The isotopic compositions of meteorites provide valuable insights into the earliest history of the Solar System and, in some cases, provide constraints on presolar components that contributed to the solar nebula. In the past decade or so, mass-independent isotope anomalies in titanium have become particularly important geochemical tracers to study the distinct isotopic reservoirs in the early Solar System. In particular, mass-independent anomalies in the most neutron-rich isotope of titanium (50Ti) have been used to distinguish between carbonaceous chondritic (CC) and non-carbonaceous chondritic (NC) materials. These two groupings likely represent distinct isotopic reservoirs in the inner (NC) and outer (CC) Solar System. However, while the titanium isotope compositions of CC and NC materials are distinct, each group's full range of compositional variability is poorly characterized. For example, only one CK carbonaceous chondrite group member has been analyzed thus far for its bulk Ti isotope composition. This work aims to characterize better the range of mass-independent Ti isotope compositions within and among the carbonaceous chondrites, which has implications for the degree and potential sources of Ti isotope heterogeneity in the early Solar System. Methods utilized in this study include column chromatography to purify Ti and high-precision multi-collector inductively coupled plasma mass spectrometry for measuring Ti isotope compositions. The Ti isotope compositions of bulk samples of nine carbonaceous chondrites are reported here. In addition, the bulk fractions of the meteorites used in this study were taken from homogenized powders of relatively large (~200 mg each) samples. This was done to assess whether variability in mass-independent Ti isotope compositions previously reported within some meteorites could be a sampling artifact. Results from this work show that the various CM2 chondrites and ungrouped carbonaceous chondrites have ε50Ti values that are similar, suggesting that the Ti in these samples was likely sourced from a common isotopic reservoir. On the other hand, the ε50Ti values reported for CI1 and CH/CBb bulk samples suggest that the parent bodies of these carbonaceous chondrite groups were formed in isotopic reservoir(s) distinct from that of the other CC groups in the early Solar System.

Meteorites provide an opportunity to reconstruct the history of the SolarSystem. Differentiated meteorites, also called achondrites, are the result of melting and differentiation processes on their parent body. Stable isotopic compositions of differentiated meteorites and their components have added to the understanding of physical parameters, such as temperature, pressure, and redox conditions relevant to differentiation processes on planetesimals and planets in the early Solar System. In particular, Fe and Si isotopes have proven to be useful in advancing the understanding of physical and chemical processes during planetary accretion and subsequent evolution. In this work, I developed a new method to simultaneously purify Fe and Si from a single aliquot of sample while ensuring consistently high yields and accurate and precise isotopic measurements. I then measured the Fe isotope compositions and Si contents of metals from aubrite meteorites to infer the structure and thermal evolution of their asteroidal parent body. Thereafter, I determined the combined Si and Fe isotope compositions of aubrite metals and the Horse Creek iron meteorite, and compared the magnitude of Si and Fe isotope fractionation factors between metal and silicates for both enstatite chondrites and aubrites to estimate the effect of high-temperature core formation that occurred on the aubrite parent body. I additionally assessed whether correlated Si and Fe isotope systematics can be used to trace core formation and partial melting processes for the aubrite parent body, angrite parent body, Mars, Vesta, Moon, and Earth. Finally, I measured the combined Fe and Si isotope composition of a variety of ungrouped achondrites and brachinites that record different degrees of differentiation under different redox conditions to evaluate the role of differentiation and oxygen fugacity in controlling their Fe and Si isotope compositions. Taken together, this comprehensive dataset reveals the thermal evolution of the aubrite parent body, provides insights into the factors controlling the Fe and Si isotope compositions of various planetary materials, and helps constrain the bulk starting composition of planets and planetesimals.

This report is on an investigation of the 26Al-26Mg isotope systematics in the NWA 10463 angrite to constrain the timing of formation of this achondrite on its parent body. The analyses of the whole rock and mineral separates of olivine, pyroxene, and plagioclase were performed using multi-collector inductively coupled plasma mass spectrometry. From the isotope systematics, no evidence of live 26Al could be resolved, but an upper limit on the 26Al/27Al ratio of <1.6 x 10-8 was estimated. This upper limit corresponds to a model age of <4560.1 Ma, which is significantly younger than the crystallization ages of the volcanic angrite ages of ~4563-4564 Ma, but is consistent with the plutonic angrite ages of ~4557-4558 Ma.

Meteorites and their components can be used to unravel the history of the early Solar System. Carbonaceous chondrites are meteorites that originated from undifferentiated parent bodies that formed within a few million years of the beginning of the Solar System. These meteorites contain calcium-aluminum-rich inclusions (CAIs), which are the oldest dated solids in the Solar System at ~4.567 billion years old and thus preserve a record of the earliest stage of Solar System formation. The isotopic compositions of CAIs and bulk carbonaceous chondrites can be used to identify the sources of material inherited by the protoplanetary disk, assess the degree of mixing in the disk, and evaluate sample origins and potential genetic relationships between parent bodies. In particular, mass-independent Cr and Ti isotopic compositions have proven to be especially useful for these purposes.

