Physical Sciences and Mathematics Commons^™

Reconstructing Surface Water Carbonate Ion Concentration Changes In The Eastern Equatorial Pacific Across Glacial Transitions, Lenzie Gail Ward

OES Theses and Dissertations

Today, the eastern equatorial Pacific (EEP) plays a critical role in the global CO₂ budget as a major source of CO₂ to the atmosphere, but recent studies suggest the region may shift to a sink for atmospheric CO₂ under different climate states. Here, I focus on two transitional periods, the last deglaciation (25 kyr to present) and last glaciation (the Marine Isotope Stage (MIS) 5a-4 transition, 96 to 60 kyr), to investigate how the carbon system in the EEP responds to major climate changes. I measured B/Ca ratios in the planktic foraminifera Globigerina bulloides from core MV1014-17JC …

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 …

The Evolution Of The El Niño-Southern Oscillation And Tropical Pacific Climate Across The Last Deglaciation, Ryan Hunter Glaubke

OES Theses and Dissertations

The El Niño – Southern Oscillation (ENSO) is the largest interannual component of Earth’s climate system, capable of exerting significant influence over global climate patterns that affect communities around the globe. Nevertheless, a comprehensive understanding of the ENSO system and its relationship to tropical Pacific climate dynamics remains unclear. Although new paleoceanographic proxies have shown promise in in their ability to constrain past ENSO change, little is known about how ENSO varied in response to millennial-scale climate events over the last 25,000 years. Here, I present new records of tropical Pacific mean state and ENSO variability over the last 25,000 …

Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. Mcmahon

OES Theses and Dissertations

Amino acids comprise up to 50% of organic matter in cellular material and are a major fraction of oceanic organic carbon. Amino acids are also considered highly labile during organic matter recycling, making them useful proxies for organic carbon cycling. Nevertheless, analysis of individual amino acids has been burdened by lengthy derivatization and complex analysis since the 1950s. In this thesis, I describe the modification of advanced analytical techniques, developed in the biomedical field, for analysis of marine matrices which allow the determination of at least 40 amino acids without the need for lengthy sample preparation and derivatization, twice the …

Selenium Distribution And Cycling In The Eastern Equatorial Pacific Ocean, Zoe Wambaugh

OES Theses and Dissertations

Oxygen minimum zones in oceanic waters have become increasingly important to the marine environment and society. Low oxygen waters affect not only the distribution and abundance of marine organisms, but also impact the solubility and transport of trace elements that are of biological importance, with the chemical speciation and solubility depending on the actual redox poise of the waters. One redox sensitive trace element of interest is selenium, which can be both toxic and essential for organisms, depending on its chemical speciation. In 2013, the US GEOTRACES program completed the GP16 transect from Peru to Tahiti, going through the oxygen …

A New Phase Speciation Leaching Procedure For The Determination Of Metals In Oxic And Anoxic Sediments, Brandon R. Gipson

OES Theses and Dissertations

Toxic trace elements such as cadmium, lead, chromium, and arsenic released by human activities can accumulate in marine and estuarine sediments, where these metals are often sequestered until local environmental changes (e.g., redox, salinity, and/or pH) allow these elements to be reintroduced into the food web. In order to assess the extent of toxic trace element contamination in sediment, numerous leaching schemes have been developed that separate sediment-bound trace metals into operationally defined geochemical phases. These "phase speciation" leaching schemes are typically designed with the purpose of being used on either oxic or anoxic sediments. However, natural sediments often contain …

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, …

Biogenic Tracers Through The Holocene On The Alaskan Shelf, Carie A. Curry

OES Theses and Dissertations

Dramatic environmental changes in the Arctic Ocean have been observed for the last two decades including changing the amount of sea ice thickness and extent, and increased river discharge. In order to put these and other current day observations into historical context and perhaps reveal mechanisms controlling them, a suite of paleo-proxies were used to analyze two high resolution cores collected on the 2005 HOTRAX expedition. The goals of this research were: (1) develop an analytical method for determining biogenic calcite, (2) identify the major sources of biogenic matter into the system over the Holocene, and (3) assemble the history …

