be sufficient to undertake a full range of geochemical, isotopic and dating studies. However, it is important that additional material is collected as a legacy sample. As a consequence, a returned sample mass of at least 100 g should be recovered.
Two scenarios for robotic sample return missions from Venus are presented, based on previous mission proposals. The most cost effective approach involves a “Grab and Go” strategy, either using a lander and separate orbiter, or possibly just a stand-alone lander. Sample return could also be achieved as part of a more ambitious, extended mission to study the venusian atmosphere. In both scenarios it is critical to obtain a surface atmospheric sample to define the extent of atmosphere-lithosphere oxygen isotopic disequilibrium. Surface sampling would be carried out by multiple techniques (drill, scoop, “vacuum-cleaner” device) to ensure success. Surface operations would take no longer than one hour.
Analysis of returned samples would provide a firm basis for assessing similarities and differences between the evolution of Venus, Earth, Mars and smaller bodies such as Vesta. The Solar System provides an important case study in how two almost identical bodies, Earth and Venus, could have had such a divergent evolution. Finally, Venus, with its runaway greenhouse atmosphere, may provide data relevant to the understanding of similar less extreme processes on Earth. Venus is Earth’s planetary twin and deserves to be better studied and understood. In a wider context, analysis of returned samples from Venus would provide data relevant to the study of exoplanetary systems.
Sample return from a main-belt asteroid has not yet been attempted, but appears technologically feasible. While the cost implications are significant, the scientific case for such a mission appears ...overwhelming. As suggested by the “Grand Tack” model, the structure of the main belt was likely forged during the earliest stages of Solar System evolution in response to migration of the giant planets. Returning samples from the main belt has the potential to test such planet migration models and the related geochemical and isotopic concept of a bimodal Solar System.
Isotopic studies demonstrate distinct compositional differences between samples believed to be derived from the outer Solar System (CC or carbonaceous chondrite group) and those that are thought to be derived from the inner Solar System (NC or non-carbonaceous group). These two groups are separated on relevant isotopic variation diagrams by a clear compositional gap. The interface between these two regions appears to be broadly coincident with the present location of the asteroid belt, which contains material derived from both groups.
The Hayabusa mission to near-Earth asteroid (NEA) (25143) Itokawa has shown what can be learned from a sample-return mission to an asteroid, even with a very small amount of sample. One scenario for main-belt sample return involves a spacecraft launching a projectile that strikes an object and flying through the debris cloud, which would potentially allow multiple bodies to be sampled if a number of projectiles are used on different asteroids. Another scenario is the more traditional method of landing on an asteroid to obtain the sample.
A significant range of main-belt asteroids are available as targets for a sample-return mission and such a mission would represent a first step in mineralogically and isotopically mapping the asteroid belt. We argue that a sample-return mission to the asteroid belt does not necessarily have to return material from both the NC and CC groups to viably test the bimodal Solar System paradigm, as material from the NC group is already abundantly available for study. Instead, there is overwhelming evidence that we have a very incomplete suite of CC-related samples.
Based on our analysis, we advocate a dedicated sample-return mission to the dwarf planet (1) Ceres as the best means of further exploring inherent Solar System variation. Ceres is an ice-rich world that may be a displaced trans-Neptunian object. We almost certainly do not have any meteorites that closely resemble material that would be brought back from Ceres. The rich heritage of data acquired by the Dawn mission makes a sample-return mission from Ceres logistically feasible at a realistic cost. No other potential main-belt target is capable of providing as much insight into the early Solar System as Ceres. Such a mission should be given the highest priority by the international scientific community.
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.