In this work, I first developed new methods for the chemical separation of Cr and Ti, improving the reliability of existing methods to ensure consistent yields and accurate isotopic measurements. I then measured the Cr and Ti isotopic compositions of CAIs from CV and CK chondrites to determine the extent of isotopic heterogeneity in the CAI-forming region and assess the role of CAIs in the preservation of planetary-scale isotopic anomalies. My results show that all measured CAIs originated from a common isotopic reservoir that incorporated material from at least three distinct nucleosynthetic sources and preserved limited isotopic heterogeneity. These results also suggest that planetary-scale isotopic anomalies cannot be attributed solely to the transport of CAIs from one part of the solar nebula to another. I finally measured the Cr and Ti isotopic compositions of bulk CM, CO, and ungrouped chondrites to evaluate the relationship between CM and CO chondrites, which have been suggested to originate from either distinct but related parent bodies or a common compositionally heterogeneous parent body. My results suggest that CM, CO, and related ungrouped chondrites originated from distinct parent bodies that formed from similar precursor materials in nearby formation regions. These results may have implications for asteroid samples returned by the OSIRIS-REx and Hayabusa2 missions.

This study explores how bulk composition and oxygen fugacity (fO2) affect the partitioning of sulfur between the molten mantle and core of an early planetesimal. The model can be used to determine the range of potential sulfur concentrations in the asteroid (16) Psyche, which is the target of the National Aeronautics and Space Administration/Arizona State University Psyche Mission. This mission will be our visit to an M-type asteroid, thought to be dominantly metallic.

The model looks at how oxygen fugacity (fO2), bulk composition, temperature, and pressure affect sulfur partitioning in planetesimals using experimentally derived equations from previous studies. In this model, the bulk chemistry and oxygen fugacity of the parent body is controlled by changing the starting material, using ordinary chondrites (H, L, LL) and carbonaceous chondrites (CM, CI, CO, CK, CV). The temperature of the planetesimal is changed from 1523 K to 1873 K, the silicate mobilization and total melting temperatures, respectively; and pressure from 0.1 to 20 GPa, the core mantle boundary pressures of Vesta and Mars, respectively.

The final sulfur content of a differentiated planetesimal core is strongly dependent on the bulk composition of the original parent body. In all modeled cores, the sulfur content is above 5 weight percent sulfur; this is the point at which the least amount of other light elements is needed to form an immiscible sulfide liquid in a molten core. Early planetesimal cores likely formed an immiscible sulfide liquid, a eutectic sulfide liquid, or potentially were composed of mostly troilite, FeS.

Short-lived radionuclides (SLRs) once present in the solar nebula can be used to probe the Solar System’s galactic formation environment. Isotopic analyses reveal that the first solids formed in the Solar System, calcium- and aluminum-rich inclusions (CAIs) in chondritic meteorites, formed with the live SLRs 10Be (t1/2 = 1.4 Ma) and 26Al (t1/2 = 0.7 Ma). Beryllium-10 is produced when high-energy ions, solar energetic particles or galactic cosmic rays (GCRs), spall nuclei in gas or dust. The most likely source of Solar System 10Be is inheritance of GCR-irradiated protosolar molecular cloud material, but only if all CAIs recorded the same initial 10Be abundance. The goal of this dissertation is to assess the homogeneity of 10Be by measuring CAIs for 10Be–10B isotope systematics, correlated to 26Al–26Mg and oxygen isotopes.

I synthesized appropriate standards for secondary ion mass spectrometry (SIMS) measurements of 10Be–10B, necessary for accurate determination of the 10Be/9Be ratio. I then analyzed 32 CAIs for 10Be–10B as well as 6 CAIs for 26Al–26Mg and 5 CAIs for oxygen isotopes within this sample set using SIMS. Previous studies analyzed CAIs primarily from CV3 chondrites, which are known to have experienced thermal metamorphism and aqueous alteration. My work included a variety of CAIs (Type A, B, fine-grained, igneous) from CV3oxidized, CV3reduced, CO3, CR2, and CH/CB chondrites. Finally, after evaluating my data and literature data consistently, I statistically tested whether all CAIs belong to a single 10Be population. I find that the majority (~85%) of the normal (i.e., without large isotopic fractionations or anomalies), 26Al-bearing CAIs recorded a single value, 10Be/9Be = (7.0 ± 0.2) × 10-4. Although 6 CAIs recorded higher or lower values, these are plausibly explained by secondary alteration processes. The galaxy-wide average value of 10Be/9Be from GCR interactions 4.56 billion years ago is predicted to be <2 × 10-4; the value I measured is more than 3 times higher. Because GCRs trace supernovae and star formation, my results suggest a similarly enhanced star formation rate in the molecular cloud within ~1 kpc of the Sun, in the ~15 Ma prior to the Sun’s birth.

