abstract: Historically, uranium has received intense study of its chemical and isotopic properties for use in the nuclear industry, but has been largely ignored by geoscientists despite properties that make it an intriguing target for geochemists and cosmochemists alike. Uranium was long thought to have an invariant 238U/235U ratio in natural samples, making it uninteresting for isotopic work. However, recent advances in mass spectrometry have made it possible to detect slight differences in the 238U/235U ratio, creating many exciting new opportunities for U isotopic research. Using uranium ore samples from diverse depositional settings from around the world, it is shown that the low-temperature redox transition of uranium (U6+ to U4+) causes measurable fractionation of the 238U/235U ratio. Moreover, it is shown experimentally that a coordination change of U can also cause measurable fractionation in the 238U/235U ratio. This improved understanding of the fractionation mechanisms of U allows for the use of the 238U/235U ratio as a paleoredox proxy. The 238U/235U ratios of carbonates deposited spanning the end-Permian extinction horizon provide evidence of pronounced and persistent widespread ocean anoxia at, or immediately preceding, the extinction boundary. Variable 238U/235U ratios correlated with proxies for initial Cm/U in the Solar System's earliest objects demonstrates the existence of 247Cm in the early Solar System. Proof of variable 238U/235U ratios in meteoritic material forces a substantive change in the previously established procedures of Pb-Pb dating, which assumed an invariant 238U/235U ratio. This advancement improves the accuracy of not only the Pb-Pb chronometer that directly utilizes the 238U/235U ratio, but also for short-lived radiometric dating techniques that indirectly use the 238U/235U ratio to calculate ages of Solar System material. / Dissertation/Thesis / Ph.D. Geological Sciences 2011

abstract: Variations of 238U/235U in sedimentary carbonate rocks are being explored as a tool for reconstructing oceanic anoxia through time. However, the fidelity of this novel paleoredox proxy relies on characterization of uranium isotope geochemistry via laboratory experimental studies and field work in modern analog environmental settings. This dissertation systematically examines the fidelity of 238U/235U in sedimentary carbonate rocks as a paleoredox proxy focusing on the following issues: (1) U isotope fractionation during U incorporation into primary abiotic and biogenic calcium carbonates; (2) diagenetic effects on U isotope fractionation in modern shallow-water carbonate sediments; (3) the effects of anoxic depositional environments on 238U/235U in carbonate sediments. Variable and positive shifts of 238U/235U were observed during U uptake by primary abiotic and biotic calcium carbonates, carbonate diagenesis, and anoxic deposition of carbonates. Previous CaCO3 coprecipitation experiments demonstrated a small but measurable U isotope fractionation of ~0.10 ‰ during U(VI) incorporation into abiotic calcium carbonates, with 238U preferentially incorporated into the precipitates (Chen et al., 2016). The magnitude of U isotope fractionation depended on aqueous U speciation, which is controlled by water chemistry, including pH, ionic strength, carbonate, and Ca2+ and Mg2+ concentrations. Based on this speciation-dependent isotope fractionation model, the estimated U isotope fractionation in abiotic calcium carbonates induced by secular changes in seawater chemistry through the Phanerozoic was predicted to be 0.11–0.23 ‰. A smaller and variable U isotope fractionation (0–0.09 ‰) was observed in primary biogenic calcium carbonates, which fractionated U isotopes in the same direction as abiotic calcium carbonates. Early diagenesis of modern shallow-water carbonate sediments from the Bahamas shifted δ238U values to be 0.270.14 ‰ (1 SD) higher than contemporaneous seawater. Also, carbonate sediments deposited under anoxic conditions in a redox-stratified lake—Fayetteville Green Lake, New York, USA— exhibited elevated δ238U values by 0.160.12 ‰ (1 SD) relative to surface water carbonates with significant enrichments in U. The significant U isotope fractionation observed in these studies suggests the need to correct for the U isotopic offset between carbonate sediments and coeval seawater when using δ238U variations in ancient carbonate rocks to reconstruct changes in ocean anoxia. The U isotope fractionation in abiotic and biogenic primary carbonate precipitates, during carbonate diagenesis, and under anoxic depositional environments provide a preliminary guideline to calibrate 238U/235U in sedimentary carbonate rocks as a paleoredox proxy. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2018

