Physical Sciences and Mathematics Commons^™

A New View Of Chlorophyll Dynamics In The Southern Mid-Atlantic Bight From A Two-Year High-Resolution Spray Glider Survey, Francesco Lane

OES Theses and Dissertations

The southern Mid-Atlantic Bight (MAB) near Cape Hatteras, NC, USA, is likely a hotspot for the episodic export of carbon-rich shelf waters to the open ocean. Over a 2 year period, from March 2017 to May 2019, Spray gliders repeatedly occupied transects, along the slope and across the shelf, generating high-resolution chlorophyll fluorescence (fChl) data in the southern MAB. This study implements an fChl calibration method utilizing remotely sensing ocean color as a standard. We validate the method’s utility by demonstrating a reduction in post-calibration cross-mission fChl variability and demonstrating close correspondence between the calibrated fChl data and an in …

Nitrogen Cycling In The Lower Chesapeake Bay And Mid- And South Atlantic Bight, Yifan Zhu

OES Theses and Dissertations

Nitrogen (N) is central to marine primary production; its availability often limits the capacity and rates of primary productivity in most of the world’s oceans. Contrastingly, estuaries frequently receive anthropogenic N loading, oftentimes resulting in eutrophication, harmful algal blooms (HABs), and substantially degraded water quality. Nutrient variability in both estuaries and oceanic regimes results from meteorological forcing and physical processes, including wind-induced, tidal, and mesoscale mixing and upwelling. In this dissertation, a comprehensive investigation of N variability and cycling and its links to physical-biogeochemical processes was conducted using time-series monitoring approaches, flux estimations, satellite imaging, biogeochemical measurements, and molecular analyses. …

Molecular Evidence For The Export Of Terrigenous Organic Matter To The North Gulf Of Mexico By Solid-State 13C Nmr And Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Of Humic Acids, Sarah Ann Ware

Chemistry & Biochemistry Theses & Dissertations

Marine organic matter is mainly believed to originate from autochthonous organic matter, while terrigenous organic matter is assumed to be largely degraded prior to reaching the open ocean or more recently replaced by marine organic matter via a stripping process. Sediment samples along a transect extending from the Mississippi River Birdsfoot Delta to the Mississippi Canyon on the Louisiana continental shelf were examined by advanced analytical techniques, electrospray ionization coupled to a 12T Fourier transform ion cyclotron resonance mass spectrometer (ESI-FTICR-MS) and quantitative solid-state multiple cross polarization magic angle spinning (multi-CPMAS) ¹³C NMR in an effort to understand the …

Advances In The Understanding Of Sourcing And Fate Of Pyrogenic Organic Matter In The Environment, Aleksandar Ivaylov Goranov

Chemistry & Biochemistry Theses & Dissertations

With higher occurrences of forest fires worldwide, there has been an increase in scientific interest surrounding the chemistry of pyrogenic organic matter (pyOM). The main structural components of pyOM, the condensed aromatic compounds (ConAC), exhibit intriguing physico-chemical properties and have been one of the main focuses of biogeochemical research. The overwhelmingly large number of scientific articles regarding pyOM and ConAC are guided by the assumption that ConAC in the environment are exclusively of pyrogenic origin, even though some recent studies have suggested that some of these ConAC could also be derived from non-pyrogenic radical-driven processes. To evaluate this controversial proposition, …

In The Margins: Reconsidering The Range And Contribution Of Diazotrophs In Nearshore Environments, Corday R. Selden

OES Theses and Dissertations

Dinitrogen (N₂) fixation enables primary production and, consequently, carbon dioxide drawdown in nitrogen (N) limited marine systems, exerting a powerful influence over the coupled carbon and N cycles. Our understanding of the environmental factors regulating its distribution and magnitude are largely based on the range and sensitivity of one genus, Trichodesmium. However, recent work suggests that the niche preferences of distinct diazotrophic (N₂ fixing) clades differ due to their metabolic and ecological diversity, hampering efforts to close the N budget and model N₂ fixation accurately. Here, I explore the range of N₂ fixation …

Sodium-Calcium Ratios In The Planktic Foraminifera Trilobatus Sacculifer As A Proxy For Sea Surface Salinity, Colton Steele Watkins

