VTechWorks Repository :: Browsing by Author "Rimstidt, J. Donald"

Browsing by Author "Rimstidt, J. Donald"

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3D Printing of Specialty Devices for Geochemical Investigations: Real-Time Studies of Goethite and Schwertmannite Formation
Kletetschka, Karel (Virginia Tech, 2018-06-29)
New types of laboratory reactors that are highly customizable, low-cost and easy to produce are needed to investigate low-temperature geochemical processes. We recently showed that desktop 3D printing stereolithography (SLA) can be used to efficiently fabricate a mixed flow reactor (MFR) with high dimensional accuracy comparable to traditional machining methods (Michel et al., 2018). We also showed that the SLA method allowed for the addition of complex features that are often beyond the capabilities of traditional methods. However, the stability of 3D printed parts at low-temperature geochemical conditions has not been fully evaluated. The objectives of this work were twofold: 1) to provide a framework for assessing the stability and compatibility of SLA printed materials at geochemically relevant conditions, and 2) to show how 3D printed specialty devices can enable new laboratory geochemical experiments. Part 1 of this Master's thesis presents findings for enhancing mechanical and solvent resistance properties of a commercial 3D printing material (Formlabs Clear) by UV post-curing procedures and also provide data showing its stability in aqueous solutions at pH 0, 5.7, and 12 for periods of up to 18 days. Thermal degradation patterns, mechanical analysis, and leachable fraction data are provided. Part 2 shows experiments coupling 3D printed reactors and flow devices for in situ small-angle x-ray scattering (SAXS). Schwertmannite (pH 2.7) and goethite (6.2) are precipitated from solution using various setups and observed differences in growth rates are discussed. The data show the potential of 3D printing for enabling novel laboratory geochemical experiments.
Adsorption Properties of Roxarsone and Arsenate on Goethite and Kaolinite
Harvey, Mary Catherine (Virginia Tech, 2006-04-28)
This study investigated the adsorption properties of roxarsone, an organoarsenic poultry feed additive, to goethite and kaolinite in order to determine what role mineral surfaces play in controlling the mobility of roxarsone in watersheds where poultry litter is applied. Adsorption edge experiments for goethite and kaolinite showed a dependence on pH for both As(V) and roxarsone. This pattern can be explained by the pH-dependent changes in the mineral surface charge and protonation of the aqueous arsenic species. Isotherms for As(V) and roxarsone on goethite and kaolinite show surface saturation for As(V), but not for roxarsone. The overall adsorption patterns show that As(V) and roxarsone adsorption is similar, suggesting that the arsenate functional group is the dominant control on roxarsone adsorption. However, there are some subtle differences between adsorption of As(V) and roxarsone, which can be explained by the relative sizes of the molecules, the presence of functional groups, differences in solubility, and differences in the type of adsorption (monolayer versus multilayer). Comparison of roxarsone adsorption to goethite and kaolinite reveals that at the low concentrations of roxarsone that are expected to leach from poultry litter into soil water, goethite adsorbs roxarsone more strongly then kaolinite. However, due to the abundance of kaolinite, both are important controls on roxarsone mobility.
Aluminum hydroxide coatings in limestone drains
Palomino-Ore, Sheyla B.; Rimstidt, J. Donald; Chermak, John A.; Schreiber, Madeline E.; Seal, Robert R. II (2019-04)
This paper describes a mixed flow reactor experiment and associated data analysis scheme that are well suited for studying the chemical and physical processes that occur in limestone drains used to treat acid mine drainage (AMD). The experiment simulates the slowly evolving, near steady state, reactions that form coatings on limestone. The resulting coatings can be recovered for analysis of their structure and composition. Analysis of the time evolution of the composition of the effluent solutions is used to isolate and understand key factors that affect limestone drain performance. The experiment investigated reactions between acidic aluminum sulfate solutions and calcite. The aluminum sulfate feed solutions contained 0.002-0.01 molal (32-329 mg/kg) Al and had pH values ranging from 3.7 to 4.2. At the beginning each experiment, the rate of H+ consumption by reaction with the calcite was fast causing a distinct increase of the effluent pH. The pH increase caused some of the dissolved Al to precipitate as a coating on the calcite surfaces. The coating blocked the transfer of ions to and from the calcite causing the reaction rates to be limited by ion diffusion through the coating. The continued growth of the coating caused it to become an increasingly effective barrier to ion transport, which caused the neutralization rate to slow and the effluent solution pH to decline toward that of the feed solution. Powder X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) suggested that the coatings were mostly poorly crystalline gibbsite. Effluent solutions were analyzed to determine pH along with Al, Ca and S concentrations. The coating thickness at each sample time was estimated from the amount of Al lost from the solution since the beginning of the experiment. This thickness and the Ca and H+ fluxes were used to find the apparent H+ diffusion coefficient in the coatings.
