Browsing by Author "Tadanier, Christopher J."

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    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.
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    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.
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    Colloid Formation for the Removal of Natural Organic Matter during Iron Sulfate Coagulation
    Masters, Erika N. (Virginia Tech, 2003-05-29)
    Removal of organic matter is increasingly important to drinking water utilities and consumers. Organic matter is a significant precursor in the formation of disinfection by-products (DBPs). The maximum contaminant levels for (DBPs) are decreasing and more DBPs are believed carcinogenic. Traditional coagulation focuses on the removal of particulate matter and in the last decade soluble species have also been targeted with high coagulant doses. However, colloidal matter is smaller than particulate matter and therefore not easily removed by conventional drinking water treatment. This research focused on the conversion of soluble organic matter to colloids using relatively low doses of ferric sulfate coagulant and the subsequent removal of the colloids by filtration during drinking water treatment. The goal is to achieve enhanced removal of soluble organic matter with minimal chemical costs and residual formation. This study investigated the effects of pH, iron coagulant dose, turbidity, organic matter concentration, and temperature on colloid formation. Characterization of the colloidal organic matter was attempted using zeta potential and sizing analyses. Cationic low molecular weight, nonionic high molecular weight, and cationic medium molecular weight polymers were evaluated on their removal of colloidal organic matter. Colloidal organic matter formation was affected by changes in coagulation pH, coagulant dose, and organic matter concentration, whereas turbidity and temperature did not significantly impact colloid formation. Decreased coagulation pH caused increased organic carbon removal. As coagulant dose was increased, colloid formation initially increased to maximum and subsequently rapidly decreased. Colloid formation was increased as the organic matter concentration increased. Due to low sample signal, the colloids could not be characterized using zeta potential and sizing analyses. In addition, polymers were ineffective for aggregating colloidal organic matter when used as flocculant aids.
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    Colloid Formation Resulting from Alum Coagulation of Organic-Laden Sourcewaters
    Hardin, William Michael (Virginia Tech, 2003-09-10)
    This research evaluated natural organic matter (NOM) dissolved-solid phase separation resulting from alum coagulation under the following sourcewater conditions: pH, initial NOM concentration, initial turbidity, and temperature. The solid phase was partitioned into two operationally defined size fractions; colloidal matter was defined as organic carbon (OC) retained by a 30 kilodalton ultrafiltration membrane, and particulate matter was defined as OC retained by a 1μm glass-fiber filter. Coagulation pH had a considerable impact on residual OC colloid formation, signified by more colloids formed as a function of alum dose at pH 6.8 as compared to pH 5.8. Initial NOM concentration strongly influenced the alum dose range over which OC colloid formation occurred and was found to be a proportional relationship. The presence of bentonite clay (used as the initial turbidity source) somewhat affected OC colloid formation by exerting some amount of coagulant demand, signified by decreasing OC colloid formation with increasing initial turbidity. Coagulation temperature had a considerable impact on particulate matter formation, as there was an increase in the dose at which particle formation first occurred at 4 ºC when compared to 25 ºC. Phase separation of OC from dissolved to colloidal matter was very similar at both 4 ºC and 25 ºC. The ability for low doses of polymers to replace a large portion of alum in order to further aggregate colloids during flocculation was unsuccessfully investigated. OC phase separation resulting from alum and iron sulfate coagulation was compared on a molar coagulant metal basis. The amount of residual OC associated with colloidal matter was similar, while the critical coagulant dose at which particulate matter formed was shifted to a much higher dose for iron.
