The Everglades is a sub-tropical coastal wetland characterized among others by its hydrological features and deposits of peat. Formation and preservation of organic matter in soils and sediments in this wetland ecosystem is critical for its sustainability and hydrological processes are important divers in the origin, transport and fate of organic matter. With this in mind, organic matter dynamics in the greater Florida Everglades was studied though various organic geochemistry techniques, especially biomarkers, bulk and compound specific δ13C and δD isotope analysis. The main objectives were focused on how different hydrological regimes in this ecosystem control organic matter dynamics, such as the mobilization of particulate organic matter (POM) in freshwater marshes and estuaries, and how organic geochemistry techniques can be applied to reconstruct Everglades paleo-hydrology. For this purpose organic matter in typical vegetation, floc, surface soils, soil cores, and estuarine suspended particulates were characterized in samples selected along hydrological gradients in the Water Conservation Area 3, Shark River Slough and Taylor Slough. This research focused on three general themes: (1) Assessment of the environmental dynamics and source-specific particulate organic carbon export in a mangrove-dominated estuary. (2) Assessment of the origin, transport and fate of organic matter in freshwater marsh. (3) Assessment of historical changes in hydrological conditions in the Everglades (paleo-hydrology) though biomarkes and compound specific isotope analyses. This study reports the first estimate of particulate organic carbon loss from mangrove ecosystems in the Everglades, provides evidence for particulate organic matter transport with regards to the formation of ridge and slough landscapes in the Everglades, and demonstrates the applicability of the combined biomarker and compound-specific stable isotope approach as a means to generate paleohydrological data in wetlands. The data suggests that: (1) Carbon loss from mangrove estuaries is roughly split 50/50 between dissolved and particulate carbon; (2) hydrological remobilization of particulate organic matter from slough to ridge environments may play an important role in the maintenance of the Everglades freshwater landscape; and (3) Historical changes in hydrology have resulted in significant vegetation shifts from historical slough type vegetation to present ridge type vegetation.