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 …

Anthropogenic Lead Deposition And Four National Parks In Poland As Determined By Lead Isotope Ratios, Shannon Simcoe

OES Theses and Dissertations

Polluted soils are recognized by having high concentrations of heavy metals, including Pb. Partitioning of metals in geochemical fractions, by sequential chemical extractions, may indicate whether a metal has been recently deposited in the soil. While concentration levels alone cannot distinguish between natural and anthropogenic Pb, studies have demonstrated that anthropogenic pollution is accurately recorded by specific Pb isotope signatures, which differ from natural Pb isotopes. The objective of this project was to use ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁴Pb isotope ratios to differentiate between the anthropogenic Pb input and the naturally occurring Pb in four national …

Dissolved Humic Substances: Characterization Of Their Sorption Onto Iron Hydroxide Aluminum Hydroxide Kaolinite And Smectite, Sarah E. Diebel

OES Theses and Dissertations

Humic (HA) and fulvic (FA) acids participate in many geochemical processes and the mechanisms of their sorption to colloidal surfaces are numerous, indicating these substances are complex and heterogeneous. The current study focuses on the interactions of the Fe hydroxide (FE), Al hydroxide, Kaolinite (KA) and Smectite (SM) and these naturally occurring organic acids using Fourier Transform Infrared Spectroscopy (FTIR) and DOC analysis at pH 4. FTIR was used for the initial functional group characterization, as well as the comparison of before and after adsorption spectra of the HA and FA. DOC examined the amounts of HA and FA adsorbed …

The Distribution Of Airborne Coal Dust In Soil Profiles Of Norfolk, Va And Its Implication For Arsenic Loading To These Soils, William Joseph Bounds

OES Theses and Dissertations

Norfolk, Virginia is home to the Northern Hemisphere's largest coal terminal the Lamberts Point Docks. The coal loading process of this terminal creates large amounts of coal dust, which subsequently is distributed throughout the local region by atmospheric transport and deposition. While the coal dust itself poses only minor health hazards, certain trace elements within the coal, particularly arsenic, may pose environmental as well as significant health hazards. Within coal, arsenic occurs primarily in the mineral pyrite. As pyrite in the coal dust is subsequently oxidized via exposure to the atmosphere and/or meteoric water, arsenic may be released to the …

Effects Of Organic Matter And Iron-Rich Clay On Mobility Of Trace Metals From Flue Dust Contaminated Soil, Scott Ephraim Lewis

OES Theses and Dissertations

The enhanced leaching of trace metals through soil becomes a concern for human health if dissolved trace metals reach groundwater and migrate into a public water system. A serial batch extraction procedure was implemented to determine the effects of Vitagrow © organic matter and Fe-Rich TM clay on the mobility of trace metals (Zn, Pb, and Cd) from a flue dust treated (0, 600, 1200, and 2400 μgig Zn) Appling soil.

The addition of an organic matter (OM) amendment to the Appling soil enhanced Pb mobility and reduced soluble Zn and Cd. In general, average solution concentrations of trace metals …

Analysis Of Lunar Basalt Flows In Oceanus Procellarum Using Clementine Data, Noel William Jackson

OES Theses and Dissertations

Remote sensing analyses of data set taken by Clementine in 1994 permit new observations about mineral distribution on the lunar surface, basalt flow stratigraphy, and thus the geologic evolution of the Moon. The northern section of Oceanus Procellarum contains numerous impact craters which penetrated the basalt and thus can be used as natural probes to estimate the number and thicknesses of flows.