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    Competitive Adsorption of Arsenite and Silicic Acid on Goethite
    Luxton, Todd Peter (Virginia Tech, 2002-12-12)
    The adsorption behavior of silicic acid and arsenite alone and competitively on goethite over a broad pH range (3-11) at environmentally relevant concentrations was investigated utilizing pH adsorption data and zeta potential measurements. Both addition scenarios (Si before As(III) and As(III) before Si) were examined. The results of the adsorption experiments and zeta potential measurements were then used to model the single ion and competitive ion adsorption on goethite with the CD-MUSIC model implemented in the FITEQL 4.0 computer program. Silicic acid adsorption was reduced by the presence of arsenite for all but one of the adsorption scenarios examined, while in contrast silicic acid had little effect upon arsenite adsorption. However, the presence of silicic acid, regardless of the addition scenario, dramatically increased the arsenite equilibrium solution concentration over the entire pH range investigated. The CD-MUSIC model was able to predict the single ion adsorption behavior of silicic acid and arsenite on goethite. The modeled zeta potential data provided further evidence of the CD-MUSIC model's ability to describe the single anion adsorption on goethite. Our model was also able to collectively describe adsorption and zeta potential data for the low Si-arsenite adsorption scenario quite well however, our model under-predicted silicic acid adsorption for the high Si-arsenite competitive scenario.
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    Experimentally Derived Sticking Efficiencies of Microparticles using Atomic Force Microscopy: Toward a Better Understanding of Particle Transport
    Cail, Tracy (Virginia Tech, 2003-12-18)
    It is estimated that there are 5x1030 microorganisms on Earth and that approximately 50% live in unconsolidated sediment on the terrestrial subsurface. Subsurface disturbances caused by the constant search for natural resources and our dependence on groundwater make the abundance and diversity of these organisms a global concern. It is vital to many environmental fields, including bioremediation, water purification, and contaminant transport, that we understand how microorganisms and other colloidal particles attach to and detach from natural sediments and ultimately how they travel through porous media. Sticking efficiency (alpha) is a major component of most particle transport theories. It is defined as the ratio of particles that adhere to a collector surface compared to the total number of particles that collide with that surface. In this study, the Interaction Force Boundary Layer (IFBL) model was used to determine the sticking efficiencies of inorganic colloidal particles and Enterococcus faecalis cells against a silica glass collector surface. Sticking efficiencies were derived from intersurface potential energies that were determined from integrated force-distance data measured by Atomic Force Microscopy (AFM). Force data were measured in buffered aqueous solutions of varying pH and ionic strength to determine the influence of solution chemistry on particle removal from solution. Zeta-potentials were measured to determine the impact of particle and collector surface charge on force measurements. The results of this study indicate that alpha is strongly influenced by solution chemistry. The response of alpha to small changes in solution pH and ionic strength may be several orders of magnitude. Zeta-potential measurements imply that sticking efficiencies are strongly influenced by the electrical charges on both the particle and collector surfaces. Zeta-potentials of bacteria did not vary significantly with changing solution pH, but did respond to changing solution ionic strength. Historically, alpha has been very difficult to predict. This study is the first to report sticking efficiencies measured using AFM and the first to successfully apply the IFBL model to colloidal particles. Æ nThe incorporation of empirical nanoscale interactions into the measurement of alpha promises to more successfully describe particle adhesion and, thus, particle transport.