A close relationship between CM and CO chondrites has been suggested by previous petrologic and isotopic studies, leading to the suggestion that they may originate from similar precursor materials or ...even a common parent body. In this study, we evaluate the genetic relationship between CM and CO chondrites using Ti, Cr, and O isotopes. We first provide additional constraints on the ranges of ε50Ti and ε54Cr values of bulk CM and CO chondrites by reporting the isotopic compositions of CM2 chondrites Murchison, Murray, and Aguas Zarcas and the CO3.8 chondrite Isna. We then report the ε50Ti and ε54Cr values for several ungrouped and anomalous carbonaceous chondrites that have been previously reported to exhibit similarities to the CM and/or CO chondrite groups, including Elephant Moraine (EET) 83226, EET 83355, Grosvenor Mountains (GRO) 95566, MacAlpine Hills (MAC) 87300, MAC 87301, MAC 88107, and Northwest Africa (NWA) 5958, and the O-isotope compositions of a subset of these samples. We additionally report the Ti, Cr, and O isotopic compositions of additional ungrouped chondrites LaPaz Ice Field (LAP) 04757, LAP 04773, Lewis Cliff (LEW) 85332, and Coolidge to assess their potential relationships with known carbonaceous and ordinary chondrite groups. LAP 04757 and LAP 04773 exhibit isotopic compositions indicating they are low-FeO ordinary chondrites. The isotopic compositions of Murchison, Murray, Aguas Zarcas, and Isna extend the compositional ranges defined by the CM and CO chondrites in ε50Ti versus ε54Cr space. The majority of the ungrouped carbonaceous chondrites with documented similarities to the CM and/or CO chondrites plot outside the CM and CO group fields in plots of ε50Ti versus ε54Cr, Δ17O versus ε50Ti, and Δ17O versus ε54Cr. Therefore, based on differences in their Ti, Cr, and O isotopic compositions, we conclude that the CM, CO, and ungrouped carbonaceous chondrites likely represent samples of multiple distinct parent bodies. We also infer that these parent bodies formed from precursor materials that shared similar isotopic compositions, which may indicate formation in regions of the protoplanetary disk that were in close proximity to each other.
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.
Late accretion of primitive chondritic material to Earth, the Moon, and Mars, after core formation had ceased, can account for the absolute and relative abundances of highly siderophile elements ...(HSEs) in their silicate mantles. Here we show that smaller planetesimals also possess elevated HSE abundances in chondritic proportions. This demonstrates that late addition of chondritic material was a common feature of all differentiated planets and planetesimals, irrespective of when they accreted; occurring < 5 to > 150 million years after the formation of the solar system. Parent-body size played a role in producing variations in absolute HSE abundances among these bodies; however, the oxidation state of the body exerted the major control by influencing the extent to which late-accreted material was mixed into the silicate mantle rather than removed to the core.
Lewis Cliff (LEW) 85311 is classified as a Mighei-like (CM) carbonaceous chondrite, yet it has some unusual properties that highlight an unrealised diversity within the CMs, and also questions how ...many parent bodies are sampled by the group. This meteorite is composed of rimmed chondrules, chondrule fragments and refractory inclusions that are set in a fine-grained phyllosilicate-rich matrix. The chondrules are of a similar size to those in the CMs, and have narrow fine-grained rims. LEW 85311 has been mildly aqueously altered, as evidenced by the preservation of melilite and kamacite, and X-ray diffraction results showing a low phyllosilicate fraction and a high ratio of cronstedtite to Fe, Mg serpentine. The chemical composition of LEW 85311 matrix, fine-grained rims, tochilinite and P-rich sulphides is similar to mildly aqueously altered CMs. LEW 85311 is enriched in refractory elements and REEs such that its CI-normalised profile falls between the CMs and CVs, and its oxygen isotopic composition plots in the CV-CK-CO field. Other distinctive properties of this meteorite include the presence of abundant refractory inclusions, and hundreds of micrometer size objects composed of needle-fibre calcite. LEW 85311 could come from part of a single CM parent body that was unusually rich in refractory inclusions, but more likely samples a different parent body to most other members of the group that accreted a subtly different mixture of materials. The mineralogical and geochemical evolution of LEW 85311 during subsequent aqueous alteration was similar to other CMs and was arrested at an early stage, corresponding to a petrologic subtype of CM2.7, probably due to an unusually low proportion of accreted ice. The CM carbonaceous chondrites sample multiple parent bodies whose similar size and inventory of accreted materials, including radiogenic isotopes, led to a comparable post-accretionary evolution.
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.
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