I constructed a mosaic taken in three frequencies ( 415 nm, 750 nm, 950 nm), and a Ratio Image (750/415 = red, 750/950 = green, 415/750 = blue). On such an image, red indicates the iron-poor mature highland …

The Geomorphological History Of An Alluvial Fan Complex In Nelson County, Virginia, Melinda Ann Youngblood

OES Theses and Dissertations

An alluvial fan complex blankets a portion of the Rockfish Valley in Nelson County Virginia, located along the eastern slope of the Blue Ridge Mountains. The seven-km² field area contains three mappable relict alluvial surfaces (Qf1, Qf2, and Qf3) and one modern surface (Qa1), each of which is underlain by fluvial deposits dominated by greenstone and charnokite cobbles. The four surfaces were mapped according to topographic position and degree of stream dissection. Alluvial deposits underlying each surface were characterized using a 3-part clast weathering scale based on greenstone clast weathering rinds and using soil development criteria (clay content, Munsell …

The Effects Of Organic Matter Rich Topsoil On The Germination Growth And Metal Uptake Of Corn (Zea Mays) Grown In Flue Dust Contaminated Soil, Christopher Allen Impellitteri

OES Theses and Dissertations

The large biomass of corn (Zea mays) and promising results from a previous experiment (Chlopecka and Adriano, 1995) concerning metal uptake by corn indicate that corn may be a good candidate for phytoremediation of trace metal contaminated soil. Appling soil (acid, thermic, typic paleudult) was treated with increasing levels of a metal rich flue dust based on Zn concentration (0, 150, 300, 600, 1200, and 2400 mg/kg). Four replicates at each Zn treatment level were either limed to pH 6.3-6.5 and covered with a two inch thick layer of organic matter rich topsoil (OM), unlimed and covered with …

Biostratigraphic Analysis Of Southern Florida's Plio-Pleistocene Shell Beds, Dalton L. Rasmussen

OES Theses and Dissertations

Four molluscan assemblage zones in southern Florida corresponding to the Pinecrest Sand Member of the Tamiami Formation, and the Caloosahatchee, Bermont and Fort Thompson shell beds were identified following quantitative and qualitative analyses of the fossil molluscan fauna. Twenty-eight bulk sediment samples collected from 16 localities across southern Florida were processed for fossil material, and yielded nearly 60,000 specimens belonging to 311 species. A Q-mode cluster analysis compared sediment samples on the basis of 188 species whose abundances had been converted to binary presence-absence form. The cluster analysis was run four times using the Jaccard and Dice similarity coefficients as …

The Speciation Of Dissolved Uranium In Marine Waters, Darrin Kent Mann

OES Theses and Dissertations

Uranium has been used extensively for quantifying geochemical processes in the marine environment. Due to its low concentration, about 3.3 μg/1, some form of preconcentration is required for analysis. The two most widely used pre-concentration schemes are co-precipitation with iron hydroxide, and chelating ion exchange chromatography. These methods were developed by following the behavior of inorganic uranium isotopes and seemed to give identical results. However, when used for trace metal analysis, these methods have been shown to extract different fractions from the same sample. Chelex-100 resin removes only inorganic or weakly bound trace metals from a solution, while the precipitates …

Fluid Inclusion Studies Of The Morefield Pegmatite Amelia County, Virginia, John Richard Smerekanicz

OES Theses and Dissertations

The Morefield Pegmatite is a planar, nearly vertical body situated in Grenville age gneisses and schists in the southeast Piedmont of Virginia. It consists of a mineralogically simple albite-quartz outer zone and a texturally and mineralogically complex inner zone of microcline-topaz-quartz, with trace amounts of rare-element minerals. Fluid inclusions in samples of quartz, topaz, beryl, spessartite and albite that span the length, width and depth of both zones can be classified by chemical composition into two main groups: H₂O-rich solutions and CO₂- H₂O -rich fluids. The H₂O -rich inclusions consist of H …

Relation Of Groundwater Fluoride Concentrations To Sediment Mineralogy, Potomac Formation (Cretaceous), Southeastern Virginia, Paul Anthony Maciuika

OES Theses and Dissertations

Thirty-seven Early cretaceous sediment samples of the Potomac Formation were obtained from four cores to determine if fluoride bearing minerals are responsible for elevated fluoride concentrations in Potomac Formation groundwaters of southeastern Virginia. Investigative methods included total sediment fluoride and particle size analysis, semiquantitative mineralogical analysis (achieved by X-Ray Diffraction) and statistical methods (cluster, canonical and regression analysis). The sediments showed wide variation in textures, ranging from clean sands and gravels to silty clays. Sediment mineralogies were dependent on the prevailing size fraction, with quartz and feldspar dominating the sand and silt fractions, muscovite primarily being found in the silt …