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    Exploring Siderophore-Mineral Interaction Using Force Microscopy and Computational Chemistry
    Kendall, Treavor Allen (Virginia Tech, 2003-04-11)
    The forces of interaction were measured between the siderophore azotobactin and the minerals goethite (FeOOH) and diaspore (AlOOH) in solution using force microscopy. Azotobactin was covalently linked to a hydrazide terminated atomic force microscope tip using a standard protein coupling technique. Upon contact with each mineral surface, the adhesion force between azotobactin and goethite was two to three times the value observed for the isostructural Al-equivalent diaspore. The affinity for the solid iron oxide surface reflected in the force measurements correlates with the specificity of azotobactin for aqueous ferric iron. Further, the adhesion force between azotobactin and goethite significantly decreases when small amounts of soluble iron are added to the system suggesting a significant specific interaction between the azotobactin and the mineral surface. Changes in the force signature with pH and ionic strength were fairly predictable when considering mineral solubility, the charge character of the mineral surfaces, the molecular structure of azotobactin, and the intervening solution. Molecular and quantum mechanical calculations which were completed to further investigate the interaction between azotobactin and iron/aluminum oxide surfaces, and to more fully understand the force measurements, also showed an increased force affinity for Fe over Al. Ab initio calculations on siderophore fragment analogs suggest the iron affinity can be attributed to increased electron density associated with the Fe-O bond compared to the Al-O bond; an observation that correlates with iron's larger electronegativity compared to aluminum. Attachment of the ligand to each surface was directed by steric forces within the molecule and coulombic interactions between the siderophore oxygens and the metals in the mineral. Chelating ligand pairs coordinated with neighboring metal atoms in a bidentate, binuclear geometry. Upon simulated retraction of azotobactin from each surface, the Fe-O(siderophore) bonds persisted into a higher force regime than Al-O(siderophore) bonds, and surface metals were removed from both minerals. Extrapolation of the model to more realistic hydrated conditions using a PCM model in the quantum mechanical calculations and water clusters in the molecular mechanical model demonstrated that the presence of water energetically favors and enhances metal extraction, making this a real possibility in a natural system.
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    Influence of Operational Characterization Methods on DOM Physicochemical Properties and Reactivity with Aqueous Chlorine
    Tadanier, Christopher J. (Virginia Tech, 1998-06-12)
    The physicochemical properties and chemical reactivity of dissolved organic matter (DOM) are of tremendous practical significance in both natural and engineered aquatic and terrestrial systems. DOM is frequently extracted, fractionated, and concentrated from environmental samples using a variety of operationally defined physical and chemical processes in order to facilitate study of specific physicochemical properties and aspects of its chemical reactivity. This study was conducted to systematically examine the influence of operationally defined physical and chemical characterization methods on observed DOM physicochemical properties and reactivity with aqueous chlorine. The effects of chemical separation were evaluated by applying an existing resin adsorption based procedure which simultaneously extracts and fractionates DOM and inorganic constituents into hydrophobic and hydrophilic acid, base, and neutral dissolved material matrix (DMM) fractions. Physical separation based on DOM apparent molecular weight (AMW) was also evaluated using batch ultrafiltration (UF) data in conjunction with a suitable membrane permeation model. Linear independence of membrane solute transport was theoretically described using non-equilibrium thermodynamics and experimentally demonstrated for AMICON® YC/YM series UF membranes. Mass balances on DMM fraction constituents in untreated and previously coagulated natural waters indicated that quantitative recovery (100 ± 2%) of DOM constituents was achieved, while recovery of inorganic constituents such as iron and aluminum was substantially incomplete (30%-74%). Comparison of whole-water DOM properties with those mathematically reconstituted from DMM fractions demonstrated a marked shift in DOM properties toward lower AMW. Evidence of pH induced partial hydrolysis of protein, polysaccharide, and ester DOM components was also observed. Decreased specific Cl2 demand (mmol DCl2/ mmol DOM) and specific trihalomethane formation (mmol THM/mmol DOM) following chemical fractionation were attributed to increased molar DOM concentration and decreased DOM association with colloidal iron oxide surfaces. Collectively, the results of this research indicate that operational characterization methods result in alteration of DOM physicochemical properties and reactivity with aqueous chlorine, and caution is therefore advisable when interpreting the results of studies conducted using chemically extracted or fractionated DOM.