Analysis of Hydrologic and Geochemical Time Series Data at James Cave, Virginia: Implications for Epikarst Influence on Recharge
Eagle, Sarah Denise (Virginia Tech, 2013-05-09)
Karst aquifers are productive groundwater systems around the world, supplying approximately 25% of the world's drinking water. However, they are highly vulnerable to contamination due to rapid groundwater transit in the transmission zone (KWI 2006). The epikarst, also known as the subcutaneous zone, is an interface between the soil overburden and the transmission zone. The epikarst is considered a critical zone as it can control hydrologic and geochemical characteristics of recharge to the underlying karst aquifer. The overall goal of this thesis is to utilize time series hydrologic and geochemical data collected at James Cave, Virginia, to examine the influence of epikarst on the quantity, quality, and rates of recharge to aquifers in Appalachian karst. Results of this study indicate a strong seasonality of both the hydrology and geochemistry of recharge. The conceptual model of the epikarst developed in this study identifies three hydrologic seasons: recharge, recession, and baseflow. Seasonality of recharge geochemistry coincides with these three hydrologic seasons. These results have implications for management of karst aquifers. First, recharge to Appalachian karst aquifers is seasonal, reaching a maximum during the winter-early spring; the onset of recharge depends on antecedent climatic conditions. Second, water that infiltrates into the epikarst will have seasonally variable residence times due to changes in hydrologic storage; these variations in attenuation affect geochemical reactions in the epikarst, which can influence recharge quality. Overall, these results point to the complex influence of epikarst on karst recharge, which necessitates collection of long-term and high resolution datasets.
Application of Fluid Inclusions and Mineral Textures in Exploration for Epithermal Precious Metals Deposits
Moncada de la Rosa, Jorge Daniel (Virginia Tech, 2008-12-09)
Fluid inclusion and mineralogical features indicative of boiling have been characterized in 855 samples from epithermal precious metals deposits along the Veta Madre at Guanajuato, Mexico. Features associated with boiling that have been identified at Guanajuato include colloform texture silica, plumose texture silica, moss texture silica, ghost-sphere texture silica, lattice-bladed calcite, lattice-bladed calcite replaced by quartz and pseudo-acicular quartz after calcite and coexisting liquid-rich and vapor-rich fluid inclusions. Most samples were assayed for Au, Ag, Cu, Pb, Zn, As and Sb, and were divided into high-grade and low-grade samples based on the gold and silver concentrations. For silver, the cutoff for high grade was 100 ppm Ag, and for gold the cutoff was 1 ppm Au. The feature that is most closely associated with high grades of both gold and silver is colloform texture silica, and this feature also shows the largest difference in grade between the presence or absence of that feature (178.8 ppm Ag versus 17.2 ppm Ag, and 1.1 ppm Au versus 0.2 ppm Au). For both Ag and Au, there is no significant difference in average grade as a function of whether or not coexisting liquid-rich and vapor-rich fluid inclusions are present. The textural and fluid inclusion data obtained in this study were analyzed using the binary classifier within SPSS Clementine. The models that correctly predicted high versus low grade samples most consistently (~70-75% of the tests) for both Ag and Au were the neural network, the C5 decision tree and Quest decision tree models. For both Au and Ag, the presence of colloform silica texture was the variable with the greatest importance, i.e., the variable that has the greatest predictive power. Boiling features are absent or rare in samples collected along a traverse perpendicular to the Veta Madre. This suggests that if an explorationist observes these features in samples collected during exploration that an environment favorable to precious metal mineralization is nearby. Similarly, good evidence for boiling is observed in the deepest levels of the Veta Madre that have been sampled in the mines and drill cores, suggesting that additional precious metal reserves are likely beneath the deepest levels sampled.