Trace Metals And Pyrite In Sediments Of Chesapeake Bay, Robert S. Kluckhohn

OES Theses and Dissertations

The formation and cycling of iron sulfides within anoxic sediments can affect the cycling of trace metals. The sediments at station CB-27 (near Annapolis, Maryland) in Chesapeake Bay were rich in FeS (39% of TS), low in greigite (3.6% of TS), and has a relatively constant pyrite concentration (50 - 60% of TS) with depth. The percent composition of total metals in pyrite were 25.7% cu, 11.8% Zn, 15.8% Fe, and non-detectable to 2.1% Cd. At Station CB- 28 (near the Choptank River), the sediments were low in FeS (1.7% of TS), richer in greigite (up to 14% of TS), …

Metal Mobilization From A Near-Shore Lake Sediment Under Simulated Acidic Groundwater Inputs, Raveendra V. Ika

OES Theses and Dissertations

Simulation of acidic groundwater passing through lake sediments was conducted under controlled conditions in a laboratory. Three sediment cores collected intact from the near-shore region of an acidic lake were subjected to simulated groundwater inputs of initially identical chemistry for a seven day period. Following this period water being used in the simulation for two of the sediment cores was acidified by hydrochloric acid (HC1) addition to examine the ability of these sediments to neutralize acidic groundwater with varying H⁺ concentration.

Simulated acidic water passing through the sediment cores mobilized significant amounts of metals. The sediment acted as a …

A Comparison Of Metals In Several Ahermatypic Corals And Surficial Sediments: Mobile Pinnacles And Hoffa Reef, Northcentral Gulf Of Mexico, Kathryn M. Conko

OES Theses and Dissertations

Metal concentrations in marine sediment and carbonate secreting invertebrates are representative of surrounding environmental chemistry. Aluminum, Ba Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr, and Zn were measured in carbonate and terrigenous phases of the $<$63 um fraction of sediment samples from two locations in the northcentral Gulf of Mexico. Enrichment factors indicate that Al, Ba, Cu, Cr, Mg, Mn, and Ni are all slightly depleted in these sediments relative to crustal abundances. Discriminant function analyses shows that the concentrations of five elements differ between locations.

Ahermatypic coral (106 specimens) from five genera collected from the study sites were analyzed for Cd, Cu, Cr, Pb, Zn, Mn, Sr, Ba, Fe, Ca and Mg. Eight elements vary between some genera, Al and Ba also vary in concentration in corals between either location. All elements except Sr are significantly depleted in the coral with respect to Ca in the …

Discrimination Of Subparallel Beach Ridges Using Detrital Ilmenite Composition And Fourier Shape Analysis, Allen E. Evans Jr.

OES Theses and Dissertations

Elemental composition (Fe, Ti, Mn, Mg, V, Cu, Ni, Zn, and Cr) and Fourier shape analysis of magnetically separated detrital ilmenite from seven Pleistocene and modern beach sand deposits of the Southeastern Virginia Coastal Plain were used to distinguish each deposit. Geomorphic expression, crosscutting relationships and proximity to the present shoreline differentiates the relative age of the seven sampled beach deposits. Analysis of ilmenite elemental composition, independent of geomorphic expression, distinguished beach sands of

different age and was successful in determining that each beach contained ilmenite similar in composition. Of the seven beach ridges tested, subtle yet significant differences in …

Sulfide In Shelf/Slope Waters Of The Western Atlantic, Christian F. Krahforst

OES Theses and Dissertations

Sulfide in the surface ocean has been recently considered as a source of hydrogen sulfide gas in the marine boundary layer. This "oxic" sulfide may also be important as a ligand in trace metal complexation. In the absence of actual data, the existence of sulfide in the ocean mixed layer remains speculative. The purpose of this study was to develop a sensitive technique (having picomolar detection limits) for the determination of sulfide in seawater, and to investigate the distribution of sulfide in the surface ocean.