abstract: Banded iron formations (BIFs) are among the earliest possible indicators for oxidation of the Archean biosphere. However, the origin of BIFs remains debated. Proposed formation mechanisms include oxidation of Fe(II) by O2 (Cloud, 1973), photoferrotrophy (Konhauser et al., 2002), and abiotic UV photooxidation (Braterman et al., 1983; Konhauser et al., 2007). Resolving this debate could help determine whether BIFs are really indicators of O2, biological activity, or neither. To examine the viability of abiotic UV photooxidation of Fe, laboratory experiments were conducted in which Fe-bearing solutions were irradiated with different regions of the ultraviolet (UV) spectrum and Fe oxidation and precipitation were measured. The goal was to revisit previous experiments that obtained conflicting results, and extend these experiments by using a realistic bicarbonate buffered solution and a xenon (Xe) lamp to better match the solar spectrum and light intensity. In experiments reexamining previous work, Fe photooxidation and precipitation was observed. Using a series of wavelength cut-off filters, the reaction was determined not to be caused by light > 345 nm. Experiments using a bicarbonate buffered solution, simulating natural waters, and using unbuffered solutions, as in prior work showed the same wavelength sensitivity. In an experiment with a Xe lamp and realistic concentrations of Archean [Fe(II)], Fe precipitation was observed in hours, demonstrating the ability for photooxidation to occur significantly in a simulated natural setting. These results lead to modeled Fe photooxidation rates of 25 mg Fe cm-2 yr-1—near the low end of published BIF deposition rates, which range from 9 mg Fe cm-2 yr-1 to as high as 254 mg Fe cm-2 yr-1 (Konhauser et al., 2002; Trendall and Blockley, 1970). Because the rates are on the edge and the model has unquantified, favorable assumptions, these results suggest that photooxidation could contribute to, but might not be completely responsible for, large rapidly deposited BIFs such those in the Hamersley Basin. Further work is needed to improve the model and test photooxidation with other solution components. Though possibly unable to fully explain BIFs, UV light has significant oxidizing power, so the importance of photooxidation in the Archean as an environmental process and its impact on paleoredox proxies need to be determined. / Dissertation/Thesis / Masters Thesis Biochemistry 2017

Indiana University-Purdue University Indianapolis (IUPUI) / Colonial settlement of Indiana changed the environment in significant ways; the aim of this study is to quantify the impacts of settlement through the use of geochemical proxies including: % lithics; the carbon (δ13C), nitrogen (δ15N), and sulfur (δ34S) isotope composition of organic matter; the elemental composition of carbon (TOC) and nitrogen (Ntot) in organic matter and their ratio (C/N); the δ34S of mineral sulfides (pyrite and acid volatile sulfides); and iron redox proxies. Lakes are a great recorder of aquatic-terrestrial linkages on both local and global scales. Martin lake’s watershed, in northeastern Indiana, was settled in 1840 by Euro-Americans, and since then clear shifts in lake chemistry are recorded in its sediments. A core spanning roughly the last 300 years taken from Martin Lake is the basis of this study. The impacts of settlement can be seen through the lenses of all the proxies that were used in this study. 1) Post-settlement deforestation increased erosion in Martin Lake’s watershed, increasing sedimentation rates and % lithics. 2) δ13C of organic matter reveals a pattern of deforestation and partial regrowth and agricultural use of land. 3) A pronounced increase in δ15N timed with the change in population at the time of settlement is consistent with the increased input of human or animal waste into Martin Lake. 4) TOC and C/N show an overall increase in the amount of organic matter within the lake caused by deforestation, and that the increased nutrient supply may have stimulated more in-lake productivity. 5) δ34S of mineral sulfides show that deforestation lead to an increase in the available sulfate pool of Martin Lake, which in combination with 6) an increase in FeHR created redox conditions in which pyrite formation was more favorable. These factors culminated in a transition in Martin Lake chemistry and redox cycling within the sediments.