Application of fluid inclusions in geological thermometry
Fall, Andras (Virginia Tech, 2008-12-10)
Many geologic processes occur in association with hydrothermal fluids and some of these fluids are eventually trapped as fluid inclusions in minerals formed during the process. Fluid inclusions provide valuable information on the pressure, temperature and fluid composition (PTX) of the environment of formation, hence understanding PTX properties of the fluid inclusions is required. The most important step of a fluid inclusion study is the identification of Fluid Inclusion Assemblages (FIA) that represent the finest (shortest time duration) geologic event that can be constrained using fluid inclusions. Homogenization temperature data obtained from fluid inclusions is often used to reconstruct temperature history of a geologic event. The precision with which fluid inclusions constrain the temperatures of geologic events depends on the precision with which the temperature of a fluid inclusion assemblage can be determined. Synthetic fluid inclusions trapped in the one-fluid-phase field are formed at a known and relatively constant temperature. However, microthermometry of synthetic fluid inclusions often reveals Th variations of about ± 1- 4 degrees Centigrade, or one order of magnitude larger than the precision of the measurement for an individual inclusion. The same range in Th was observed in well-constrained natural FIAs where the inclusions are assumed to have been trapped at the same time. The observed small variations are the result of the effect of the fluid inclusion size on the bubble collapsing temperature. As inclusions are heated the vapor bubble is getting smaller until the pressure difference between the pressure of the vapor and the confining pressure reaches a critical value and the bubble collapses. It was observed that smaller inclusions reach critical bubble radius and critical pressure differences at lower temperatures than larger inclusions within the same FIA. Homogenization temperature (Th) variations depend on many factors that vary within different geological environments. In order to determine minimum and acceptable Th ranges fro FIAs formed in different environments we investigated several geologic environments including sedimentary, metamorphic, and magmatic hydrothermal environments. The observed minimum Th ranges range from 1-4 degrees Centigrade and acceptable Th range from 5-25 degrees Centigrade. The variations are mostly caused by the fluid inclusion size, natural temperature and pressure fluctuations during the formation of an FIA and reequilibration after trapping. Fluid inclusions containing H₂O-CO₂-NaCl are common in many geologic environments and knowing the salinity of these inclusions is important to interpret PVTX properties of the fluids. A technique that combines Raman spectroscopy and microthermometry of individual inclusions was developed to determine the salinity of these inclusions. In order to determine the salinity, the pressure and temperature within the inclusion must be known. The pressure within the inclusions is determined using the splitting in the Fermi diad of the Raman spectra of the CO₂ at the clathrate melting temperature. Applying the technique with to synthetic fluid inclusions with known salinity suggests that the technique is valid and useable to determine salinity of H₂O-CO₂-NaCl fluid inclusions with unknown salinity.
Applications of Melt Inclusions to Problems in Igneous Petrogenesis
Severs, Matthew Jeremiah (Virginia Tech, 2007-06-22)
Understanding the different igneous processes that magmas undergo is important for a variety of reasons including potential hazards associated with volcanoes in populated regions, magmatic hydrothermal ore deposition, and tectonic processes. One method of obtaining geochemical data that can help constrain petrogenetic processes is through the study of melt and fluid inclusions. The research presented here examines melt inclusions through experimental, analytical and field studies to better understand igneous petrogenesis. One potential problem associated with melt inclusions is water-loss during laboratory heating. A Raman spectroscopic technique was developed to determine water contents of silicate glasses, and this technique was applied to monitor water loss from natural melt inclusions that were heated for varying lengths of time. The results suggest that water loss is insignificant when heated for less than 12 hours but significant water loss can occur with longer duration heating. The distribution of trace elements between silicate melts and phenocrysts growing from that melt can constrain igneous processes such as fractional crystallization, assimilation, and partial melting. Partition coefficients were determined for syngenetic clinopyroxene, orthopyroxene, and plagioclase in equilibrium with a dacitic melt using the Melt Inclusion-Mineral (MIM) technique. Melt inclusion chemistry is the same regardless of mineral host phase, suggesting that the melt inclusions have not been subjected to re-equilibration processes or boundary layer development. Partition coefficients from this study are similar but typically lower than published values. Three closely-spaced monogenetic eruptive units from the active Campi Flegrei volcanic system (Italy) with similar eruptive styles were examined to better understand the evolution of the magmatic system. Results suggest fractional crystallization as the dominant process taking place over time but that magma mixing was significant for one of the eruptions. Trace element geochemical data suggest a mixed magma source of within-plate and volcanic arc components, and still retain a T-MORB signature from the subducting slab.
Arsenic mobilization through bioreduction of iron oxide nanoparticles
Roller, Jonathan William (Virginia Tech, 2004-07-21)
Arsenic sorbs strongly to the surfaces of Fe(III) (hydr)oxides. Under aerobic conditions, oxygen acts as the terminal electron acceptor in microbial respiration and Fe(III) (hydr)oxides are highly insoluble, thus arsenic remains associated with Fe(III) (hydr)oxide phases. However, under anaerobic conditions Fe(III)-reducing microorganisms can couple the reduction of solid phase Fe(III) (hydr)oxides with the oxidation of organic carbon. When ferric iron is reduced to ferrous iron, arsenic is mobilized into groundwater. Although this process has been documented in a variety of pristine and contaminated environments, minimal information exists on the mechanisms causing this arsenic mobilization. Arsenic mobilization was studied by conducting controlled microcosm experiments containing an arsenic-bearing ferrihydrite and an Fe(III)-reducing microorganism, Geobacter metallireducens. Results show that arsenic mobility is strongly controlled by microbially-mediated disaggregation of arsenic-bearing iron nanoparticles. The most likely controlling mechanism of this disaggregation of iron oxide nanoparticles is a change in mineral phase from ferrihydrite to magnetite, a mixed Fe(III) and Fe(II) mineral, due to the microbially-mediated reduction of Fe(III). Although arsenic remained associated with the iron oxide nanoparticles and was not released as a hydrated oxyanion, the arsenic-bearing nanoparticles could be readily mobilized in aquifers. These results have significant implications for understanding arsenic behavior in aquifers with Fe(III) reducing conditions, and may aid in improving remediation of arsenic-contaminated waters.