The co-evolution of life and the environment stands as a cornerstone in Earth's 4.5-billion-year history. Environmental fluctuations have wielded substantial influence over biological evolution, while life forms have, in turn, reshaped Earth's surface and climate. This dissertation centers on a critical period in Earth's history—the Neoproterozoic Era—when profound environmental shifts potentially catalyzed pivotal eukaryotic evolutionary events. By delving deeper into Neoproterozoic paleoenvironments, I aim at a clearer understanding of life-environment co-evolution in this crucial era. The first chapter focuses on an important juncture—the transition from prokaryote to eukaryote dominance in marine ecosystems during the Tonian Period (1000 Ma to 720 Ma). To assess whether the availability of nitrate, an important macro-nutrient, played a critical role in this evolutionary event, nitrogen isotope compositions (δ¹⁵N) of marine carbonates from the early Tonian (ca. 1000 Ma to ca. 800 Ma) Huaibei Group in North China were measured. The data indicate nitrate limitation in early Neoproterozoic oceans. Further, a compilation of Proterozoic sedimentary δ¹⁵N data, together with box model simulations, suggest a ~50% increase in marine nitrate availability at ~800 Ma. Limited nitrate availability in early Neoproterozoic oceans may have delayed the ecological rise of eukaryotes until ~800 Ma when increased nitrate supply, together with other environmental and ecological factors, may have contributed to the transition from prokaryote-dominant to eukaryote-dominant marine ecosystems. Recognizing the spatial and temporal variations in Neoproterozoic oceanic environments, the second chapter lays the groundwork for a robust stratigraphic framework for the early Tonian Period. Employing the dynamic time warping algorithm, I constructed a global stratigraphic framework for the early Tonian Period using δ¹³C_carb data from the North China, São Francisco, and Congo cratons. This exercise confirms the generally narrow range of δ¹³C_carb fluctuations in the early Tonian, but also confirms the presence of a negative δ¹³C_carb excursion of notable magnitude (~9 ‰) at ca. 920 Ma in multiple records, suggesting that it was global in scope. This negative excursion, known as the Majiatun excursion, is likely the oldest negative excursion in the Neoproterozoic Era and marks the onset of the dynamic Neoproterozoic carbon cycle. Shifting focus to the late Neoproterozoic, the third chapter delves into the origins of Neoproterozoic superheavy pyrite, whose bulk-sample δ³⁴S values are greater than those of contemporaneous seawater sulfate and whose origins remain controversial. Two supervised machine learning algorithms were trained on a large LA-ICP-MS pyrite trace element database to distinguish pyrite of different origins. The analysis validates that two models built on the co-behavior of 12 trace elements (Co, Ni, Cu, Zn, As, Mo, Ag, Sb, Te, Au, Tl, and Pb) can be used to accurately predict pyrite origins. This novel approach was then used to identify the origins of pyrite from two Neoproterozoic sedimentary successions in South China. The first set of samples contains isotopically superheavy pyrite from the Cryogenian Tiesi'ao and Datangpo formations. The second set of samples contains pyritic rims from the Ediacaran Doushantuo Formation; these pyrite rims are associated with fossiliferous chert nodules and do not have superheavy sulfur isotopes. For the superheavy pyrite, the models consistently show high confidence levels in identifying its genesis type, and three out of four samples were inferred to be of sedimentary origins. For the pyritic nodule rims, the models suggest that early diagenetic pyrite was subsequently altered by hydrothermal fluids and therefore shows mixed signals. The third chapter highlights the importance of pyrite trace elements in deciphering and distinguishing the origins of pyrite in sedimentary strata. / Doctor of Philosophy / Understanding how life and the environment have shaped our planet's story over 4.5 billion years is like piecing together an intricate puzzle. On the one hand, changes in the environment kickstarted big shifts in how life evolved. On the other hand, living creatures have also left their mark on Earth's landscapes and climate. This dissertation focuses on unraveling the mysterious Neoproterozoic Era (1 billion to 538 million years ago), a time when Earth saw some of its most dramatic changes. A significant aspect of my investigation delves into the evolutionary dynamics within ancient marine ecosystems. Specifically, I'm exploring a critical juncture when organisms with more complex cellular structures, known as eukaryotes, became ecologically more important than prokaryotic life forms in many aspects of Earth systems. By examining ancient rock formations from China, I have found evidence suggesting that nitrate, a vital nutrient, was scarce in the Neoproterozoic oceans. However, around 800 million years ago, there appears to have been a significant surge in nitrate availability. This surge potentially catalyzed a pivotal phase in evolution, possibly driving the shift from prokaryote to eukaryote dominance in these ancient waters. Second, there is a challenge to delineate a robust timeline for the early Neoproterozoic Era. Imagine trying to piece together a story from a time when there were no calendars or clear dates. Employing advanced statistical methods and comparing chemical signals preserved in carbonate rocks from disparate global locations, I endeavor to craft a coherent timeline for this crucial period. Within this timeline, a noteworthy anomaly in the carbon cycle emerged around 920 million years ago known as the Majiatun excursion. This anomaly represents a significant shift in the Neoproterozoic carbon cycle. Furthermore, my investigation plunges into the geochemistry of sulfur, an important element in shaping ancient marine environments. Certain sedimentary rocks harbor anomalous sulfur isotope signatures in the mineral pyrite (also known as fool's gold), hinting at dramatic environmental transformations during the late Neoproterozoic. Employing advanced analytical techniques and machine learning methodologies, I seek to discern the origins and implications of these anomalous sulfur isotope signals found in pyrite, unraveling their significance in reconstructing the environmental dynamics of ancient oceans.

