Thesis (Ph. D.)--University of California, San Diego, 2001. / Vita. Includes bibliographical references.

Volatiles are critical in understanding the history of the solar system. We conducted two case studies intended to further this understanding. First, we analyzed the presence of CO2 on Iapetus. Second, we evaluated aqueous alteration in CM chondrites.We studied the distribution, stability and production of CO2 on Saturn's moon Iapetus. We determined that CO2 is concentrated exclusively on Iapetus' dark material with an effective thickness of 31 nm. The total CO2 on Iapetus' surface is 2.3x108 kg. However, CO2 should not be present because it has a limited residence time on the surface of Iapetus. Our thermal calculations and modeling show that CO2 in the form of frost will not remain on Iapetus' surface beyond a few hundred years. Thus, it must be complexed with dark material. However, photodissociation will destroy the observed inventory in ~1/2 an Earth year.The lack of thermal and radiolytic stability requires an active source. We conducted experiments showing UV radiation generates CO2 under Iapetus-like conditions. We created a simulated regolith by mixing crushed water ice with isotopically labeled carbon. We then irradiated it with UV light at low temperature and pressure, producing 1.1x1015 parts m-2 s-1. Extrapolating to Iapetus, photolysis could generate 8.4x107 kg y-1, which makes photolytic production a good candidate for the source of the CO2 detected on Iapetus.We also studied the aqueous alteration of metal-bearing assemblages in CM chondrites. We examined Murchison, Cold Bokkeveld, Nogoya, and Murray using microscopy, electron microprobe analysis and scanning electron microscopy. Alteration on CM meteorites occurred within at least three microchemical environments: S-rich water, Si-rich water and water without substantial reactive components. Kamacite alters into tochilinite, cronstedtite, or magnetite. Sulfur associated alteration can form accessory minerals: P-rich sulfides, eskolaite and schreibersite.Additionally, we determined that there were two alteration events for some CM chondrites. The first formed a hydrated matrix prior to accretion, indicated by unaltered kamacite surrounded by a hydrated matrix. The second occurred after parent body formation. This event is indicated by large regions with consistent alteration features, surrounded by other regions of less altered material.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

abstract: An exhaustive parameter study involving 133 dynamic crystallization experiments was conducted, to investigate the validity of the planetary embryo bow shock model by testing whether the cooling rates predicted by this model are consistent with the most dominant chondrule texture, porphyritic. Results show that using coarse-grained precursors and heating durations ≤ 5 minutes at peak temperature, porphyritic textures can be reproduced at cooling rates ≤ 600 K/hr, rates consistent with planetary embryo bow shocks. Porphyritic textures were found to be commonly associated with skeletal growth, which compares favorably to features in natural chondrules from Queen Alexandra Range 97008 analyzed, which show similar skeletal features. It is concluded that the experimentally reproduced porphyritic textures are consistent with those of natural chondrules. This work shows heating duration is a major determinant of chondrule texture and the work further constrains this parameter by measuring the rate of chemical dissolution of relict grains. The results provide a robust, independent constraint that porphyritic chondrules were heated at their peak temperatures for ≤ 10 minutes. This is also consistent with heating by bow shocks. The planetary embryo bow shock model therefore remains a viable chondrule mechanism for the formation of the vast majority of chondrules, and the results presented here therefore strongly suggest that large planetary embryos were present and on eccentric orbits during the first few million years of the Solar System’s history. / Dissertation/Thesis / Masters Thesis Geological Sciences 2018

abstract: Remote sensing in visible to near-infrared wavelengths is an important tool for identifying and understanding compositional differences on planetary surfaces. Electronic transitions produce broad absorption bands that are often due to the presence of iron cations in crystalline mineral structures or amorphous phases. Mars’ iron-rich and variably oxidized surface provides an ideal environment for detecting spectral variations that can be related to differences in surface dust cover or the composition of the underlying bedrock. Several imaging cameras sent to Mars include the capability to selectively filter incoming light to discriminate between surface materials. At the coarse spatial resolution provided by the wide-angle Mars Color Imager (MARCI) camera aboard the Mars Reconnaissance Orbiter (MRO), regional scale differences in reflectance at all wavelengths are dominated by the presence or absence of Fe3+-rich dust. The dust cover in many regions is highly variable, often with strong seasonal dependence although major storm events can redistribute dust in ways that significantly alter the albedo of large-scale regions outside of the normal annual cycle. Surface dust reservoirs represent an important part of the martian climate system and may play a critical role in the growth of regional dust storms to planet-wide scales. Detailed investigation of seasonal and secular changes permitted by repeated MARCI imaging coverage have allowed the surface dust coverage of the planet at large to be described and have revealed multiannual replenishing of regions historically associated with the growth of storms. From the ground, rover-based multispectral imaging acquired by the Mastcam cameras allows compositional discrimination between bedrock units and float material encountered along the Curiosity rover’s traverse across crater floor and lower Mt. Sharp units. Mastcam spectra indicate differences in primary mineralogy, the presence of iron-bearing alteration phases, and variations in iron oxidation state, which occur at specific locations along the rover’s traverse. These changes represent differences in the primary depositional environment and the action of later alteration by fluids circulating through fractures in the bedrock. Loose float rocks sample materials brought into the crater by fluvial or other processes. Mastcam observations provide important constraints on the geologic history of the Gale Crater site. / Dissertation/Thesis / Supplemental Animations for Chapter 2 / Doctoral Dissertation Geological Sciences 2018