Arsenic Release from Chlorine Promoted Oxidation of Pyrite in the St. Peter Sandstone Aquifer, Eastern Wisconsin
West, Nicole Renee (Virginia Tech, 2008-04-25)
High arsenic concentrations (>100 ppb) have been measured in wells completed in the Ordovician St. Peter sandstone aquifer of eastern Wisconsin. The primary source of arsenic is As-bearing sulfide minerals within the aquifer. There is concern that periodic disinfection of wells by chlorination may facilitate arsenic release to groundwater by increasing the rate of sulfide mineral oxidation. Current guidance from the Wisconsin Department of Natural Resources recommends a "low-dose" treatment of 20% of the chlorine strength and 10% of the of the contact time of chlorine treatments used in non-arsenic impacted wells for well disinfection and biofilm removal. In order to provide information pertaining to WDNR's recommendations, St. Peter sulfide minerals were reacted with a range of chlorine "shock-treatments" similar to those occurring in wells. This study focuses on abiotic processes that mobilize arsenic from the solid phase during controlled exposure to chlorinated solutions. Thin sections were made from aquifer material collected at Leonard's Michael quarry, located in Winnebago County, Wisconsin. Bulk arsenic content of this material was measured as 674 ppm. Quantitative EPMA analysis shows As zoning in pyrite grains with concentrations up to 1 wt. % As. After mineral characterization, the thin sections were exposed to solutions of 60 mg/L "free chlorine," 1200 mg/L "free chlorine," and nanopure water (control) at pH 7.0 and pH 8.5 for 24 hours. Thin sections were then analyzed to measure changes in the pyrite surfaces. For solution experiments, aquifer material was crushed to between 250 μm and 355 μm mesh sizes (S.A. ~ 50 cm2/g – 60 cm2/g, Foust et al. 1980) and reacted under the same conditions as the thin sections in a batch reactor. Solution samples were collected periodically during the 24 hour exposure and analyzed for arsenic, iron, and sulfate ion. Pyrite oxidation is shown to dramatically increase with increasing chlorine concentrations as shown by measurements of released sulfate ion, used here as the reaction progress variable. EPMA maps also reveal complete oxidation of pyrite cements to Fe-oxyhydroxides at 1200 mg/L "free chlorine" and pH 7.0. This behavior does not occur at lower concentrations or higher pH. Arsenic release to solution does not appear to be directly correlated to increasing chlorine concentrations, but is governed by Fe-oxyhydroxide nucleation, which inhibits the release of dissolved arsenic at higher concentrations of chlorine.
Assessing the geologic sources of manganese in the Roanoke River watershed
Kiracofe, Zachary Aaron (Virginia Tech, 2015-06-01)
Elevated manganese (Mn) concentrations have been measured in groundwater within the Roanoke River watershed, Virginia. Concentrations of Mn often exceed the secondary drinking water standard. A historic belt of Mn ores, the James River-Roanoke River Manganese District (JRRRMD), occurs in the eastern part of the watershed. The project objectives were to 1) evaluate the formation of the JRRRMD ore deposits and 2) analyze existing groundwater chemistry data to evaluate sources and processes that control groundwater Mn. Analysis of ore minerals, morphologies, and chemistry provides support that the ore deposits are supergene in origin, consistent with previous work. Spatial correlations between Mn ore locations and stream terrace deposits support a model of ore formation in which Mn-oxides were precipitated near discharge zones as anoxic groundwater mixed with oxic groundwater. Terrace deposits present at elevations higher than modern streams suggests that topography has been inverted, allowing ores to be found at higher elevations than what is typically associated with ores formed in discharge zones. Analysis of groundwater chemistry data shows positive correlations between Mn, calcium and bicarbonate concentrations in groundwater, suggesting that carbonate-bearing lithologies are probable sources of Mn to groundwater. Regionally, groundwater flows toward the Roanoke River where the flowpath terminus is marked by elevated Mn. The inverse correlation of Mn with dissolved oxygen suggests that reducing conditions that develop along flowpaths allow for Mn to persist in groundwater. Overall, results suggest that the same processes that allowed for formation of the JRRRM ore deposits continue to occur today.
