Geochemistry Commons^™

A Seasonal Study Of Dissolved Cobalt In The Ross Sea, Antarctica: Micronutrient Behavior, Absence Of Scavenging, And Relationships With Zd, Cd, And P., M. A. Saito, T. J. Goepfert, A. E. Noble, E. M. Bertrand, Peter N. Sedwick, Giacomo R. Ditullio

OES Faculty Publications

We report the distribution of cobalt (Co) in the Ross Sea polynya during austral summer 2005-2006 and the following austral spring 2006. The vertical distribution of total dissolved Co (dCo) was similar to soluble reactive phosphate (PO(4)(3-)), with dCo and PO(4)(3-) showing a significant correlation throughout the water column (r(2) = 0.87, 164 samples). A strong seasonal signal for dCo was observed, with most spring samples having concentrations ranging from similar to ~ 45-85 pM, whereas summer dCo values were depleted below these levels by biological activity. Surface transect data from the summer cruise revealed concentrations at the low range …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Early Neoproterozoic Origin Of The Metazoan Clade Recorded In Carbonate Rock Texture: Reply, Fritz Neuweiler, Elizabeth C. Turner, David J. Burdige

OES Faculty Publications

We (Neuweiler et al., 2009) used scanning electron microscopic, fluorescence spectroscopic, fluorescence microscopic, and thin-section analytical work from modern, Cretaceous, Silurian, and early Neoproterozoic reefal material to make a geological case for an early Neoproterozoic origin of animals. In a modern analogue for ancient petrographic textures, degradative calcification of the extracellular collagenous matrix (ECM) of a modern siliceous sponge can be directly observed (Neuweiler et al., 2007).

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 …

Arctic Perennial Ice Cover Over The Last 14 Million Years, Dennis A. Darby

OES Faculty Publications

Knowledge of the long-term history of the perennial ice is an important issue that has eluded study because the Cenozoic core material needed has been unavailable until the recent Arctic Coring Expedition (ACEX). Detrital Fe oxide mineral grains analyzed by microprobe from the last 14 Ma (164 m) of the ACEX composite core on the Lomonosov Ridge were matched to circum-Arctic sources with the same mineral and 12-element composition. These precise source determinations and estimates of drift rates were used to determine that these sand grains could not be rafted to the ACEX core site in less than a year. …

Turbulent Lifestyle: Microbial Mats On Earth’S Sandy Beaches—Today And 3 Billion Years Ago, Nora Noffke

OES Faculty Publications

Archean Earth history is very difficult to reconstruct. Until recently, only bacterial cells preserved in chert, microborings, and stromatolites provided the few clues to ancient life. Now, siliciclastic “microbially induced sedimentary structures” (MISS) are adding to our knowledge of both past life and paleoenvironments. MISS rise from the interaction of photoautotrophic microbial mats with physical sediment dynamics in siliciclastic, shallow-marine settings. Archean MISS can be understood through observations of living microbial mats and modern biotic-physical sedimentary processes. Such geobiological studies are key to the interpretation of the early evolution of prokaryotes. For example, the 2.9 Ga Pongola Supergroup, South Africa, …

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 …

Impact Of Anthropogenic Combustion Emissions On The Fractional Solubility Of Aeroosol Iron: Evidence From The Sargasso Sea, Peter N. Sedwick, Edward R. Sholkovitz, Thomas M. Church

OES Faculty Publications

We report empirical estimates of the fractional solubility of aerosol iron over the Sargasso Sea during periods characterized by high concentrations of Saharan dust (summer 2003) and by low concentrations of aerosols in North American/maritime North Atlantic air masses (spring 2004 and early summer 2004). We observed a strong inverse relationship between the operational solubility of aerosol iron (defined using a flow-through deionized-water leaching protocol) and the total concentration of aerosol iron, whereby the operational solubility of aerosol iron was elevated when total aerosol iron loadings were low. This relationship is consistent with source-dependent differences in the solubility characteristics of …

Western Caribbean Sea Surface Temperatures During The Late Quaternary, Matthew W. Schmidt, Maryline J. Vautravers, Howard J. Spero

OES Faculty Publications

[1] Mg/Ca ratios in the planktonic foraminifera Globigerinoides ruber from Colombian Basin core ODP 999A suggest that Caribbean sea surface temperatures ( SSTs) were from 2.1 to 2.7°C colder than the present during the last three glacial maximums. In comparison, faunal derived SSTs ( SIMMAX method) show that August SSTs in the Caribbean varied < 2° over the past 360 kyr, whereas February SSTs varied between 21.0°C and 26.5°C. Changes in the Mg/Ca-SST record contain a strong 23 kyr periodicity, suggesting the Mg/Ca-SST record reflects a warm season weighted SST average rather than an annual mean SST. Combining several dissolution indices, we identify brief periods of decreased carbonate preservation in our record and show that MIS 11 stands out as the most intensive dissolution cycle in the Caribbean over the last 460 kyr. Comparison of Caribbean SST change with a similar estimate of tropical SST variability in the western Pacific over the past 360 kyr reveals shifts in the east-west tropical SST gradient that are coeval with glacial-interglacial climate change and consistent both with a southward migration of the glacial ITCZ and with a glacial El Niño-like mode of tropical circulation.