OES Theses and Dissertations

Recent culture and field studies have found a significant positive correlation between seawater salinity and the incorporation of sodium into foraminiferal calcite, suggesting a potential new proxy for reconstructing past changes in sea surface salinity (SSS) (Mezger et al., 2016 and Bertlich et al., 2018). In order to test the applicability of this new proxy in an open-ocean setting, Na/Ca ratios in the planktic foraminifera Trilobatus sacculifer (T. sacculifer Na/Ca) were measured from a suite of sediment core tops spanning a natural salinity gradient from the North Atlantic subtropical gyre to the South Atlantic subtropical gyre. Initial results from …

Diatom Community Composition Shifts Driven By Coherent Cyclonic Mesoscale Eddies In The California Current System, Zuzanna Maria Abdala

OES Theses and Dissertations

The California Current System (CCS) is characterized by an equatorward flowing eastern boundary current, as well as seasonal wind-driven coastal upwelling which supplies nutrient-rich waters to the surface and drives high coastal productivity. Cyclonic mesoscale eddies form off the coast in the CCS where they trap the highly productive upwelled coastal waters, along with their resident planktonic communities, and transport them offshore into the more oligotrophic California Current waters. The interaction between waters within and outside of the eddies is limited, and so the eddies act as natural mesocosms, where the resident phytoplankton population undergo ecological succession as the eddy …

Lipid Biomarkers Of Bering And Chukchi Sea Euphausiids And Their Application To Diet History, Rachel L. Pleuthner

OES Theses and Dissertations

In the eastern Bering Sea, Thysanoessa raschii are the most abundant krill species and a keystone trophic member that serve as both an important grazer and link to upper level consumers. In this system krill experience large annual variation in food resources, especially during ice advance and retreat; multiple lipid classes are used to temper the effects of those fluctuations, as well as to fuel reproduction and growth. Two shipboard feeding experiments that occurred during late spring and early summer of 2010, respectively, monitored the lipid retention in adult T. raschii and examined the fluctuation of specific lipid biomarkers under …

Coupling Metaproteomics With Taxonomy To Determine Responses Of Bacterioplankton To Organic Perturbations In The Western Arctic Ocean, Molly P. Mikan

OES Theses and Dissertations

Understanding how the functionality of marine microbial communities change over time and space, and which taxonomic groups dominate distinct metabolic pathways, are essential to understanding the ecology of these microbiomes and the factors contributing to their regulation of elemental cycles in the oceans. The primary goal of this dissertation was to investigate the community metabolic and taxonomic responses and the degradation potential of two compositionally distinct marine microbiomes within the shallow shelf ecosystem of the Chukchi Sea after rapid fluctuations in algal organic matter availability. Novel bioinformatics tools were collaboratively developed and used together with community proteomics (metaproteomics) to characterize …

Biogeochemical Cycling Of Selenium In The Arctic Ocean, Kyle M. Mcquiggan

OES Theses and Dissertations

Changes in the global climate may have a pronounced effect on the biogeochemical cycling of trace elements like selenium (Se) in the Arctic Ocean. This study described the first quantitative examination of the biogeochemical cycle of selenium in the Amerasian Basin, providing the baseline from which future changes can be identified. Aerosol, dissolved and particulate water samples were collected for Se determinations during the U.S. GEOTRACES GN01 Arctic expedition that sampled the two parts of the Amerasian Basin in 2015: The Makarov Basin on the way to the North Pole and the Canada Basin on the return trip to Dutch …

The Marine Cyanate Cycle, Brittany Widner

OES Theses and Dissertations

Cyanate (OCN-) is a reduced nitrogen compound with the potential to serve as a nitrogen and carbon source for marine microbes. Evidence from genomes and culture studies indicated that several marine cyanobacterial groups, including representatives of the globally important genera Synechococcus and Prochlorococcus, might be capable of cyanate assimilation. However, prior to this study, the distribution, bioavailability, and production pathways of cyanate were unknown in natural systems due to the absence of a sensitive cyanate assay; and the ability of organisms to assimilate cyanate on relevant timescales was unknown because we lacked a suitable tracer for measuring uptake. I developed …

Source-Specific Molecular Signatures For Light-Absorbing Organic Aerosols, Amanda Susan Willoughby

Chemistry & Biochemistry Theses & Dissertations

Organic aerosols (OA) are universally regarded as an important component of the atmosphere based on quantitative significance as well as the far-reaching impact they have on global climate forcing and human health. Despite the acknowledged importance, OA amounts and impacts remain the largest uncertainties regarding radiative forcing estimates. Incomplete chemical characterization of aerosol organic matter (OM) and a lack of concrete source apportionment is a major source of this uncertainty. The primary focus of this study is to provide much needed molecular details regarding ambient OA from key emission sources, and establish links between molecular and optical properties.