Assessing the Reactive Surface Area of Phlogopite during Acid Dissolution: An Atomic Force Microscopy, X-ray Photoelectron Spectroscopy, and Low Energy Electron Diffraction Study
Rufe, Eric (Virginia Tech, 2000-01-14)
The behavior during dissolution of edge and basal surfaces of the mica phlogopite were examined using in situ atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED) in an attempt to characterize the reactive surface area during dissolution. Mica minerals are the ideal material for this study because they offer a high degree of structural anisotropy. Therefore surfaces with different structures are easily identified. Dissolution is shown to proceed preferentially by removal of material from {hk0} edges. Dissolution rates were calculated by measuring the volume of material removed from etch pits, and normalizing to either the "reactive" surface area of {hk0} edges exposed at pit walls, or to a total "BET-equivalent" surface area. Rates normalized to total surface area are in the range of dissolution rates reported in the literature. Edge surface normalized rates are about 100 times faster. Long-term in situ AFM observations of phlogopite dissolution reveal that exposed (001) surfaces also display a distinct reactivity, though it operates on a different time scale. The top layer is shown to expand between 39 and 63 hours in contact with pH 2 HCl solution. Subsequent LEED analysis shows that the (001) surface becomes amorphous upon reacting with pH 2 HCl. Compositional characterization of the phlogopite after reaction shows that for pitted phlogopite surfaces, dissolution is characterized by leaching of octahedral cations and polymerization of the silica-enriched residual layer. No chemical changes or polymerization are observed for freshly cleaved unpitted phlogopite after reaction with pH 2 HCl for 24 hours. This suggests a gallery access mechanism is facilitated by edge attack, and is only significant on exposed (001) surfaces after a certain amount of dissolution by edge attack.
Assessment of Arsenic Mobility Using Sequential Extraction and Microscopic Methods
Basu, Ankan (Virginia Tech, 2006-08-09)
The mobility of arsenic is controlled by the mineral source of arsenic and a host of biogeochemical factors such as pH, oxidation-reduction reactions, precipitation-dissolution reactions, adsorption-desorption processes, and the activity of microorganisms. In this study, sequential extraction and microscopic methods were used to evaluate arsenic partitioning in different phases in sediments and host rock at the Brinton arsenic mine (BAM) site. Results demonstrate spatial variability of arsenic in sediments, although the partitioning of arsenic in different phases was similar in both mine tailing and stream channel sediments. The sequential extraction results demonstrate that between 60 and 80 % of the total arsenic in sediments is associated with iron oxides, and an additional phosphate extraction showed that the majority (80%) of arsenic associated with the oxides is adsorbed. Imaging and analysis by scanning electron microscopy (SEM) and electron microprobe analysis (EMPA) show the presence of three arsenic bearing minerals, arsenopyrite, scorodite and arsenic-rich iron oxides, in both sediment and the host rock. In sediment, the minerals are present as individual grains, but in the host rock, they are present together, often with arsenopyrite at the core, surrounded by scorodite and/or elemental sulfur, which is rimmed by iron oxides. This spatial arrangement illustrates two weathering patterns of arsenopyrite, one that involves oxidation to form scorodite, which further dissolves to form arsenic-rich iron oxides; in this weathering series, sulfur presumably forms dissolved species which migrate away from the mineral. Another pattern, observed in several samples of host rock, involves formation of elemental sulfur in addition to scorodite and iron oxides. Results of this study have implications for arsenic mobility at the Brinton site and other mine sites where arsenic minerals are present. Although arsenopyrite is the main ore mineral, the main reservoir of arsenic in sediments is iron oxides. However, in the end it is the biogeochemical mechanism that releases arsenic from the mineral that will control arsenic mobility. In the case of iron oxides, desorption or reductive dissolution will promote arsenic release, whereas oxidizing conditions are required for arsenopyrite to release arsenic.
Atomic Force Microscopy Study of Clay Mineral Dissolution
Bickmore, Barry Robert (Virginia Tech, 1999-12-09)
An integrated program has been developed to explore the reactivity of 2:1 phyllosilicates (biotite and the clays montmorillonite, hectorite, and nontronite) with respect to acid dissolution using in situ atomic force microscopy (AFM). Three techniques are described which make it possible to fix these minerals and other small particles to a suitable substrate for examination in the fluid cell of the atomic force microscope. A suite of macros has also been developed for the Image SXM image analysis environment which make possible the accurate and consistent measurement of the dimensions of clay particles in a series of AFM images, so that dissolution rates can be measured during a fluid cell experiment. Particles of biotite and montmorillonite were dissolved, and their dissolution rates normalized to their reactive surface area, which corresponds to the area of their edge surfaces (A_e). The A_e-normalized rates for these minerals between pH 1-2 are all ~10E^-8 mol/m²*s, and compare very well to other A_e-normalized dissolution rates in the literature. Differences between the A_e-normalized rates for biotite and the BET-normalized rates (derived from solution chemical studies) found in the literature can be easily explained in terms of the proportion of edge surface area and the formation of leached layers. However, the differences between the A_e-normalized montmorillonite rates and the literature values cannot be explained the same way. Rather, it is demonstrated that rates derived from solution studies of montmorillonite dissolution have been affected by the colloidal behavior of the mineral particles. Finally, the dissolution behavior of hectorite (a trioctahedral smectite) and nontronite ( a dioctahedral smectite) were compared. Based on the differential reactivity of their crystal faces, a model of their surface atomic structures is formulated using Hartman-Perdock crystal growth theory, which explains the observed data if it is assumed that the rate-determining step of the dissolution mechanism is the breaking of connecting bonds between the octahedral and tetrahedral sheets of the mineral structure.
