Geochemistry Commons^™

Phosphate Speleothems In Caves Developed In Iron Ores And Laterites Of The Carajás Mineral Province (Brazil) And A New Occurrence Of Spheniscidite, Alan R.L. Albuquerque, Rômulo S. Angélica, Daniele F. Gonçalves, Simone P.A. Paz

International Journal of Speleology

The Carajás Mineral Province has one of the largest concentrations of caves in Brazil, and its iron ore is among the country’s main exports. As a result of iron ore intense extraction, new environmental policies have been implemented. In an attempt to balance economic activity and environmental conservation, an inventory and a relevance-based classification of caves were implemented in 2008 as criteria for environmental licensing of mining ventures. This implementation motivated the present study of phosphate speleothems in Carajás’ caves developed in ferriferous rocks. The objectives of this study are to describe the phosphate minerals and their formation processes based …

Catalyzed Synthesis Of Zinc Clays By Prebiotic Central Metabolites, Marcelo I. Guzman, Ruixin Zhou, Kaustuv Basu, Hyman Hartman, Christopher J. Matocha, S. Kelly Sears, Hajatollah Vali

Chemistry Faculty Publications

How primordial metabolic networks such as the reverse tricarboxylic acid (rTCA) cycle and clay mineral catalysts coevolved remains a mystery in the puzzle to understand the origin of life. While prebiotic reactions from the rTCA cycle were accomplished via photochemistry on semiconductor minerals, the synthesis of clays was demonstrated at low temperature and ambient pressure catalyzed by oxalate. Herein, the crystallization of clay minerals is catalyzed by succinate, an example of a photoproduced intermediate from central metabolism. The experiments connect the synthesis of sauconite, a model for clay minerals, to prebiotic photochemistry. We report the temperature, pH, and concentration dependence …

Rock Magnetic Investigation Of The Michigan Basin Soils And Sediments Overlying The Oil-Bearing Silurian Pinnacle Reefs, Jake Tresnak

Dissertations, Master's Theses and Master's Reports

A relationship between the hydrocarbon migration and magnetic properties of near-surface sediments was investigated from several hundreds of samples collected over the hydrocarbon-bearing Silurian pinnacle reef belt of the Michigan Basin. The collected samples were investigated using several rock magnetic methods and optical microscopy. The investigation has not revealed a straightforward relationship between the magnetic susceptibility and hydrocarbon reservoirs within the reef belt; both anomalously high and low susceptibility values were observed. The elevated values are associated with newly formed magnetite in the form of spheroidal grains produced by hydrocarbon-related diagenesis while the extremely low susceptibilities may reflect dissolution of …

High-Resolution Signatures Of Oxygenation And Microbiological Activity In Speleothem Fluid Inclusions, Nigel Blamey, Penelope J. Boston, Laura Rosales-Lagarde

International Journal of Speleology

Speleothems frequently host “fossil” fluids that were trapped in small inclusions during growth. Such fluids may provide valuable clues to past microbial, geochemical, and climatic processes during their formation. However, one difficulty is to understand which gases represent background atmosphere and fluids within a given cave system at a particular time, and which may be the product of post-trapping residual microbial activity or abiotic chemical reactions? Do we have any hope of sorting out these differences? The success depends on a quantitative understanding of the gas composition trapped in the inclusions and an understanding of the interactions of cave mineralogy, …

Development And Curation Of The Sample Data Library For The Astrobiogeochemistry Laboratory, Meika R. Nwaomah, Lorenia Jimenez, Michael Tuite

STAR Program Research Presentations

In 2011, the National Science Foundation (NSF) initiated EarthCube, an integrated cyber infrastructure initiative, to tackle challenges within geoscience research. EarthCube’s goal is to improve public access and collaboration within the geoscience community. During the summer of 2015, the Astrobiogeochemistry Laboratory (abcLab) joined the collective efforts of EarthCube by developing the Sample Data Library (SDL) for the Jet Propulsion Laboratory (JPL). The main focus of the SDL concentrates on effectively curating the samples collected by researchers within the Planetary Chemistry and Astrobiology section at JPL. The goal of this summer internship was to assimilate field notes, images, and from data …

Cone In Cone Concretions Of The Stanley Group In Southeastern Oklahoma, Kyle B. Ayres