Complete chemical …

A Survey Of Aquatic Organisms For The Cyanotoxin Beta-Methylamino-L-Alanine (Bmaa), Ian M. Sammler

OES Theses and Dissertations

Cyanobacteria blooms are increasing globally as a result of eutrophication. Many cyanobacteria are potentially harmful, not only because of the oxygen depleted zones created when they decay, but also because of the toxins they produce. β- Methylamino-L-alanine (BMAA), reportedly produced by many species of cyanobacteria, is a non-proteinogenic amino acid that has been linked to the development of neurodegenerative diseases (amyotrophic lateral sclerosis (ALS) and Alzheimer's) in humans. This study presents results from an assessment of BMAA in cyanobacteria and their grazers from the lower Chesapeake Bay and Lake Erie regions. BMAA was analyzed in samples prepared with the EZ:Faast™ …

Organic Copper Binding Ligands And Thiol Compounds Produced By Bacteria And In The Elizabeth River, Virginia, Christina Louise Dryden

OES Theses and Dissertations

This dissertation presents work focusing on copper and organic copper binding ligands in laboratory cultures and the Elizabeth River, Virginia. Laboratory cultures of the marine bacterium Vibrio parahaemolyticus were used to demonstrate the influence of elevated copper concentrations on copper-complexing ligand and thiol production. Copper-complexing ligands similar in binding strength to the strongest natural ligands were detected in V. parahaemolyticus cultures (log K′_CuL = 11.8–13.2). A strong correlation (r² = 0.973) was found between total thiol and copper-complexing ligand concentrations at all copper concentrations examined.

A yearlong seasonal study was undertaken in a heavily polluted estuary to ascertain …

Implications Of Climate Change For Cyanobacteria Over The Western Florida Shelf In The Gulf Of Mexico, Ivy Mara Osmon

OES Theses and Dissertations

Concentrations of atmospheric CO₂ are expected to double by year 2100 as a result of anthropogenic activities. Under elevated CO₂ conditions, cyanobacteria may reallocate energy from active accumulation and transport of dissolved inorganic carbon (C) required for photosynthesis to other growth processes. Stimulation of cyanobacterial production on the Western Florida Shelf in the Gulf of Mexico (GOM) could lead to improved nutritional status for the toxic, mixotrophic dinoflagellate Karenia brevis that utilizes newly fixed N₂ from co-occurring diazotrophic cyanobacteria and consumes unicellular cyanobacteria via grazing for growth. Culture studies performed by other researchers on the climate induced …

A Comprehensive Evaluation Of C25 Highly Branched Isoprenoid Alkenes Of Marine Diatoms As Proxies For Sea Ice Extent In The Arctic Ocean, Tetiana Muniak

OES Theses and Dissertations

Sea Ice extent is one of the major factors regulating carbon cycling and ecosystem function in the modern Arctic Ocean. It is an essential component of climate models and is crucial for the evaluation of various oceanographic processes that influence a particular region. Yet it is also one of the most difficult attributes of the ocean with respect to our ability for its accurate reconstruction from paleo records. The lack of the detailed records prior to satellite information has encouraged the development of new proxy records for the reconstruction of past

sea ice conditions. In recent years, a new monounsaturated …

Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen

Chemistry & Biochemistry Theses & Dissertations

Molecular characterization and photochemical transformation of dissolved organic matter (DOM) in both rivers and the ocean is the main research focus of this dissertation. Chemical characterization of DOM is hampered by the limited application of advanced techniques to desalt, concentrate, isolate and then molecularly characterize DOM. An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated and recommended for the efficient desalting of small volume samples of seawater prior to analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS).

A high-recovery technique of DOM isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate …

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into The Linkage Between Sources And Chemical Composition, Xiaoyan Cao

Chemistry & Biochemistry Theses & Dissertations

This dissertation investigated the chemical structure of DOM by advanced solid-state nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques, as well as isotopic measurements and UV-visible spectroscopy, to shed light on the linkages between DOM sources and DOM composition. Unique and extensive sets of DOM samples studied here were isolated from various aquatic systems, covering end-member environments in which DOM is considered either microbially derived or terrestrially derived, and areas in which DOM has characteristics intermediate between the two end members. Important insights into specific site-related questions were also gained such as …

Phosphorus Cycling In Tropical Carbonate Sediment-Seagrass Systems, Zachary Howerton

OES Theses and Dissertations

This thesis presents two studies focusing on phosphorus cycling in calcium carbonate sediments inhabited by seagrasses. Phosphorus is a major limiting nutrient for primary productivity in these sediments as well as in the overlying waters. In large part this is due to removal of phosphate from solution by adsorption and precipitation reactions.