Biogeochemical controls on arsenic cycling in a hydrocarbon plume
Ziegler, Brady Allen (Virginia Tech, 2018-07-30)
Arsenic (As) in drinking water poses a critical threat to public health. More than 150 million people worldwide are at risk of developing diseases from unsafe concentrations of As in groundwater. Arsenic occurs naturally in rocks, soils, and sediments and generally remains associated with solid phases. However, changes in aquifer geochemistry can mobilize As into groundwater, contaminating drinking water sources. This dissertation investigates As cycling in an aquifer contaminated by petroleum hydrocarbons near Bemidji, Minnesota, where As is mobilized into groundwater due to biodegradation of hydrocarbons coupled to reduction of ferric oxides. The first project describes how aquifer sediments act as both sources and sinks for As in groundwater, depending on the prevailing redox conditions. Results show that As is released to groundwater near the hydrocarbon source but is removed near the hydrocarbon plume's leading edge. Comparison of data from 1993 to 2016 shows that As has been redistributed in aquifer sediment as the plume has expanded over time. The second project presents a mass balance for As, which shows that despite elevated As in groundwater (up to 230 μg/L), >99.7% of As mass in the aquifer is in sediments. Calculations demonstrate that As in sediment can be 22x less than the method detection limit and still cause unsafe concentrations in groundwater, suggesting that the use of standard methods limits our ability to predict where naturally occurring As poses a threat to groundwater. In the third project, a reactive transport model simulates As cycling for 400 years. Results show that sorption of As to ferrihydrite limits As transport within 300 m of the hydrocarbon source. Modeling predicts that over the plume's lifespan, more groundwater will be contaminated by As than benzene, the primary contaminant of concern in hydrocarbon plumes. Combined, these studies suggest that many aquifers are vulnerable to unsafe As concentrations due to mobilization of natural As if bioavailable organic carbon is introduced. Although aquifers can attenuate As, it may take centuries for As to be fully removed from groundwater, suggesting it is prudent to account for natural contaminants like As when developing remediation strategies at petroleum spill sites.
Biologically Controlled Mineralization and Demineralization of Amorphous Silica
Wallace, Adam F. (Virginia Tech, 2008-04-24)
Living systems possess seemingly bottomless complexity. Attempts to parse the details of one cellular process from all other concurrent processes are challenging, if not daunting undertakings. The apparent depth of this problem, as it pertains to biomineralization, is related to the small number of existing studies focused on the development of a mechanism-based understanding of intracellular mineralization processes. Molecular biologists and geneticists have only begun to turn their attention towards identification and characterization of molecules involved in regulating and controlling biomineral formation. With this new knowledge, a number of new and exciting research opportunities are currently awaiting development upon a barren landscape. Silica biomineralization is one of these emerging frontiers. As new information about the chemical and structural nature of the macromolecules involved in biosilicification is revealed, the means these species employ to control the temporal and spatial onset of silica deposition in vivo become available for exploration. The first chapter of this dissertation outlines those aspects of silicate metabolism that are directly relevant to the controlled biomineralization of silica in eukaryotic organisms and identifies pervasive and unanswered questions surrounding biosilica formation. Particular attention is paid to the diatoms, which are the most abundant, and extensively investigated silica-mineralizing organisms in modern seas. The extent, and mechanism through which specific organic moieties work individually or in concert to direct mineral formation at biological interfaces is a central concern of modern biomineralization research. Chapter two addresses this forefront issue for silica mineralizing systems, and reports the results of an experimental investigation designed to measure the effects of individual surface-bound organic functional groups on the rate of surface-directed silica nucleation. Chapter three discusses an additional aspect of this research aimed at investigating the reactivity of nanoparticulate biogenic silica produced by marine phytoplankton and terrestrial plants in natural environments. Density Functional Theory and ab initio molecular orbital calculations are employed to explore potential mechanisms underlying the catalytic activity of divalent metal cations during the hydrolysis of Si – O bonded networks.
