A new method was developed for the measurement of titanium isotopes in calcium-aluminum-rich inclusions (CAIs) by laser ablation multi-collector inductively coupled plasma mass spectrometry. The isotopic compositions of 17 Allende CAIs define a narrow range with clearly resolved excesses in 46Ti and 50Ti and suggests that "normal" CAIs formed from a relatively uniform reservoir. Petrologic and isotopic analysis of a new FUN (Fractionated and Unknown Nuclear effects) CAI suggests that normal and FUN CAIs condensed in similar environments, but subsequently evolved under vastly different conditions.
Volatiles may have influenced the formation and evolution of basaltic magmas on Mars. Light lithophile element (LLE) and fluorine (F) concentrations and isotopic compositions of pyroxene determined in situ in several Martian meteorites suggests that the primary magmatic signature of LLE and F zonation in Shergottite pyroxene has been disturbed by post-crystallization diffusive equilibration. Using relevant crystal-melt partition coefficients the F contents for Martian meteorite parental melts are ~910 and ~220 ppm. Estimates of the F content in the Shergottite and Nakhlite source regions are similar to that of mid-ocean ridge basalts (MORB) and ocean island basalts (OIB), respectively, here on Earth.
Noble gas systematics of OIBs relative to MORBs, suggests OIBs preferentially sample a primordial reservoir located within Earth's mantle. Geodynamic calculations were performed to investigate the time-dependent rate of material entrained into plumes from these primordial reservoirs. These models predict melts rising to the surface will contain variable proportions of primordial material. The results demonstrate that although high 3He/4He ratios may mandate a mantle plume that samples a primordial reservoir, more MORB-like 3He/4He ratios in OIBs do not preclude a deep plume source.
CC materials previously resided on asteroidal parent bodies, relic planetesimals of Solar System formation which never accreted enough material to develop long-lived, large-scale geological processes. These bodies were large enough, however, to experience some degree of heating due to the decay of radiogenic isotopes, and the meteorite record suggests the existence of 100-150 parent bodies which experienced varying degrees of thermal and aqueous alteration for the first several 10 Myr of Solar System history.
The first chapter of this dissertation reviews literature addressing aqueous alteration as an essential participant in parent body geochemistry, organic synthesis, or both (though papers which address both are rare). The second chapter is a published organic analysis of the soluble organic material of Bells, an unclassified type 2 chondrite. Analytical approaches to assess terrestrial contamination of meteorite samples are also reviewed in the first chapter to allow introduction in chapter 3 of kinetic modeling which rules out certain cases of contamination and constrains the timing of thermal and aqueous alteration. This is the first known application of isoleucine epimerization for either of these purposes. Chapter 4 is a kinetic study of D-allo-isoleucine epimerization to establish its behavior in systems with large, relative abundances of alloisoleucine to isoleucine. Previous epimerization studies for paleontological or geological purposes began with L-isoleucine, the only protein amino acid of the four isoleucine stereoisomers.
Kinetic model calculations using isoleucine stereoisomer abundances from 7 CR chondrites constrain the total duration of the amino acids' residence in the aqueous phase. The comparatively short timescales produced by the presented modeling elicit hypotheses for protection or transport of the amino acids within the CR parent body.
I then combine the two numerical methods to study starburst outflows as they interact with satellite halos. This process leads to shocks catalyzing the formation of molecular coolants that lead to bursts in star formation, a process that is better captured in grid methods. The resultant clumps of stars are removed from their initial dark matter halo, resemble precursors to modern-day globular clusters, and their formation may be observable with upcoming telescopes.
Finally, I perform two simulation suites, comparing each numerical method's ability to model the impact of energetic feedback from accreting black holes at the core of giant clusters. With these comparisons I show that black hole feedback can maintain a hot diffuse medium while limiting the amount of gas that can condense into the interstellar medium, reducing the central star formation by up to an order of magnitude.
Humans have dramatically increased phosphorus (P) availability in terrestrial and aquatic ecosystems. As P is often a limiting nutrient of primary production, changes in its availability can have dramatic effects on ecosystem processes. I examined the effects of calcium carbonate (CaCO3) deposition, which can lower P concentrations via coprecipitation of phosphate, on P availability in two systems: streams in the Huachuca Mountains, Arizona, and a stream, Río Mesquites, in Cuatro Ciénegas, México. Calcium carbonate forms as travertine in the former and within the microbialites of the latter. Despite these differences, CaCO3 deposition led to lowered P availability in both systems. By analyzing a three-year dataset of water chemistry from the Huachuca Mountain streams, I determined that P concentrations were negatively related to CaCO3 deposition rates. I also discovered that CaCO3 was positively correlated with nitrogen concentrations, suggesting that the stoichiometric effect of CaCO3 deposition on nutrient availability is due not only to coprecipitation of phosphate, but also to P-related constraints on biotic nitrogen uptake. Building from these observations, bioassays of nutrient limitation of periphyton growth suggest that P limitation is more prevalent in streams with active CaCO3 deposition than those without. Furthermore, when I experimentally reduced rates of CaCO3 deposition within one of the streams by partial light-exclusion, areal P uptake lengths decreased, periphyton P content and growth increased, and periphyton nutrient limitation by P decreased. In Río Mesquites, CaCO3 deposition was also associated with P limitation of microbial growth. There, I investigated the consequences of reductions in CaCO3 deposition with several methods. Calcium removal led to increased concentrations of P in the microbial biomass while light reductions decreased microbial biomass and chemical inhibition had no effect. These results suggest that CaCO3 deposition in microbialites does limit biological uptake of P, that photoautotrophs play an important role in nutrient acquisition, and, combined with other experimental observations, that sulfate reduction may support CaCO3 deposition in the microbialite communities of Río Mesquites. Overall, my results suggest that the effects of CaCO3 deposition on P availability are general and this process should be considered when managing nutrient flows across aquatic ecosystems.