Individual niche variation is increasingly being demonstrated in animal populations in a wide variety of species and taxa. Niche variation among individuals has important implications for the ecology, evolution and management of animal populations and is a subject of increasing interest. However, despite its widespread occurrence the causes and consequences of individual niche variation remain poorly understood. In this thesis I use the European badger (Meles meles), a well studied species of high ecological interest, as a model system to investigate individual niche variation. In order to achieve this I combine information on individual foraging niches derived via stable isotope analysis (SIA) of badger vibrissae with detailed life history and ecological data from a long-term study population to investigate the incidence, cause and consequence of individual niche variation within badger social groups. First I use the biomarker Rhodamine B to investigate vibrissae growth rates and patterns in badgers and demonstrate that the isotopic composition of a single vibrissa likely reflects diet over several months (Chapter 2). Next I explore the use of SIA as a tool to investigate badger diet, by comparing isotopic patterns to seasonal changes in diet measured using faecal analysis (Chapter 3). My results provide validation that SIA is powerful tool for investigating foraging variation in this species, and suggest that within badger populations substantial dietary variation may occur among individuals. Further investigation of isotopic variation Indicates that individuals within social groups differ markedly and consistently in their isotopic signature, independent of age and sex effects and that in some instances these differences are remarkably consistent across year (Chapter 4).This suggesting long term individual specialisation (Chapter 4). I find that the degree of this individual specialisation, and the relationship between specialisation and body condition is influenced by competition for resources (Chapter 5). Social groups with higher levels of competition exhibit greater specialisation and specialised individuals within these highly competitive environments are in better condition. Finally, I discuss the implications of these results for individual niche variation, for the application of SIA to study this behaviour and for badger ecology generally (Chapter 6). I also outline future directions for further research.

Sublimation experiments have been carried out to determine the effect of the mineral dust content of porous ices on the isotopic composition of the sublimate gas over medium (days to weeks) timescales. Whenever mineral dust of any kind was present, the D/H ratio of the sublimated gas was seen to decrease with time from the bulk ratio. Fractionations of up to 2.5 were observed for dust mixing ratios of 9 wt% and higher of JSC MARS-1 regolith simulant 1-10 mum crushed and sieved fraction. These favored the presence of the light isotope, H2O, in the gas phase. The more dust was added to the mixture, the more pronounced was this effect. Theoretical modeling of gas migration within the porous samples and adsorption on the excavated dust grains was undertaken to explain the results. Adsorption onto the dust grains is able to explain the low D/H ratios in the sublimate gas if adsorption favors retention of HDO over H2O. This leads to significant isotopic enrichment of HDO on the dust over time and depletion in the amount of HDO escaping the system as sublimate gas. This effect is significant for planetary bodies on which water moves mainly through the gas phase and a significant surface reservoir of dust may be found, such as on Comets and Mars. For each of these, inferences about the bulk water D/H ratio as inferred from gas phase measurements needs to be reassessed in light of the volatile cycling history of each body.PACS CODES:98.80.Ft Isotopes, abundances and evolution (astronomy)], 64.70.Hz Sublimation], 68.43.-h Adsorption at solid surfaces]

The marine silicon and carbon cycles are intrinsically linked by a unique group of primary producers; the diatoms. These siliceous-walled phytoplankton play a significant role in carbon export, making them a critical component of the global biological carbon pump with the power to affect climatic change. In this thesis, the silicon isotope composition (δ30Si) preserved in diatom opal is used together with the δ30Si of sponge opal, a powerful new proxy for deepwater silicic acid concentration, to document the Cenozoic Silicon cycle, shedding light on its role in carbon cycling and global climatic change. This study has developed a novel size-separation methodology to produce the first core top calibration of diatom δ30Si. The calibration demonstrates that diatom δ30Si exhibits a strong negative correlation with surface water silicic acid concentration, supportive of its application as a proxy for silicic acid utilisation. The refined method is used to produce a diatom δ30Si record, for the first time combined with sponge δ30Si, to gain insight into the Southern Ocean silicon cycle over one of the largest Cenozoic climatic shifts; the onset of Antarctic glaciation (~33.7 Ma). The two δ30Si records yield the first geochemical footprint to demonstrate that diatom proliferation, coincident with the onset of Antarctic circumpolar current flow, was a precursor event to the Eocene-Oligocene Transition. Diatoms are shown to have played a role in climate cooling through enhanced export and burial of organic carbon on the seafloor. The first long term reconstruction of silicic acid concentration in subsurface waters of the Southern Ocean, which spans the Late Eocene to the earliest Pliocene, provides new evidence that oceanic vertical mixing rates, coupled with the efficient removal of silicon from the surface by the diatoms, have been the most important factor in controlling the silicon chemistry of the ocean over the Cenozoic.