Biomolecular Controls on Calcium Carbonate Formation by Amorphous and Classical Pathways: Insights from Measurements of Nucleation Rates and Isotope Tracers
Giuffre, Anthony J. (Virginia Tech, 2015-04-26)
Calcified skeletons are produced within complex assemblages of proteins and polysaccharides whose roles in mineralization are not well understood. Researchers have long postulated that living organisms utilize the macromolecules of organic matrices to actively guide the formation of crystal structures. The timing and placement of the subsequent minerals that form are most easily controlled during nucleation; however, a physical and chemical picture of how organic functional group chemistry influences the initial stages of nucleation is not yet established. These processes are further complicated by the realization that carbonate biominerals can form by an amorphous to crystalline transformation process, which has prompted the question of how chemical signatures are recorded during mineralization. Investigations of mineralization processes such as the kinetics of nucleation and the transformation of amorphous calcium carbonate (ACC) to crystalline products are critical to building a better understanding of biomineral formation. Only from that fundamental basis can one begin to decipher changes in climate and seawater chemistry over geologic time and by recent anthropogenic effects. This dissertation presents the findings from experimental studies of the thermodynamics and kinetics of multiple mineral formation processes, including nucleation and transformation from an amorphous phase. The kinetics of calcite nucleation onto a suite of high-purity polysaccharide (PS) substrates were quantified under controlled conditions. Nucleation rates were measured as a function of 1) supersaturation extending above and below ACC solubility and 2) ionic strength extending to seawater salinity. These conditions decipher the chemical interactions between the PS substrate, calcite crystal, and solution. These investigations show the energy barrier to calcite formation is regulated by competing interfacial energies between the substrate, crystal, and liquid. The energy barriers to nucleation are PS-specific by a systematic relationship to PS charge density and substrate structure that is rooted in minimization of the competing substrate-crystal and substrate-liquid interfacial energies. The data also suggest ionic strength regulates nucleation barriers through substrate-liquid and crystal-liquid interfacial energetics. In a second experimental study, stable isotope labeling was used to directly probe the transformation pathway. Four processes were considered: dissolution-reprecipitation, solid-state, or combinations of these end member processes. Isotope measurements of calcite crystals that transform from ACC have signatures that are best explained by dissolution-reprecipitation. The extent of isotopic mixing correlates with the amount of ACC transferred and the time to transformation, suggesting the calcite crystals are recording the changing local solution environment during the transformation. These investigations into different mineralization mechanisms build a framework for how functional group chemistries of organic molecules regulate mineralization and the resulting isotopic and elemental signatures in the calcite. This may provide useful insights to interpreting chemical signatures of carbonate biominerals in fossil record and understanding ocean chemistry changes throughout geologic time.
Bioreduction of Hematite Nanoparticles by Shewanella oneidensis MR-1
Bose, Saumyaditya (Virginia Tech, 2006-12-08)
A dissertation is presented on the bioreduction of hematite (α-Fe2O3) nanoparticles. The study shows that an alternative extracellular electron transfer mechanism other than the classical 'direct-contact' mechanism may be simultaneously employed by Shewanella oneidensis MR-1 during solid-phase metal reduction. This conclusion is supported by analysis of the bioreduction kinetics of hematite nanoparticles coupled with microscopic investigations of cell-mineral interactions. The reduction kinetics of metal-oxide nanoparticles were examined to determine how S. oneidensis utilizes these environmentally-relevant solid-phase electron acceptors. Nanoparticles involved in geochemical reactions show different properties relative to larger particles of the same phase, and their reactivity is predicted to change as a function of size. To demonstrate these size-dependent effects, the surface area normalized reduction rates of hematite nanoparticles by S. oneidensis MR-1 with lactate as the sole electron donor were measured. As evident from whole cell TEM analysis, the mode of nanoparticle adhesion to cells is different between the more aggregated, pseudo-hexagonal to irregular shaped 11 nm, 12 nm, 99 nm and the less aggregated 30 nm and 43 nm rhombohedral particles. The 11 nm, 12 nm and 99 nm particles show less cell contact and coverage than the 30 nm and 43 nm particles but still show significant rates of reduction. This leads to the provisional speculation that S. oneidensis MR-1 employs a pathway of indirect electron transfer in conjunction with the direct-contact pathway, and the relative importance of the mechanism employed depends upon aggregation level and the shape of the particles or crystal faces exposed. In accord with the proposed increase in electronic band-gap for hematite nanoparticles, the smallest particles (11 nm) exhibit one order of magnitude decrease in reduction when compared with larger (99 nm) particles, and the 12 nm rates fall in between these two. This effect may also be due to the passivation of the mineral and cell surfaces by Fe(II), or decreasing solubility due to decrease in size.