Isotope ratios of some trace metals have proven useful for tracking Earth’s ocean oxygenation history. As the limitations of some of these isotope systems are realized, it becomes increasingly important to develop new and complementary systems. This dissertation examines the utility of molybdenum (98Mo) and thallium (205Tl) isotope compositions preserved in ancient marine shales to track past ocean oxygenation. My approach is as follows: (1) as an initial exercise, apply the well-established Mo isotope system to a set of ancient shales; (2) validate the use of the newly developed Tl isotope system; and finally (3) examine the potential of applying Mo and Tl isotopes in tandem.

Increasingly heavier 98Mo are found in shales deposited during the Neoarchean (2,800 to 2,500 million years ago, or Ma), which would be a predicted consequence of progressive ocean oxygenation across this timeframe. Increasingly heavier 205Tl across a well-documented Mesozoic Oceanic Anoxic Event (~94 Ma), on the other hand, would be a predicted consequence of progressive ocean de-oxygenation. An anti-correlation in the first combined application of Mo and Tl isotopes in ancient shales provides a strong fingerprint for previously unrecognized levels of ocean oxygenation at ~2,500 Ma. Lastly, neither 98Mo or 205Tl behave as predicted in shales deposited during three Ediacaran Ocean Oxygenation Events (~635 Ma, ~580 Ma, and ~560 Ma). These unexpected trends are due, at least in part, to local-scale overprints that must be taken into consideration when pairing together Mo and Tl isotopes in shales.

The ability of the Mo and Tl isotope systems to track changes in past ocean oxygenation is confirmed in this dissertation. Both isotope systems have the potential to track these changes independently, but their combined utility is particularly powerful. Under ideal conditions, their combined application can provide an even more robust fingerprint for changes in past ocean oxygenation. Even under non-ideal conditions, their combined application makes it possible to decipher local-scale overprints from signals of past ocean oxygenation. It is therefore ideal, whenever possible, to measure both 98Mo and 205Tl in the same shale samples to assess past changes in ocean oxygenation.

During the early Solar System many physiochemical processes were taking place that would shape the formation and evolution of rocky bodies. Growth of these rocky objects was rapid, with some growing to sizes of 10s – 1000s km (“planetesimals”) in the first few million years. Because these objects formed early, they contained sufficient 26Al (an isotope of Al with a short half-life of ~705,000 yrs) to heat the interiors to melting temperatures, resulting in the formation of the first igneous rocks in nascent Solar System. Depending on the size and time of accretion, some bodies experienced high degrees of melting (with some having global magma oceans) while others experienced lower degrees of partial melting, and yet others did not experience any melting at all. These varying degrees of heating and melting processes on early-formed planetesimals produced a variety of achondritic meteorite types. These achondrites have bulk compositions ranging from ultramafic to basaltic, with some rare types having more highly “evolved” (i.e., high-SiO2) compositions. Determining the detailed chronology of their formation with fine time resolution is key for understanding the earliest stages of planet formation, and there are high resolution chronometers that are ideally suited for this application. Three such chronometers (i.e., the 26Al-26Mg, 53Mn-53Cr, and 207Pb-206Pb chronometers) are the focus of this work. Based on investigations of these chronometers in several achondritic meteorites, the implications for the formation and evolution of planetesimals in the early Solar System will be discussed.

The lunar poles have hydrated materials in their permanently shadowed regions (PSRs), also known as lunar cold traps. These cold traps exist because of the Moon’s slight tilt of 1.5, which consequently creates these PSRs. In these shadows, the temperature remains cold enough to prevent the sublimation of volatile materials for timescales spanning that of geologic times [Hayne et. al 2015]. PSRs are significant because they create an environment where water ice can exist within the first meter of regolith at the lunar poles, where many cold traps are present. These volatile materials can be observed through a process called neutron spectroscopy. Neutron spectroscopy is a method of observing the neutron interactions caused by galactic and extragalactic cosmic ray proton collisions. Neutron interactions are more sensitive to hydrogen than other elements found in the regolith, and thus are a good indicator of hydrated materials. Using neutron spectroscopy, it is possible to detect the hydrogen in these cold traps up to a meter deep in the regolith, thus detecting the presence of hydrated materials, water, or ice.
For this study, we used the Monte Carlo Neutral Particle Transport Code (MCNP6) to create a homogenous sphere that represented the PSRs on Moon, and then modeled five differing water contents for the lunar regolith ranging from 0-20 percent weight. These percent weights were modeled after the estimates for Shackleton crater, data from Lunar Reconnaissance Orbiter (LRO) mission, and data from Lunar Orbiter Laser Altimeter (LOLA).
This study was created with the LunaH-Map mission as motivation, seeking to exhibit what neutron data might be observed. The LunaH-Map mission is an array of mini-Neutron Spectrometers that will orbit the Moon 8-20 km away from the lunar surface and map the spatial
distribution of hydrogen at the lunar poles. The plots generated show the relationship between neutron flux and energy from the surface of the Moon as well as from 10km away. This data provides insight into the benefits of collecting orbital data versus surface data, as well as illustrating what LunaH-Map might observe within a PSR.