High precision measurements of Ti isotopes within terrestrial and extra-terrestrial materials were made in order to investigate the processes at work within the early solar system. Variations of Ti isotopes also enabled the investigation of the specific stellar sources that created the material that formed the solar system. Titanium was chosen as it is a refractory element, relatively resistant to secondary processes and found abundantly in all solar system materials. Measurements were performed using a Thermo Fischer Neptune MC-ICPMS at the Open University, Milton Keynes. Various samples of carbonaceous chondrites, ordinary chondrites, enstatite chondrites, achondrites, lunar, terrestrial and early solar system components were analysed. Mass independent measurements of various solar system materials revealed a correlation between ε50/47Ti49/47 and ε46/47Ti49/47 defining a best line with a slope of 5.34 ± 0.34. The correlation indicates that solar system materials contain nucleosynthetic components that match a SNII stellar source. Utilising aliquots previously analysed for Zr isotopes for Ti isotope analyses revealed a correlation between ε50/47Ti49/47 and ε96/90Zr94/90 for the carbonaceous chondrites that is controlled by the CAI content of the particular carbonaceous chondrite group. Step wise dissolution of ordinary chondrites and carbonaceous chondrites revealed multiple nucleosynthetic Ti components contributing to the solar system. Stepwise leachate dissolutions were conducted on the carbonaceous chondrites Allende, Murchison and Orgueil to compliment the study of the same samples for Zr by Schönbächler et al. (2005). In addition, sample aliquots of QUE 97008 and Murchison from the work of Qin et al. (2011) were also investigated for Ti. The two investigations allow the comparison of Ti in different phases to be compared with other isotope systems such as Zr (Schönbächler et al. 2005) and Cr, Sr, Ba, Sm, Nd and Hf (Qin et al. 2011).Mass dependent fractionation and absolute nucleosynthetic anomalies of Ti within solar system materials was determined by utilising the double spike procedure. Mass dependent analysis enabled the Stable isotope composition of terrestrial materials to be investigated, revealing mass dependent fractionation between terrestrial basalts and andesite’s. Utilising the double spike procedure also enabled the calculation of absolute nucleosynthetic anomalies for Ti within solar system materials. The absolute nucleosynthetic anomalies data revealed that CAI’s contain two different compositions with one representing an exotic stellar source and the other representing the mainstream solar system composition.

Laboratory measurements of primitive and differentiated meteorites have been made in order to understand the origin of isotopic anomalies. The element Zr is chosen for analysis, due to its potential for nuclear and astrophysical applications. Zirconium has five stable isotopes that are produced in different (neutron–capture) nucleosynthetic processes. By analysing the Zr isotope composition of meteorites, we are able to track the mixing of various neutron capture processes in the early Solar System. Measurements have been performed on carbonaceous, ordinary and enstatite chondrites, eucrites, the Moon and Earth. Samples are crushed, digested and passed through a two stage anion exchange separation to obtain a clean Zr fraction. All Zr measurements are made on a Nu Plasma multiple–collector inductively coupled plasma mass spectrometer (MC–ICPMS). The results indicate that the bulk of refractory Ca–Al rich inclusions of the Allende meteorite are characterised by uniform enrichments (around 2ε) of the neutron–rich isotope 96Zr, and potentially coupled with excesses reported for the neutron rich isotope 50Ti, indicating that both nuclides may have similar astrophysical origins. Analysis of bulk rock carbonaceous chondrites reveal 96Zr excesses (not exceeding 1ε) that scale with the abundance of CAIs. However, widespread 96Zr correlations are also seen, accompanied by minor depletions in 91Zr, which suggest the solar nebular had experienced thermal heating of some sort, altering the initial (possibly uniform) Zr isotope composition of the early Solar System from which planetary bodies formed.