Calcification by amorphous carbonate precursors: Towards a new paradigm for sedimentary and skeletal mineralization
Wang, Dongbo (Virginia Tech, 2010-11-29)
A new paradigm for the formation of calcified skeletons suggests mineralization proceeds through amorphous calcium carbonate (ACC) precursors. The implications of this strategy in carbonate crystallization are widespread, particularly for understanding factors controlling impurity and isotopic signatures in calcium carbonates. The first chapter is a literature review of the biomineralization processes used by two important model organisms: the sea urchin larva and the foraminifera. Sea urchin larvae provide a thoroughly studied example of mineralization by an ACC pathway that is under biological control through regulation of protein chemistry and the local mineralization environment. A review of how foraminifera produce their test structures is also examined to explore the question of how organisms regulate the Mg content in proportion to the temperature their environments of formation. The second chapter demonstrates that acidic biomolecules regulate the composition of ACC for a suite of model carboxylated molecules. The physical basis for the systematic trend in Mg content is related to the ability of the affinity of the biomolecule for binding Ca versus Mg. The third chapter builds on these findings to explore the transformation of Mg-rich ACC precursors to calcites of exceptionally high Mg-contents that could not be produced by classical step-dominated growth processes. The data indicate that these materials are likely a result of a nucleation-dominated pathway. The final, fourth chapter develops Raman spectroscopy-based calibrations for determining Mg contents in ACC. The calibrations are based upon peak position or peak width of the carbonate υ₁ stretch.
Calcium carbonate biomineralization: A theoretical and experimental investigation of biomolecular controls on nucleation and growth
Hamm, Laura Mae (Virginia Tech, 2012-04-30)
Organisms have evolved a remarkable ability to mineralize complex skeletons and functional biomaterials. These structures are nucleated and grown in close associaiton with macromolecular assemblages of proteins and polysaccharides that are implicated in regulating all stagees of mineralization. Because of this intimate association of organic with inorgaic components, many studies have investigated the effects of particular organic species on mineral morphology, phase, and growth rate. However, the diversity and species-specific nature of the organic assemblages associated with biominerals across a wide variety of taxa, has limited our understanding of how organisms use biomolecules to regulate skeletal formation. It is clear that a mechanistic picture of biomolecular controls on mineralization requires molecular-level investigations of the interplay between organic and inorganic components at all stages of crystallizaiton. This dissertation presents the findings from theoretical and experimental studies of the physical mechanisms that underlie biomolecule controls on mineral formation. Molecular dynamics simulations probe the effects of acidic molecules on the hydration of alkaline earth cations. After first calculating baseline hydration properties for magnesium, calcium, strontium, and barium, I determine the effects of carboxylate-containing molecules on cation hydration state as well as the kinetics and thermodynamics of water exchange. Experimental work utilizes self-assembled monolayers as proxies for matrix macromolecules in order to understand their effects on CaCO3 nucleation kinetics and thermodynamics. Estimates of nucleation rates and barriers are made from optical microscopy data and correlated with measurements of crystal – substrate rupture force from dynamic force microscopy. These investigations show that an important function of biomolecules in directing mineralization lies in their ability to modulate cation hydration. Both chemical functionality and molecular conformation are influential in regulating the kinetics and thermodynamics of mineral nucleation, and these effects may be predicted by the strength of interaction between organic and inorganic components. These findings contribute to a mechanistic understanding of how organic matrices act to regulate biomineral formation. They demonstrate a plausible physical basis for how carboxyl-rich biomolecules accelerate the kinetics of biomineral growth and suggest roles for organic species in the nucleation and pre-nucleation stages of mineralization.
Carbon dioxide (CO2) sorption to Na-rich montmorillonite at Carbon Capture, Utilization and Storage (CCUS) P-T conditions in saline formations
Krukowski, Elizabeth Gayle (Virginia Tech, 2013-01-24)
Carbon capture, utilization and storage (CCUS) in confined saline aquifers in sedimentary formations has the potential to reduce the impact of fossil fuel combustion on climate change by storing CO2 in geologic formations in perpetuity. At PT conditions relevant to CCUS, CO2 is less dense than the pre-existing brine in the formation, and the more buoyant CO2 will migrate to the top of the formation where it will be in contact with cap rock. A typical cap rock is clay-rich shale, and interactions between shales and CO2 are poorly understood at PT conditions appropriate for CCUS in saline formations. In this study, the interaction of CO2 with clay minerals in the cap rock overlying a saline formation has been examined, using Na-rich montmorillonite as an analog for clay-rich shale. Attenuated Total Reflectance -- Fourier Transform Infrared Spectroscopy (ATR -FTIR) was used to identify potential crystallographic sites (AlAlOH, AlMgOH and interlayer space) where CO2 could interact with montmorillonite at 35"C and 50"C and from 0-1200 psi. Analysis of the data indicates that CO2 that is preferentially incorporated into the interlayer space, with dehydrated montmorillonite capable of incorporating more CO2 than hydrated montmorillonite. No evidence of chemical interactions between CO2 and montmorillonite were identified, and no spectroscopic evidence for carbonate mineral formation was observed. Further work is needed to determine if reservoir seal quality is more likely to be degraded or enhanced by CO2 - montmorillonite interactions.

Browsing by Author "Rimstidt, J. Donald"

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