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 …

Relating Water And Otolith Chemistry In Chesapeake Bay, And Their Potential To Identify Essential Seagrass Habitats For Juveniles Of An Estuarine-Dependent Fish, Spotted Seatrout (Cynoscion Nebulosus), Emmanis Dorval

Biological Sciences Theses & Dissertations

A quantitative understanding of habitat use of estuarine-dependent fishes is critical to the conservation of their most essential habitats. Because recruitment and fitness may be influenced by the quality of juvenile habitats, developing methods to quantify habitat-specific survivorship is pivotal to such understanding. An initial step to quantify survivorship is to validate the habitat-specific natural tags contained in otoliths. To this aim I investigated the variability in the chemistry of surface waters and otoliths of juvenile spotted seatrout, Cynoscion nebulosus, in five seagrass habitats of Chesapeake Bay, namely: Potomac, Rappahannock, York, Island, and Eastern Shore. I measured Mg, Ca, …

Potential Contaminants At A Dredged Spoil Placement Site, Charles City County, Virginia, As Revealed By Sequential Extraction, Jianwu Tang, G. Richard Whittecar, Karen H. Johannesson, W. Lee Daniels

OES Faculty Publications

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total …

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 …

Nitrate Anomaly In The Upper Nutricline In The Northern South China Sea - Evidence For Nitrogen Fixation, George T. F. Wong, Shi-Wei Chung, Fuh-Kwo Shiah, Chung-Chi Chen, Liang-Saw Wen, Kon-Kee Liu

OES Faculty Publications

[1] Up to 2 μM of nitrate anomaly, N*, were found in the upper nutricline at the South East Asia Time-series Study (SEATS) site in the northern South China Sea (SCS). These concentrations were among the higher values reported in the Pacific and indicate the significant contribution of the remineralization of nitrogen-rich organic matter formed by nitrogen fixation to the nutrient dynamics of the area. The concentrations were systematically higher, by up to 2.5 μM, in the Fall through the early Spring, during the northeast monsoon, than in the Summer, suggesting that the impact of nitrogen fixation was higher during …

Intra-Annual Variation In The Stable Oxygen And Carbon And Trace Element Composition Of Sclerosponges, P. K. Swart, S. Thorrold, B. Rosenheim, A. Eisenhauer, C. G. A. Harriason, M. Grammer, C. Latkoczy

Biological Sciences Faculty Publications

This paper presents data to support the presence of (1) intra-annual signals in the chemical composition (δ¹⁸O and Sr/Ca) of the skeletons ofsclerosponges from the Bahamas and (2) variable rates of skeletal accretion. These conclusions are based on data obtained by using a microsampling method for the stable oxygen and carbon isotopes in which material was extracted at a resolution of one sample every 34 μm and a laser microprobe which obtained trace element data every 20 μm (Sr, Mg, and Pb). An age model was established using a combination of changes in the concentration of Pb, the …

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 …

Zinc Speculation And Ligand Fluxes In Chesapeake Bay And Elizabeth River Pore Waters, Duncan Glover Byers

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on the vertical concentrations, complexation, speciation, and fluxes of total dissolved zinc and zinc complexing ligands, and zinc speciation in sediment pore waters in the Chesapeake Bay and Elizabeth River, Virginia.

Sediment pore waters were collected in mid and southern Chesapeake Bay in November 1997 and in the Elizabeth River (Pinner's Point) in March, April, and July 1998. Flux experiments were conducted in Elizabeth River sediment cores in April and July 1998. [TDZn] and zinc complexation were determined using differential pulse anodic stripping voltammetry at a hanging mercury drop electrode (DPASV-HMDE).

[TDZn] in 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 …

A Geochemical Study Of Marine Sediments From The Mac. Robertson Shelf, East Antarctica: Initial Results And Palaeoenvironmental Implications, Peter N. Sedwick, P. T. Harris, L. G. Robertson, G. M. Mcmurtry, M. D. Cremer, P. Robinson

OES Faculty Publications

Sediments from the Antarctic continental margin may provide detailed palaeoenvironmental records for Antarctic shelf waters during the late Quaternary. Here we present results from a palaeoenvironmental study of two sediment cores recovered from the continental shelf off Mac. Robertson Land, East Antarctica. These gravity cores were collected approximately 90 km apart from locations on the inner and outer shelf. Both cores are apparently undisturbed sequences of diatom ooze mixed with fine, quartz-rich sand. Core stratigraphies have been established from radiocarbon analyses of bulk organic carbon. Down-core geochemical determinations include the lithogenic components Al and Fe, biogenic components opal and organic …

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 …

Identification And Quantitation Of Volatile Amines In Chesapeake Bay Sediments, Neeraja Y. Krishna

Chemistry & Biochemistry Theses & Dissertations

Sediments from different parts of the Chesapeake Bay were analyzed to determine the presence of volatile amines. A HF-HCl extraction method was used to extract both exchangeable and fixed amines from the sediments and a purge-and-trap technique was used to concentrate the amines. Following derivatization with heptafluorobutyric anhydride (HFBA), the HFBA-amines were analyzed by gas chromatography with electron capture detection and with mass spectrometric detection. One primary amine, i-amylamine with a concentration ranging from 0. 78 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty seven samples collected on three different dates in 1993. Another primary amine, 2-methylbutylamine with a concentration ranging from 0.18 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty three samples collected on three different dates in 1993. A secondary amine, diethylamine was detected but could not be quantified in a total of seven samples collected in September 1993. The concentrations of these amines varied with location in the Bay, depth in the sediment, and time of year the sediments were collected. The origin of i-amylamine and 2-methylbutylamine might be from the biological decarboxylation of amino acids leucine and isoleucine, respectively. The origin of diethylamine is unknown.

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 …