M.Sc. / This dissertation deals with meteorites, but from a few different perspectives. As of 2000, there are 49 known meteorites that have been recovered from South Africa, including the new Merweville chondrite, which is first described and classified here. This represents only about 1.5% of worldwide falls and finds. Perhaps because of the relatively small number of specimens, and a possible resulting drop in interest amongst the scientific community, research on extant South African meteorites has declined in recent years. In this study, new results are presented for two South African meteorites, the Malvern howardite, and the newly recovered Merweville chondrite. In addition, South African public knowledge and awareness of meteorites and planetary sciences is discussed, and remedial recommendations are made. The Malvern howardite is a rare type of polymictbreccia. New petrographic, mineralogical and geochemical studies of clasts reveal an abundance of impact-melt clasts, with lesser amounts of cataclastic, granoblastic and metal and sulphide-rich clasts. The matrix of Malvern is dominated by comminuted pyroxene, very likely derived from mechanical degradation of pre-existing, pyroxene-richimpact-meltclasts. Chondritic clasts, including carbonaceous chondrites, have been reported in similar howardites (e.g. Washougal, Jodzie and Kapoeta); such clasts were searched for, but not found in our specimens of Malvern. To investigate the social impact of meteorite studies, a survey of Grade 11 and 12 pupils and first year university students in South Africa was undertaken to determine their level of literacy, interest and awareness of meteorites and planetary sciences. Students in Johannesburg and Cape Town were chosen to represent different societal sectors, including school students from disadvantaged and advantaged communities. The results indicate that learners with poor results in awareness and literacy are still very keen on the subject. The advantaged learners outperformed their disadvantaged colleagues in most categories, proving that the discrepancy between them is still a factor and should be dealt with, but only 20% of all students asked have visited a museum before. Based on these results, it is recommended that much more emphasis be put on science and technology in South African schools. Taking learners to science and natural history museums or associated institutions are also very important in generating interest.

Chondritic meteorites are undifferentiated fragments of asteroids that contain the oldest solids formed in our Solar System. Their primitive, solar-like chemical compositions indicate that they experienced very little processing following accretion to their parent bodies. As such, they retain the best records of chemical and physical processes active in the protoplanetary disk during planet formation. Chondritic meteorites are depleted relative to the sun in volatile elements such as S and O. In addition to being important components of organic material, these elements exert a strong influence on the behavior of other more refractory species and the composition of planets. Understanding their distribution is therefore of key interest to the scientific community. While the bulk abundance of volatile elements in solid phases present in meteorites is below solar values, some meteorites record volatile-rich gas phases. The Rumuruti (R) chondrites record environments rich in both S and O, making them ideal probes for volatile enhancement in the early Solar System. Disentangling the effects of parent-body processing on pre-accretionary signatures requires unequilibrated meteorite samples. These samples are rare in the R chondrites. Here, I report analyses of unequilibrated clasts in two thin sections from the same meteorite, PRE 95404 (R3.2 to R4). Data include high resolution element maps, EMP chemical analyses from silicate, sulfide, phosphate, and spinel phases, SIMS oxygen isotope ratios of chondrules, and electron diffraction patterns from Cu-bearing phases. Oxygen isotope ratios and chondrule fO2 levels are consistent with type II chondrules in LL chondrites. Chondrule-sized, rounded sulfide nodules are ubiquitous in both thin sections. There are multiple instances of sulfide-silicate relationships that are petrologically similar to compound chondrules, suggesting that sulfide nodules and silicate chondrules formed as coexisting melts. This hypothesis is supported by the presence of phosphate inclusions and Cu-rich lamellae in both sulfide nodules and sulfide assemblages within silicate chondrules. Thermodynamic analyses indicate that sulfide melts reached temperatures up to 1138 °C and fS2 of 2 x 10^(-3) atm. These conditions require total pressures on the order of 1 atm, and a dust- or ice-rich environment. Comparison with current models suggest that either the environmental parameters used to model chondrule formation prior to planetesimal formation should be adjusted to meet this pressure constraint, or R chondrite chondrules may have formed through planetesimal bow shocks or impacts. The pre-accretionary environment recorded by unequilibrated R chondrites was therefore highly sulfidizing, and had fO2 higher than solar composition, but lower than the equilibrated R chondrites.Chalcopyrite is rare in meteorites, but forms terrestrially in hydrothermal sulfide deposits. It was previously reported in the R chondrites. I studied thin sections from PRE 95411 (R3 or R4), PCA 91002 (R3.8 to R5), and NWA 7514 (R6) using Cu X-ray maps and EMP chemical analyses of sulfide phases. I found chalcopyrite in all three samples. TEM electron diffraction data from a representative assemblage in PRE 95411 are consistent with this mineral identification. TEM images and X-ray maps reveal the presence of an oxide vein. A cubanite-like phase was identified in PCA 91002. Electron diffraction patterns are consistent with isocubanite. Cu-rich lamellae in the unequilibrated clasts of PRE 95404 are the presumed precursor materials for chalcopyrite and isocubanite. Diffraction patterns from these precursor phases index to bornite. I hypothesize that bornite formed during melt crystallization prior to accretion. Hydrothermal alteration on the parent body by an Fe-rich aqueous phase between 200 and 300°C resulted in the formation of isocubanite and chalcopyrite. In most instances, isocubanite may have transformed to chalcopyrite and pyrrhotite at temperatures below 210°C. This environment was both oxidizing and sulfidizing, suggesting that the R chondrites record an extended history of volatile-rich interaction. These results indicate that hydrothermal alteration of sulfides on the R chondrite parent body was pervasive and occurred even in low petrologic types. This high temperature aqueous activity is distinct from both the low temperature aqueous alteration of the carbonaceous chondrites and the high temperature, anhydrous alteration of the ordinary chondrites.