The environmental processes and conditions controlling productivity and organic matter (OM) accumulation/preservation as well as bottom–water redox conditions in the lower black shale (LBS) and upper black shale (UBS) members of the Devonian-Mississippian (D–M) Bakken Formation were evaluated utilizing trace metal (TM) concentrations, degree of pyritization (DOPT), enrichment factors (EF) of TMs, bi–metal ratios (V/Cr, V/(V+Ni), Ni/Co, U/Th), total sulfur (ST) vs. iron (Fe), total organic carbon (TOC), carbon–sulfur–iron relationships (C–S–Fe), as well as Mo–TOC and Mo EF–U EF relationships. High-resolution (1- to 3-cm scale) chemostratigraphic records were generated for twelve drill cores, four of which closely flank the N–S-trending axis of the Nesson Anticline, proximal to the center of the Williston Basin in northwest North Dakota, USA. Furthermore, five of the twelve drill cores were selected (sample selection was based on down–core spacing and TM concentrations) for petrographic and Rock-Eval analysis to assess variations in kerogen type, quantity, quality, and thermal maturity (based on solid bitumen reflectance (%SBRo), vitrinite reflectance equivalence (%VRE), Rock–Eval Tmax–derived vitrinite reflectance (%Ro)) from immature to condensate, wet gas hydrocarbon generation windows. Degree of pyritization (DOPT) values (0.25 to 1.0) indicate that bottom waters were frequently dysoxic (> 60%) with intermittent aerobic and anoxic/euxinic conditions which is in agreement with C–S–Fe and total ST vs. Fe assessments of paleoredox conditions and sedimentological evidence. Furthermore, using published Mo–TOC relationships from modern anoxic-euxinic basins, it is estimated that renewal time of the sub-chemoclinal water mass during accumulation of the LBS and UBS approximated 10 and 30 yrs., respectively. Agreement is also seen between Mo/TOC and Mo EF/U EF where both suggest the Bakken shales were deposited under relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. However, bi–metal ratios suggest > 80% of samples were deposited under suboxic to anoxic/euxinic conditions. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5x greater than those reported for other D–M black shale formations. The Bakken black shales represent a unique sedimentary system where the EF of various TMs such as Cu (6.2–7.7), Mo (219.7–237.8), Ni (9.4–10.2), U (20.6–29.3), V (9.9–14.2), and Zn (10.4–12.2) as well as total organic carbon contents (LBS = 10.80 and UBS = 11.80 avg. wt.%) are considerably higher than other Devonian–Mississippian black shales. In this study, raw distributions of elemental concentrations combined with bivariate and principal component analysis (PCA) were used to elucidate the processes that could have contributed to the high EF of TMs in the Bakken shales. Total organic carbon shares heavier PCA component loadings (>0.445) and stronger correlation coefficients (r) with Cu, Mo, Ni, U, V, and Zn rather than with pyrite-associated (As, Co, Fe, and S) elements, suggesting that TOC played a primary role in the scavenging and accumulation of TMs in the sediments. Reducing conditions within bottom waters or sediment pore waters may have accelerated the accumulation of redox-sensitive Cu, Mo, Ni, V, and Zn introduced into the sediments via primarily an organic matter (OM) detritus host and most likely played a secondary role in the enrichment of TMs. The high EF of TMs observed in the Bakken shales may be the result of the frequent resupply of TMs into basin waters, enhanced primary productivity that is necessary in scavenging TMs from the water column, the presence of H2S within sediment pore or bottom waters, or possibly secondary processes associated with basin-wide fluid and hydrocarbon migration. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios (i.e., V/Cr, V/(V+Ni), Ni/Co, U/Th) in assessing bottom–water conditions for the Bakken shales. Solid bitumen (SB), a secondary organic matter formed as a residue after hydrocarbon generation (through either sufficient thermal maturation or microbial degradation) and expulsion, is primarily dispersed within the mineral matrix and increases in quantity with increasing thermal maturity. Rock-Eval II and HAWK analyzers were used to measure and estimate the hydrogen index (HI; avg. 201 mg HC/g TOC), oxygen index (OI; avg. 7mg CO2/g TOC), S1 (free hydrocarbons; avg. 8.0 mg HC/g rock), S2 (hydrocarbons generated after cracking kerogen; avg. 24.3 mg HC/g rock), and %Ro (0.60–1.03%; estimated from Tmax). The HI and OI values are calculated from TOC as well as S2 and S3 (oxygen bonded to hydrocarbons). Plots