Electronic Theses and Dissertations

Cone in cone concretions found in the Stanley Group of Southeastern Oklahoma have a variety of external and internal attributes which allow diagenetic and theoretical models of formation to be hypothesized. Stanley Group carbonate cone in cone concretions are initially formed in sulfur reducing horizons at shallow burial depths in a poorly circulated possibly deep trough containing siliceous sediments and organic matter. Collected concretions near the town of Smithville, Oklahoma displayed four different external morphologies and four variations of mineral constituents. All concretions contained microscopic cones which initiated diffusion and/or fluid patterns and is an early cementation process that directly …

Testing Of The Late-Ordovician Pre-Gice Warm Water Carbonate Hypothesis In Alabama, Brandon Euker, Stacey Law

Senior Honors Projects, 2010-2019

The Guttenberg Carbon Isotope Excursion (GICE) (uppermost Sandbian-lower Katian, Late Ordovician) has been suggested to represent the transition from a Cambrian-Ordovician greenhouse world to Late Ordovician icehouse world. This transition is thought to coincide with a proposed shift from deposition of warm water carbonate rocks to cool water carbonate rocks in the North American midcontinent. We used oxygen isotopes (d¹⁸O) of conodonts to test the idea that the rocks below the GICE interval represent a consistently warm environment. Conodonts were isolated from samples of the Chickamauga Group collected at the Tidwell Hollow section in Blount County, AL, from …

Biogeochemical Cycling In A Headwater Stream And Riparian Zone, A. Capri Gillam

Graduate Theses & Non-Theses

Several teams of researchers at multiple universities are currently measuring annual and seasonal fluxes of carbon dioxide and other greenhouses gases (nitrous oxide and methane) in riparian wetlands and upland forests in the Tenderfoot Creek Experimental Forest (TCEF), a subalpine watershed in the Little Belt Mountains, Montana. In the current thesis, the author characterized the geochemistry and stable carbon isotope composition of shallow groundwater, soil water, and stream water in upper Stringer Creek, near sites that are being investigated for gas chemistry and microbial studies. It was hypothesized that if methanogenesis were a dominant process in the riparian wetlands of …

Ecosystem Regime Change Inferred From The Distribution Of Trace Metals In Lake Erie Sediments, Fasong Yuan, Richard Depew, Cheryl Soltis-Muth

Biological, Geological, and Environmental Faculty Publications

Many freshwater and coastal marine ecosystems across the world may have undergone an ecosystem regime change due to a combination of rising anthropogenic disturbances and regional climate change. Such a change in aquatic ecosystems is commonly seen as shifts in algal species. But considerably less detail is known about the eutrophication history in terms of changes in algal productivity, particularly for a large lake with a great deal of spatial variability. Here we present an analysis of trace metals (Cu, Ni, Cd, and Pb) on a sediment core recovered from Lake Erie, off the Vermilion coast of northern Ohio, USA, …

Ice Caves On Extraterrestrial Bodies: What Are The Prospects For Speleogenesis And Detection?, Penelope J. Boston

The International Workshop on Ice Caves

Potential mechanisms for creating cavities in icy extraterrestrial bodies have been tentatively explored by several authors. On one hand we have examples of mechanisms that create caves in water ice here on Earth. In addition, there may be unique mechanisms on other Solar System objects that do not occur on Earth but might produce cavities, e.g. sublimation of comets upon perihelion passage. The methods of detecting such cavities depend upon the nature of the icy body in question, the potential for orbital or landed missions to visit those bodies in the future, and remote or landed methods for detecting the …

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 …

A Coupled Geochemical And Biogeochemical Approach To Characterize The Bioreactivity Of Dissolved Organic Matter From A Headwater Stream, Rachel L. Sleighter, Rose M. Cory, Louis A. Kaplan, Hussain A.N. Abdulla, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% …

Spectroscopic Study Of Uranium (Vi) Reduction By Plant Biomass, Margaret C. Murphy, John Bargar, Noémie Janot

STAR Program Research Presentations

Uranium is a common and problematic groundwater contaminant at Department of Energy legacy sites. At the former uranium ore processing plant at Rifle, Colorado, sediments rich in decayed plant biomass contain large concentrations of uranium that are slowly being released back to the aquifer. To simulate the reaction that occurs in organic rich sediments of the Rifle aquifer, biomass was incubated in U (VI) bearing groundwater. Carbon X-ray absorption spectroscopy (XAS) was then used to measure if uranium was bound to the biomass. When uranium binds to biomass the peaks in the C XAS spectra will change shape. Uranium L …

Chemostratigraphy Of The Early Pliocene Diatomite Interval From Mis And-1b Core (Antarctica): Paleoenvironment Implications, Giovanna Scopelliti, Adriana Bellanca, Donata Monien, Gerhard Kuhn