published_or_final_version / Radio Chemistry / Master / Master of Philosophy

published_or_final_version / abstract / Earth Sciences / Doctoral / Doctor of Philosophy

Many tropical trees do not form reliable annual growth rings, making it a challenge to develop tree-ring width chronologies for application to paleoclimatology in these regions. Here, I seek to establish high-resolution proxy climate records from trees without rings from the Monteverde Cloud Forest in Costa Rica using stable isotope dendroclimatology. Neotropical cloud forest ecosystems are associated with a relatively narrow range of geographic and hydroclimatic conditions, and are potentially sensitive to climate variability and change at time scales from annual to centennial and longer. My approach takes advantage of seasonal changes in the d18O of water sources used by trees over a year, a signature that is imparted to the radial growth and provides the necessary chronological control. A rapid wood extraction technique is evaluated and found to produce cellulose with d18O values indistinguishable from conventional approaches, although its application to radiocarbon requires a statistical correction. Analyses of plantation-grown Ocotea tenera reveal coherent annual d18O cycles up to 9 permil. The width of these cycles corresponds to observed basal growth increments. Interannual variability in d18O at this site is correlated with wet season precipitation anomalies. At higher elevations within the orographic cloud bank, year-to-year changes in the amplitude of oxygen isotope cycles show a relationship with dry season climate. Longer d18O chronologies from mature Pouteria (Sapotacae) reveal that dry season hydroclimatology is controlled at interannual time scales by variability in the eastern equatorial Pacific (ENSO) and the Western Hemisphere Warm Pool (WHWP), which are correlated with trade wind strength and local air temperature. A change in the late 1960s toward enhanced annual d18O amplitude may reflect low frequency changes in the Atlantic and Pacific ocean-atmosphere system. This study establishes the basis for cloud forest isotope dendroclimatology and demonstrates that the local climate of neotropical cloud forests is sensitive to interannual, and perhaps, multidecadal changes in important large-scale modes of climate variability.

Applications of in situ cosmogenic nuclides to problems in Quaternary geology require increasingly accurate and precise knowledge of nuclide production rates. Production rates depend on the terrestrial cosmic-ray intensity, which is a function of the elevation and geomagnetic coordinates of a sample site and the geomagnetic field intensity. The main goal of this dissertation is to improve the accuracy of cosmogenic dating by providing better constraints on the spatial variability of production rates.In this dissertation I develop a new scaling model that incorporates the best available cosmic-ray data into a framework that better describes the effects of elevation and geomagnetic shielding on production rates. This model is based on extensive measurements of energetic nucleon fluxes from neutron monitor surveys and on more limited data from low-energy neutron surveys. A major finding of this work is that neutron monitors yield scaling factors different from unshielded proportional counters. To verify that the difference is real I conducted an airborne survey of low-energy neutron fluxes at Hawaii (19.7° N 155.5° W) to compare with a nearby benchmark neutron monitor survey. Our data confirm that the attenuation length is energy dependent and suggest that the scaling factor for energetic nucleons is 10% higher between sea level and 4000 m than for low-energy neutrons at this location. An altitude profile of cosmogenic 36Cl production from lava flows on Mauna Kea, Hawaii, support the use of neutron flux measurements to scale production rates but these data do not have enough precision to confirm or reject the hypothesis of energy-dependent scaling factors.

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