of HI vs. Tmax (ºC) and HI vs. OI as well as S2 vs. S3 ratio were utilized to determine the type of kerogen, primary OM that is insoluble in organic solvents. However, these relationships are not in agreement with kerogen typing based on petrographic observations, where samples from more thermally mature cores plot as Type III (vitrinite) kerogen instead of observed Type I/II (marine algae) kerogen. This is largely due to the abundant presence of SB in the more thermally mature section of the Bakken (Rock-Eval Ro = 0.83–1.03%) as SB is known to have a lower HI content than Type II kerogen. Petrographic evidence shows greater abundance of alginite and amorphous organic matter (AOM or bituminite) in the thermally less mature (Rock-Eval Ro = 0.60–0.83%) section of the Bakken compared to the greater abundance of dispersed SB in the more thermally mature section where AOM is absent. Early research on the Bakken Fm. reported lower than expected vitrinite reflectance values attributed to vitrinite “suppression". The overall lack of vitrinite and abundance of solid bitumen in these shales suggests that these early attempts likely reported solid bitumen reflectance rather than vitrinite reflectance. More recent attempts to assess the thermal maturity of the Bakken Fm. black shales have measured and converted SBRo to vitrinite reflectance equivalent (VRE). However, samples selected for SBRo by some previous workers have included heterogenous, granular as well as high reflecting SB samples, which introduce error in the measurements. As such, reported reflectance values are most likely lower than they would be if smooth, homogenous solid bitumen with no inclusions were measured. For this project, smooth and homogenous SB was measured to produce consistent and reliable VRE values to assess the thermal maturity gradient from the Bakken Fm. basin margins to the depocenter. Blue-light fluorescence petrography was done to support thermal maturity assessments. Results from SBRo, Rock-Eval Ro, VRE, and blue-light fluorescence observations suggest that cores from the current study range from early oil window into condensate, wet gas.

Indiana University-Purdue University Indianapolis (IUPUI) / The Ordovician (485-444 Ma) was a highly dynamic period, characterized by significant evolutionary and climatic change. Paleozoic fauna which evolved during the Great Ordovician Biodiversification Event (GOBE) populated extensive epicontinental seaways. Major sea level fluctuations during The Hirnantian glaciation are believed to have led to a mass extinction event at the End Ordovician. However, a reassessment of Early Paleozoic fossil assemblages suggests the onset of extinctions began in the mid-Katian, ~3 million years before the Hirnantian. The Kope formation, within the North American succession of the Katian, was deposited during the peak biodiversification of the GOBE at the point which a biological crisis begins. The well-studied series of interbedded shale and fossiliferous limestone beds, deposited within a shallow epeiric sea, provide ideal sedimentological and paleontological context to interpret sediment geochemistry recorded at the onset of a global mass extinction. For a high-resolution section of the Kope, δ34Spyrite show an extraordinary range of variability, up to 64.5‰, with systematic oscillations throughout the core. The isotope signal represents a mix of pyrite formed at the time of deposition and during diagenesis. As sea levels fluctuated, the amount of sediment delivery influenced the connection of sediment porewaters to overlying seawater sulfate and the location of the sulfate reduction zone, which in turn, masked the primary signal. Reactive iron data suggest low oxygen concentrations in the water column, however fossil assemblages found throughout the Kope suggest otherwise. Changes in sedimentation can mask the water column signal, so these data also capture an aggregate signal. δ15Nbulk show an upsection decrease of 4.4‰, followed by a 3.4‰ increase. Though this excursion can be interpreted as a switch to increased denitrification in a low oxygen environment, the fossil record suggests the data capture localized diagenetic reactions that occur below an oxic water column. Perturbations in the ocean-climate system is often based on the interpretation of stable isotope excursions, and although excursions are diagnostic of changes to biogeochemical cycles, they may not fully account for diagenetic reactions that mask primary signals. The results from the Kope demonstrate strong localized, not global, controls on the sediment geochemistry.