ANDRILL Research and Publications

The AND-1B drill core (1285 m-long) was recovered, inside the ANDRILL (ANtarctic geological DRILLing) Program, during the austral summer of 2006/07 from beneath the floating McMurdo Ice Shelf. Drilling recovered a stratigraphic succession of alternating diamictites, diatomites and volcaniclastic sediments spanning about the last 14 Ma. A core portion between 350 and 480 mbsf, including a 80 m-thick diatomite interval recording the early Pliocene warming event, was investigated in term of opal biogenic content and element geochemistry. Across the diatomite interval, in spite of the lithological uniformity, a fluctuating biogenic opal profile mirrors the δ18O record, testifying a decrease in …

Abiotic Nitrate And Nitrite Reactivity With Iron Oxide Minerals, Prakash Dhakal

Theses and Dissertations--Plant and Soil Sciences

Under iron (Fe³⁺)-reducing conditions where aqueous Fe²⁺ and unreduced solid Fe³⁺-oxides commonly coexist, soil Fe²⁺ oxidation has been shown to be coupled with nitrate (NO₃^-) reduction. One possible secondary reaction is the involvement of NO₃^- and nitrite (NO₂^-) with Fe-oxide minerals found in many natural environments. Yet, spectroscopic measurements and kinetic data on reactivity of NO₃^- and NO₂^- with Fe-containing oxide minerals such as goethite (a-FeOOH), and magnetite (Fe₃O­₄) are not found in the literature. The reactivity of …

Are 34s-Enriched Authigenic Sulfide Minerals A Proxy For Elevated Methane Flux And Gas Hydrates In The Geologic Record?, Walter S. Borowski, Nancy M. Rodriguez, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

The sulfate–methane transition (SMT) zone is a diagenetic transition within anoxic marine sediments created by the metabolic activity of a consortium of sulfate-reducing bacteria and methane-oxidizing Archaea. As interstitial dissolved sulfate is consumed by microbially mediated sulfate reduction of sedimentary organic matter (SOM) and anaerobic oxidation of methane (AOM) large enrichments of ³⁴S occur in the interstitial sulfate pool. These isotopic enrichments are transmitted to the dissolved sulfide pool (∑HS⁻) and subsequently into sulfide minerals (So, ∼FeS, FeS₂).

We investigate the sulfur isotopic composition of pore-water sulfate and sulfide minerals at three sites underlain …

A Geochemical Analysis Of Fulgurites: From The Inner Glass To The Outer Crust, Michael L. Joseph

USF Tampa Graduate Theses and Dissertations

Cloud-to-ground lightning strikes produce natural glasses on the surface of the Earth, called fulgurites. These natural glasses are tubular in shape with a central void surrounded by an inner glass, and the inner glass is surrounded by an outer crust or toasted region. Previous studies report different kinds of melts existing in several different types of fulgurites; however, little to no chemical data has been collected that tracks chemical variations from the inner glass to the outer crust of a fulgurite. This study uses microprobe and laser ablation inductively coupled plasma mass spectrometer analytical techniques to collect transects of chemical …

Evaluation Of The Carbon Budgets In The Forested And Agricultural Soils Of The Semi-Arid Mogollon-Datil Highlands And Rio Grande Basin, Ryan Reeves^, Lixin Jin*

COURI Symposium Abstracts, Summer 2011

No abstract provided.

Early Season Depletion Of Dissolved Iron In The Ross Sea Polynya: Implications For Iron Dynamics On The Antarctic Continental Shelf, Peter N. Sedwick, C. M. Marsay, B. M. Sohst, A. M. Aguilar-Islas, M. C. Lohan, M. C. Long, K. R. Arrigo, R. B. Dunbar, M. A. Saito, W. O. Smith, G. R. Ditullio

OES Faculty Publications

The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO₂sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a "winter reserve" of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (~ 0.1 nM) that limit phytoplankton growth in the austral summer (December-February). Here we report new iron data for the Ross Sea polynya during austral summer 2005-2006 (27 December-22 January) and the following austral spring 2006 (16 November-3 December). The summer 2005-2006 data show …

Investigating The Influence Of Organic Acids On Uraninite Solubility And Uranyl Sorption Onto Kaolinite, Michelle L. Barger