In chapter II, the relationship between the size of the sedimentary phosphorus pool and the abundance of seagrass on the Great Bahama Bank, as well as the relationship between phosphorus content and grain size in the sediments, were examined to better understand the biogeochemistry of carbonate sediments and …

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into Composition, Photochemical Transformation And Carbon Cycling, John Robert Helms

Chemistry & Biochemistry Theses & Dissertations

This dissertation explores processes affecting the composition of dissolved organic matter (DOM) and how DOM composition changes in sunlit surface waters and in the dark interior ocean. Simulated solar irradiations were used to investigate the impact of photochemistry on terrestrial waters and deep ocean DOM. The photochemically mediated processes observed in Dismal Swamp samples included (i) light induced flocculation of up to 12% of the organic matter and 84% of the dissolved iron originally present; (ii) 74-88% mineralization of dissolved organic carbon (DOC) and 95-99% bleaching of chromophoric DOM (CDOM) during 110 days of irradiation; and (iii) nearly complete loss …

Effect Of Reworking And Bioturbation On Sedimentary Reactive Iron Within A Microtidal Estuary, Amy Kathleen Pitts

OES Theses and Dissertations

Mixed redox conditions in sediments due to physical reworking may allow for enhanced remineralization of refractory organic matter due to Fe(III) redox cycling. In part this may occur because easily reducible iron oxides can be used by heterotrophic bacteria to remineralize the organic carbon. This phenomena has been observed in bioturbated sediments and in areas where physical factors (such as strong bottom currents) constantly rework the sediments. To specifically determine the effects of physical reworking and bioturbation on concentrations of easily reducible iron oxides, reactive iron concentrations were measured in surface sediments taken from two contrasting sites in the York …

Model-Based Analyses Of Nitrogen On The Mid-Atlantic Bight Continental Shelf, Tian Tian

OES Theses and Dissertations

The biogeochemistry of continental shelf systems is an important, but poorly quantified, component of the global cycling of nitrogen and carbon. In this study, simulations obtained from a one-dimensional (ID) biogeochemical model developed for the Middle Atlantic Bight (MAB) portion of the U.S. eastern continental shelf were analyzed to investigate nitrogen cycling processes. The 1D model included lower trophic level interactions and was forced by advective fields obtained from a corresponding three-dimensional biogeochemical model. Taylor and target diagram analyses, which compared in situ measurements of sea surface temperature (SST) and salinity, and chlorophyll and particulate organic carbon (POC) derived from …

Phosphorus Uptake In Rhodomonas Salina (Wislouch) And Its Effect On Allocation And Elimination In Acartia Tonsa (Dana), Danna Palladino

OES Theses and Dissertations

Phosphorus is a key element in important biochemical compounds, such as RNA and phospholipids, and can become limiting in a variety of marine systems. The uptake of phosphorus into biochemical fractions (protein, low molecular weight (LMW) compounds, lipid, polysaccharide and nucleic acid) in Acartia tonsa fed ³³P -labeled Rhodomonas salina was examined. R. salina was cultured on two variations of one media that in one case contained phosphorus in balance and the other out of balance with relation to other standard f/2 components. The P-balanced (PB) media had a N:P ratio of 24.5, which is higher than that found …

Trace Metal Biogeochemistry In The Western North Pacific, Peter Lynn Morton

OES Theses and Dissertations

Dissolved and suspended particulate samples collected during the Intergovernmental Oceanographic Commission 2002 Contaminant Baseline Survey were analyzed to determine the surface and vertical distributions of Cd, Co, Cu, Mn, Ni Zn and Pb across the western and central North Pacific.