In order to assess the abundance and distribution of sulfide in surface waters, samples were …

Leachate Monitoring In Naturally Saline Groundwater Chesapeake Landfill Chesapeake Virginia, T. Britt Mcmillan

OES Theses and Dissertations

Groundwater chemistry around the Chesapeake municipal landfill was monitored over a one year period. Ten sample sites as well as two surface water sites were used to monitor water quality. Two wells, one at 3 m and the other at 10 m were located at each site. Surface water samples were taken from the Elizabeth River, north of the landfill, and a tidal channel, west of the landfill. Seven groundwater sites were downgradient of the landfill and three sites were upgradient (control sites).

The landfill overlies a tidal marsh, approximately 100 m south of the intracoastal waterway (Elizabeth River). Dredge …

The Use Of Ilmenite Element Composition For The Determination Of Provenance, Yu W. Tsang

OES Theses and Dissertations

Fifty three samples were taken from three major rivers and their tributaries in Virginia: the James, Roanoke. and Potomac-Shenandoah Rivers. Samples were obtained from the Valley and Ridge. Blue Ridge and Piedmont provinces. The possible source rock types for these samples were determined by comparison of tributary ilmenite composition with drainage basin rock types. Ilmenite element concentration varied with different rock types. Ti was usually high for the ilmenite derived from non-mafic igneous rocks. Mg and Cr were high for the ilmenite from mafic igneous rocks. Zn was low for metamorphic ilmenite. The ilmenite from sedimentary rocks tended to have …

The Aquatic Geochemistry Of The Particle-Reactive Radionuclides Po-210, Pb-210, And Be-7, James Forrest Todd

OES Theses and Dissertations

Integrated monthly wet-only and bulk precipitation samples for Be-7 and Pb-210 analysis were collected from November 1982 through October 1983 at two sites in lower Chesapeake Bay. Atmospheric deposition fluxes for Be-7 in wet-only and bulk precipitation averaged 0.013 and 0.014 pCi/cm²/d, respectively, and for Pb-210 averaged 0.36 and 0.40 pCi/cm²/yr, respectively, suggesting that dry deposition makes only a minor contribution to the total fluxes.

A seasonal trend was observed in the depositional flux of Be-7, with a pronounced maximum in the Spring. Approximately 40 percent of the annual Be-7 deposition occurred between February and April, …

A Method For Determining Creosote Contamination Of Sediment From The Elizabeth River, Norfolk, Va, Elizabeth G. Merrill

OES Theses and Dissertations

Hydrocarbon input sources to the Elizabeth River were investigated. Carbonized coal products (creosote, coal tar, and roof tar), petroleum products (Kuwait Crude Oil, No. 2 Fuel Oil, and a fuel oil spill sample) and soot (woodstove and diesel engine) have unique hydrocarbon distributions. Elizabeth River sediment hydrocarbon distributions indicate that they are contaminated with both carbonized coal and petroleum products. Using a simple two member mixing model, greater than 65 percent of Elizabeth River sediments' resolved aromatic compounds were determined to originate from carbonized coal products. These aromatic hydrocarbons include the EPA priority pollutant polynuclear aromatic hydrocarbons which are known …

The Effect Of Polynuclear Aromatic Hydrocarbons On The Fecundity Of Acartia Tonsa (Calanoid Copepoda), Juanita Y. Grabarczyk

OES Theses and Dissertations

The concentrations of polynuclear aromatic hydrocarbons (PNAHs) were determined for several stations in the Elizabeth River. Thirteen PNAHs of the sixteen EPA priority pollutant PNAHs were present in the particulate fraction. The concentrations ranged from 10.0 ng/1 to 1000 ng/1. Ten of the sixteen EPA priority pollutant PNAH were present in the dissolved phase. Concentrations ranged from 2.0 ng/1 to 100 ng/1.

The environmental PNAHs concentrations were used to determine test concentrations. Bioassays were conducted to determine the effects of indigenous concentrations of seven predominant PNAHs (0.01 mg/1 to 2.4 mg/1 concentrations) on the fecundity of Acartia tonsa (calanoid Copepoda). …