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    Mineral-Microbe Interactions Probed in Force, Energy, and Distance Nanospace
    Lower, Steven K. (Virginia Tech, 2001-02-22)
    Biological force microscopy (BFM) was developed to quantitatively measure pico- to nano-Newton forces (10-9 to 10-12 N) as a function of the nanoscale distance (nanometers) between living bacteria and mineral surfaces, in aqueous solution. Native cells were linked to a force-sensing probe, which was used in a force microscope to measure attractive and repulsive forces as a mineral surface approached, made contact with, and subsequently withdrew from a bacterium on the probe. The resulting data were used to interpret the interactive dynamics operative between bacteria and mineral surfaces under environmentally relevant conditions. BFM was used to study bacterial adhesion to mineral surfaces. In the case of Escherichia coli interactions with goethite, graphite, and muscovite, attractive and repulsive forces were detected at ranges up to 400 nanometers, the magnitude and sign depending on the ionic strength of the intervening solution and the mineral surface charge and hydrophobicity. Adhesion forces, up to several nanoNewtons in magnitude and exhibiting various fibrillation dynamics, were also measured and reflect the complex interactions of structural and chemical functionalities on the bacteria and mineral surfaces. In the study of Burkholderia cepecia interactions with mica, it was found that the physiological condition of the cell affected the observed adhesion forces. Cells grown under oligotrophic conditions exhibited an increased affinity for the mineral surface as opposed to cells grown under eutropic conditions. BFM was also used to characterize the transfer of electrons from biomolecules on Shewanella oneidensis to Fe(III) in the structure of goethite. Force measurements with picoNewton resolution were made in aqueous solution under aerobic and anaerobic conditions. Energy values (in attoJoules) derived from these measurements show that the affinity between S. oneidensis and goethite rapidly increases by two to five times under anaerobic conditions where electron transfer from bacterium to mineral is expected. Specific signatures in the force curves, analyzed with the worm-like chain model of protein unfolding, suggest that the bacterium recognizes the mineral surface such that a 150 kDa putative, iron reductase is quickly mobilized within the outer membrane of S. oneidensis and specifically interacts with the goethite surface to facilitate the electron transfer process.
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    Nanoscience Meets Geochemistry: Size-Dependent Reactivity of Hematite
    Madden, Andrew Stephen (Virginia Tech, 2005-06-02)
    Recent studies have demonstrated that nanoscale crystalline iron oxide minerals are common in natural systems. The discipline of nanoscience suggests that these particles in the size range of approximately 1-50 nm will have properties that deviate from the bulk properties of the same material and that these properties will change as a function of particle size. This study begins to fill the void of corresponding experimental investigations that apply the principles of nanoscience to the geochemical reactivity of nanominerals. The rate of Mn²⁺(aq) oxidation on hematite with average diameters of 7.3 nm and 37 nm was measured in the presence of O₂(aq). In the pH range of 7-8, the surface area normalized rate was one to two orders of magnitude greater on the 7.3 nm average diameter particles. Based on the application of electron transfer theory, it is hypothesized that the particles with diameters less than approximately 10 nm have surface crystal chemical environments which distort the symmetry of the MnMn²⁺ surface complex, reducing the energy required to reorganize the coordinated ligands after oxidation to Mn³⁺. Cu²⁺, an analog for Mn³⁺, was used to probe for the presence and nature of the proposed changes in surface structure. Cu²⁺ and Mn³⁺ show similar electronic structure changes in response to the surrounding crystal field due to their d-electron configurations and Jahn-Teller coordinative distortions. Batch sorption experiments on hematite nanoparticles revealed a shift in the pH-dependent adsorption of Cu²⁺(aq). Specifically, an affinity sequence of 7 nm > 25 nm = 88 nm was determined based on the shift of the 7 nm sorption edge to approximately 0.8 pH units lower than that for the 25 nm and 88 nm samples. These data support the hypothesis that unique binding sites exist on the 7 nm nanoparticles that are not significantly present on the larger particles. The National Nanotechnology Initiative stresses the need to address the broader societal impacts of nanoscale research. This dissertation embraces this viewpoint through the development and inclusion of "Nano2Earth: Introducing Nanotechnology Through Investigations of Groundwater," a curriculum which combines nanoscience with the Earth sciences for high school students.