Dissolved trace metal concentrations were measured using a novel isotope dilution-ICP-MS method after extraction over an 8-hydroxyquinoline resin column and validated through the use of the SAFe consensus reference materials. Filtered suspended particulate matter was digested using an HCl/HNO3/HF mixture and analyzed by HR-ICP-MS to obtain total particulate concentrations for the trace metals and other tracer elements such as Al, …

Concentrations, Distributions And Chemical Speciation Of Zinc And Cadmium In The Equatorial And South Atlantic Ocean, Gonzalo G. Carrasco

OES Theses and Dissertations

Certain trace metals are important cofactors in enzymatic systems and are thus, essential for life in the world's oceans. Two of these metals, Zn and Cd, are required by phytoplankton for enzymes that facilitate carbon uptake (Morel and Price, 2003). In seawater the total dissolved concentration of a metal (MTD) is distributed among different chemical species and this chemical speciation dictates a metal's bioavailability. Strong organic metal-binding ligands greatly affect the metal's chemical speciation in the ocean, potentially limiting phytoplankton growth by reducing the concentrations of Zn²⁺ and Cd²⁺, the bioavailable forms of these two metals to …

Reactivity And Chemical Characterization Of Dissolved Organic Matter In An Estuary, Hussain A. Abdulla

OES Theses and Dissertations

This dissertation used Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C-NMR) data to quantify the changes of major chemical compound classes in high molecular weight (HMW, >1kDa) DOM isolated along a transect from Great Dismal Swamp through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that both carboxylic acids and aromatic compounds are lost along the transect, while amide, and carbohydrate moieties could have a mid-transect source.

Addressing the seasonal and spatial changes in the chemical composition of high molecular weight DOM using C/N ratio and δ^{13 …}

A Bio-Optical Model For Syringodium Filiforme Canopies, Margaret A. Stoughton

OES Theses and Dissertations

Seagrasses are significant ecological and biogeochemical agents in shallow water ecosystems throughout the world. In many regions, seagrass meadows occupy a sufficient fraction of the coastal zone, and generate optical signatures that can be observed from space. Bio-optical models of light absorption and scattering by submerged plant canopies for certain species such as Thalassia testudinum and Zostera marina have successfully modeled the plane irradiance distribution and photosynthesis within the submerged canopies. Syringodium filiforme differs &om T. testudinttm and Z marina, in leaf morphology and canopy architecture. The objective of this study was to develop a radiative transfer model that …

Nutrient And Carbon Dynamics In The Chesapeake Bay Outflow Plume And Their Effect On The Coastal Ocean Environment, Katherine C. Filippino

OES Theses and Dissertations

Seasonally resolved nutrient and carbon fluxes from estuaries to the coastal ocean are poorly constrained. Nutrient and carbon cycling in highly productive regions like the Chesapeake Bay outflow plume and surrounding coastal environments greatly affect our global understanding of carbon cycling. The overall questions for the research described in this dissertation stem from the need to close global carbon budgets, and obtain a fundamental understanding of nutrient dynamics in a coastal region heavily influenced by seasonality and human impacts.

Within the framework of physical characteristics of the outflow plume and through the characterization of nutrient concentrations, primary productivity rates, and …

The Observation, Modeling, And Retrieval Of Bio-Optical Properties For Coastal Waters Of The Southern Chesapeake Bay, Xiaoju Pan

OES Theses and Dissertations

The primary purpose of this study was to develop an inverse method to retrieve the inherent optical properties (IOPs) and biogeochemical parameters (e.g. chlorophyll a concentration and salinity) appropriate to monitor the water quality and biogeochemical processes from remote sensing of the coastal waters in the southern Chesapeake Bay and coastal Mid-Atlantic Bight region (MAB) dominated by Case 2 waters. For this purpose, knowledge of the relationship between remote sensing reflectance (R_rs) and IOPs and the effect from bottom reflectance on R_rs, is required.

A substantial investigation of IOPs has been conducted for the coastal …

Seagrass-Mediated Carbonate Dissolution And Early Diagenesis In Bahamas Bank Sediments, Xinping Hu

OES Theses and Dissertations

This dissertation presents the results of studies examining the role that seagrasses play in carbonate dissolution and early diagenesis of Bahamas Bank sediments. Three aspects of this problem are addressed: (1) stable carbon isotopes as an indicator of early diagenesis of carbonates, using results of a field study; (2) carbonate dissolution stoichiometry and carbonate reprecipitation, using the results from closed-system sediment incubation studies; (3) carbonate dissolution and reprecipitation across the broader Bahamas Bank. In Chapter II, I examined δ¹³C in the dissolved inorganic carbon (DIC) of sediments with various degrees of seagrass densities. In low seagrass density and …