Dissertations

Within anoxic near surface aqueous settings where U0_2(S) may be released an opportunity to encounter and complex with organic acids may occur. Reactions between U0_2(S) and ligands may promote the solubility and mobility of uranium. Organic ligands investigated in the dissolution work include citric acid, NTA and EDTA. Exposure to the ligands had little effect on U0_2(S) solubility. The log activity of U0_2(S) hydrolysis under reduced conditions was -6.56. Under all measured conditions of ligand concentration, the data consistently show an increase in uranium concentration to a median log U activity of -4.89. The observed solubility …

Iron Oxide And Calcite Associated With Leptothrix Sp. Biofilms Within An Estavelle In The Upper Floridan Aquifer, Lee J. Florea, Chasity L. Stinson, Josh Brewer, Rick Fowler, B Joe Kearns, Anthony M. Greco

International Journal of Speleology

In Thornton’s Cave, an estavelle in west-central Florida, SEM, EDS, and XRD data reveal biofilms that are predominantly comprised of FeOOH-encrusted hollow sheaths that are overgrown and intercalated with calcite. Fragments of this crystalline biofilm adhere to the walls and ceiling as water levels vary within the cave. Those on the wall have a ‘cornflake’ appearance and those affixed to the ceiling hang as fibrous membranes. PCR of DNA in the active biofilm, combined with morphologic data from the tubes in SEM micrographs, point to Leptothrix sp., a common Fe-oxidizing bacteria, as the primary organism in the biofilm. Recent discoveries …

Carbon Isotopic Fractionation Across A Late Cambrian Carbonate Platform: A Regional Response To The Spice Event As Recorded In The Great Basin, Jonathan Lloyd Baker

UNLV Theses, Dissertations, Professional Papers, and Capstones

Geochemical models have suggested that the late Cambrian was characterized by a greenhouse climate with high pCO2. Furthermore, stableisotope analyses within the Great Basin have documented a large carbonate isotope (δ13Ccarb) excursion, known as the Steptoean Positive Carbon Isotope Excursion (SPICE). This event has been documented globally, and is interpreted as having resulted from enhanced organic carbon burial. Unless the size of carbon reservoirs in the Cambrian ocean was significantly different from those of the Cenozoic, this forcing should have resulted in a comparable carbon-isotope excursion in organic matter (δ13Corg). It is also predicted that increased organic carbon burial would …

Enrichments Of Heavy Sulfur (34s) In Sulfide Minerals: Gas Hydrates, Methane Delivery, And Anaerobic Methane Oxidation, Walter S. Borowski, Namcy M. Rodriguez, Charles K. Paull, William Ussler Iii

EKU Faculty and Staff Scholarship

The sulfur isotopic composition of authigenic, sedimentary sulfide minerals is largely controlled by sulfate reduction and related processes within sedimentary environments. Histograms show that that d³⁴S values of sulfide minerals forming in depositional and diagenetic environments are most often negative (d³⁴S < 0^o/_oo CDT) reflecting the original isotopic composition of seawater sulfate (now ~21^o/_oo), microbially-mediated fractionations of ~-8 to -40^o/_oo (a = 1.029-1.059) during sulfate reduction, and more extreme fractionations caused by sulfur disproportionation. Enrichments of heavy sulfur (d³⁴S > 0^o/_oo) in sulfide …

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, …

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 …

Copper Isotope Fractionation During Surface Adsorption And Intracellular Incorporation By Bacteria, Jesica Urbina Navarrete

Open Access Theses & Dissertations

Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data that constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study we utilized Cu isotopes (65Cu) as a tool to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacterial species as well as with bacterial consortia from several natural environments. Adsorption experiments were conducted with live or dead cells over the pH range 2.5 to 6. Surface adsorption of Cu …

Researching Nitrite Oxidation At High Temperatures, Dolores A. Huang, Jeremy A. Dodsworth, Brian P. Hedlund

Undergraduate Research Opportunities Program (UROP)

15N-nitrate (NO3 -) pool dilution experiments show that ammonia (NH3) is oxidized to nitrate in geothermal springs up to at least 85C; however, nitrite (NO2 -)- oxidizing microorganisms are only known to grow up to 66°C. We hypothesize that thermophilic microorganisms oxidize nitrite to nitrate at high temperatures. Alternatively, it is possible that nitrite is oxidized abiotically. We propose to test these hypotheses by setting up microbial enrichments designed to grow thermophilic nitrite oxidizing bacteria by varying incubation temperature (50, 65, 80°C), oxygen concentration (20% and 5%), and cultivation media. A negative control consisting of filtered spring water (0.1 μm) …

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).

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 …