The research presented here is an effort to characterize changes in marine oxygen availability across a portion of the later Cambrian noted for unique evolutionary dynamics and which includes a significant global oceanographic event known as the SPICE event (Steptoean Positive Carbon Isotope Excursion). Previous studies have revealed the SPICE caused large changes to the global cycles of carbon, sulfur, uranium, molybdenum and the overall trace metal content of seawater. Furthermore, the initiation of these changes appears to have been temporally coupled with marine extinctions across several paleocontinents raising the possibility of a common causal linkage between all these features. In particular, expanding marine anoxia has been invoked as the most parsimonious explanation for these co-occurring features. The research presented here tests this hypothesis directly across a range of spatial scales using the iron speciation paleoredox proxy to characterize redox conditions within individual basins and to facilitate comparison of conditions between basins. In addition to these analyses, we apply a new proxy, thallium stable isotopes to this interval to assess potential global changes in deoxygenation across the event. These iron speciation analyses showed shallow environments deoxygenated coincident with the initiation of the SPICE and extinction horizons, and these conditions were dominantly ferruginous. Importantly, this work also shows deeper-water environments were deoxygenated prior to and remained so across the event and these environments were also largely. Last we looked at changes in thallium isotopes during this same interval to see if this deoxygenation would be recorded as a positive shift across the interval if expanded anoxia were to impact the areal extent of manganese-oxide sedimentation and burial. We found it did record these changes, but with a different expression than during other more recent events explored using the isotope system. We attribute these differences to the unique chemical structure of the oceans during the Cambrian, which as documented herein were widely oxygen-deficient in their deeper depths. Given this recognition we suggest that thallium isotope studies in deep time should account for this redox structure of ancient oceans likely common under the less-oxygenated atmospheres of the ancient Earth. / Doctor of Philosophy / The research presented here is a story about oxygen in the oceans during an ancient portion of Earth history within the Cambrian Period (around 500 million years ago), soon after animal life first appears in the geologic record. The emerging biosphere of this time seems to have been particularly prone to extinctions, leading to the idea that environmental conditions, such as oxygen availability at the seafloor created difficult circumstances for animals in these ancient seas. This work seeks to quantify the levels of marine oxygenation at this time, however this remains a fundamental challenge because they cannot be directly measured from the rocks we study. Therefore, we rely on how the presence or absence of oxygen changed the chemistry of these rocks at the time they were sediments deposited on the seafloor. Here we use the behavior of two different elements, iron (Fe) and thallium (Tl), to understand changes in oxygen in the oceans around a large, globally-recorded extinction event called the SPICE event. Studying how much iron is concentrated in certain minerals in the rocks formed during this event allowed us to track how changes in oxygen may relate to these notable extinctions. We found that shallow coastal areas changed from oxygenated to deoxygenated at the same time of the extinctions, suggesting a direct role for this environmental shift in the biological crisis. Furthermore, we compared other locations from around the world using more new iron measurements in conjunction with previously published ones compiled by a collaborative geochemistry database project. This work revealed the deeper oceans were deoxygenated prior to and across the SPICE event and that the decline in oxygen in shallower environments was where most environmental change occurred during this time. Last we looked at changes in thallium isotopes during this same interval to see if this deoxygenation changed its global cycle. We found it did record global changes, but they were expressed differently than during other more recent events that have been studied. We attribute these differences to the unique chemical structure of the oceans during the Cambrian, which were widely oxygen-deficient in their deeper depths.