L’étude en laboratoire de matériaux extraterrestres provenant d’objets ayant peu ou pas évolué depuis leur formation il y a environ 4.6 milliards d’années, peut améliorer notre connaissance sur les débuts de notre système planétaire. Par ailleurs, la simulation en laboratoire de certains processus que ces matériaux sont susceptibles de subir au cours de leur histoire apporte également de précieuses informations pour l’interprétation des données issues des observations astronomiques ainsi que pour la compréhension de l’évolution des solides du Milieu Interstellaire jusqu’à leur incorporation dans des objets planétaires, objets incluant aussi toutes sortes de débris tels que les astéroÏdes, les comètes et toutes sortes de poussières accessibles à la collecte et/ou à l’observation.Au cours de cette thèse, l’analyse des matériaux organiques ainsi que des matériaux silicatés, jusqu’alors peu étudiés conjointement, dans les poussières stratosphériques d’origine cosmique, révèle une corrélation entre la minéralogie des grains et la longueur des chaînes carbonées. Ce lien ne semble pas le fruit de processus à la surface des corps parents des grains mais semble plutôt tracer des processus pré-accrétionnels. La conservation de composants peu altérés sur les corps parents dans les matériaux extraterrestres est encore une fois confirmée par la découverte, au cours de cette thèse, d’inclusions dans la météorite carbonée « Paris » dont les spectres infrarouges sont très similaires à ceux des composés carbonés observés dans le Milieu Interstellaire. L’étude de grains cométaires issus de la mission spatiale Stardust a montré, contrairement à l’idée que les comètes soient composées uniquement de matériaux primitifs puisque conservés dans un réservoir froid, que celles-ci contiennent aussi un certain nombre de matériaux formés à haute température, confirmant alors de précédentes analyses d’échantillons de Stardust et impliquant des échanges de matériaux à grande échelle radiale dans le jeune Système solaire.La deuxième partie de ce travail, consacrée à l’étude d’analogues de matière extraterrestre, porte sur le rôle qu’ont pu jouer les matériaux à partir desquels les planètes telluriques se sont formées dans l’apport de l’eau sur la Terre dans le cadre du scénario dit de « wet accretion ». Les expériences effectuées au cours de cette thèse visant à simuler les interactions entre silicates et vapeur d’eau ont montré que ces matériaux permettent de stocker d’importantes quantités d’eau à leur surface par adsorption des molécules de la phase gazeuse. / Laboratory analyses performed on extraterrestrial materials originating from primitive bodies of our Solar System, that are bodies known to have suffered low alteration since their formation 4.6 billion years ago, can improve our knowledge on processes that have occurred in the early phase of our planetary system. Furthermore, laboratory simulations of some processes that these materials are likely to suffer during their life cycle also bring precious indications for interpreting observational data as well as for understanding the evolution of solids from the Interstellar Medium to their incorporation into planetary bodies, these latter including asteroids, comets and all kinds of dust that may be observed and/or collected back to Earth.During this thesis, the analysis of silicate as well as organic materials, which have not been much studied jointly so far, in stratospheric particles of cosmic origin, reveals a correlation between the mineralogy of the grains and the lengths of the chains of their carbonaceous component. This link does not seem to be due to parent body processing but rather to trace pre-accretionnal processes. The preservation of pristine components in extraterrestrial materials slightly altered on their parent bodies is again confirmed by the discovery in this work, of inclusions in the “Paris” carbonaceous chondrite whose infrared spectra are similar to the interstellar carbonaceous species. The study of cometary grains from the Stardust space mission showed, unlike the common idea that comets should be composed only of primitive materials since they reside in a cold reservoir, that comets do also contain a number of materials formed at high temperature, thus confirming results from previous studies of Stardust samples and implying large-scale radial mixing of materials in the young Solar system disk.The second part of my work, dedicated to experiments on primitive extraterrestrial amorphous silicates analogs, is aimed to study the role that materials from which Earth has accreted could have played in its water budget in the frame of the “wet accretion” scenario. The experiments performed along this thesis simulating interactions between silicates and water vapor, showed that silicates allow the storage of large quantities of water by adsorption onto their surface of molecules directly from the gas phase.