Browsing by Author "Schreiber, Madeline E."

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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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    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.
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    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.
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    Analyzing a 10-Year Cave Drip Record in James Cave, Virginia: Implications for Storage and Recharge in Shallow Appalachian Karst Systems
    Groce-Wright, Nigel C. (Virginia Tech, 2021-07-16)
    Karst aquifers, characterized by soluble rocks such as limestone and dolostone, provide drinking water to 20-25% of the world's population and are thus critical global water sources. However, recent work suggests that rapid alteration of karst aquifers due to the impact of climate change on precipitation patterns may affect recharge to these aquifers. Much of the research on recharge in karst aquifers has relied on using patterns of spring discharge to quantify recharge. Spring outlets allow for continuous monitoring of discharge from karst aquifers, making them easily accessible monitoring sites. However, because springs can integrate multiple flow paths, it is difficult to rely on spring discharge patterns to get information on where and how karst aquifers are receiving recharge. Monitoring closer to the source of recharge through the measurement of cave drips allows for a more accurate analysis of recharge timing and mechanisms. In this study, I conducted recession analyses on cave drip hydrographs from a 10-year record (2008-2018) of three drip monitoring stations within James Cave (Pulaski Co., VA) to: 1) examine differences in hydrologic characteristics of the epikarst (the zone of soil and weathered bedrock above a karst aquifer); 2) quantify the storage volume of the epikarst and 3) investigate seasonal, and annual trends in recharge. Results of recession analysis show heterogeneity in epikarst hydrologic characteristics, reflected by calculations of the recession coefficient, , and storage volume. Calculations of the recession coefficient show subtle differences between the three drip sites, suggestive of spatial heterogeneity in permeability and storage in the overlying epikarst. The storage volume calculations show that during the recharge season (winter- spring), up to 95% of recharge through the unsaturated zone to the cave occurs through rapid pathways (i.e., fractures), and 5% through diffuse pathways (i.e., pores). However, during the recession period (spring-summer), when evapotranspiration is active, recharge through cave drips decreases and occurs predominantly through diffuse flow. Combined, these results underscore the importance of both spatial and temporal characterization of drip rates and other recharge inputs into karst aquifer systems.
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    Anoxia decreases the magnitude of the carbon, nitrogen, and phosphorus sink in freshwaters
    Carey, Cayelan C.; Hanson, Paul C.; Thomas, R. Quinn; Gerling, Alexandra B.; Hounshell, Alexandria G.; Lewis, Abigail S.; Lofton, Mary E.; McClure, Ryan P.; Wander, Heather L.; Woelmer, Whitney M.; Niederlehner, B.R.; Schreiber, Madeline E. (Wiley, 2022-05-05)
    Oxygen availability is decreasing in many lakes and reservoirs worldwide, raising the urgency for understanding how anoxia (low oxygen) affects coupled biogeochemical cycling, which has major implications for water quality, food webs, and ecosystem functioning. Although the increasing magnitude and prevalence of anoxia has been documented in freshwaters globally, the challenges of disentangling oxygen and temperature responses have hindered assessment of the effects of anoxia on carbon, nitrogen, and phosphorus concentrations, stoichiometry (chemical ratios), and retention in freshwaters. The consequences of anoxia are likely severe and may be irreversible, necessitating ecosystem-scale experimental investigation of decreasing freshwater oxygen availability. To address this gap, we devised and conducted REDOX (the Reservoir Ecosystem Dynamic Oxygenation eXperiment), an unprecedented, 7-year experiment in which we manipulated and modeled bottom-water (hypolimnetic) oxygen availability at the whole-ecosystem scale in a eutrophic reservoir. Seven years of data reveal that anoxia significantly increased hypolimnetic carbon, nitrogen, and phosphorus concentrations and altered elemental stoichiometry by factors of 2–5× relative to oxic periods. Importantly, prolonged summer anoxia increased nitrogen export from the reservoir by six-fold and changed the reservoir from a net sink to a net source of phosphorus and organic carbon downstream. While low oxygen in freshwaters is thought of as a response to land use and climate change, results from REDOX demonstrate that low oxygen can also be a driver of major changes to freshwater biogeochemical cycling, which may serve as an intensifying feedback that increases anoxia in downstream waterbodies. Consequently, as climate and land use change continue to increase the prevalence of anoxia in lakes and reservoirs globally, it is likely that anoxia will have major effects on freshwater carbon, nitrogen, and phosphorus budgets as well as water quality and ecosystem functioning.
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    Applying the RUSLE and SEDD Equations to an Agricultural Watershed in Southwest Virginia - A Case Study in Sediment Yield Estimation Using GIS
    Lally, Lindsay Backus (Virginia Tech, 2013-06-12)
    The goal of this study is to develop a model using GIS to estimate the source and quantity of accumulated sediment in the Emory & Henry College (EHC) duck pond.  Located in the Highlands of Southwest Virginia, the 1,194 acre duck pond watershed consists primarily of agricultural, forested, and low density urban land uses. The Revised Universal Soil Loss Equation (RUSLE) and the Sediment Distributed Delivery (SEDD) prediction models were used to determine the quantity of eroded sediment and the sediment yield at the duck pond, respectively.  These models require numerous computations, which were performed at the watershed scale with the aid of ArcGIS software.  In ArcGIS the watershed was broken into a raster grid of approximately 5,200 discrete 100 foot by 100 foot grid cells. The resulting watershed erosion model identified two main sources of sediment: a cluster of farms relatively close to and east of the duck pond, and a harvested timber site north of the duck pond.  The model predicted that 1,076 tons of sediment are delivered into the duck pond annually. The estimated sediment yield was then compared to the estimated amount deposited between October 2011 and September 2012, as measured by a topographic survey.  The model prediction was found to be within a factor of 6.3x of the measured value.  The predicted and measured sediment yields as well as identified erosion sources can be used to develop a water quality improvement plan and to help alleviate the need for periodic dredging.
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    Arsenic in Petroleum-Contaminated Groundwater near Bemidji, Minnesota Is Predicted to Persist for Centuries
    Ziegler, Brady A.; Ng, G.-H. Crystal; Cozzarelli, Isabelle M.; Dunshee, Aubrey J.; Schreiber, Madeline E. (MDPI, 2021-05-26)
    We used a reactive transport model to investigate the cycling of geogenic arsenic (As) in a petroleum-contaminated aquifer. We simulated As mobilization and sequestration using surface complexation reactions with Fe(OH)3 during petroleum biodegradation coupled with Fe-reduction. Model results predict that dissolved As in the plume will exceed the U.S. and EU 10 µg/L drinking water standard for ~400 years. Non-volatile dissolved organic carbon (NVDOC) in the model promotes As mobilization by exerting oxygen demand, which maintains anoxic conditions in the aquifer. After NVDOC degrades, As re-associates with Fe(OH)3 as oxygenated conditions are re-established. Over the 400-year simulation, As transport resembles a “roll front” in which: (1) arsenic sorbed to Fe(OH)3 is released during Fe-reduction coupled to petroleum biodegradation; (2) dissolved As resorbs to Fe(OH)3 at the plume’s leading edge; and (3) over time, the plume expands, and resorbed As is re-released into groundwater. This “roll front” behavior underscores the transience of sorption as an As attenuation mechanism. Over the plume’s lifespan, simulations suggest that As will contaminate more groundwater than benzene from the oil spill. At its maximum, the model simulates that ~5.7× more groundwater will be contaminated by As than benzene, suggesting that As could pose a greater long-term water quality threat than benzene in this petroleum-contaminated aquifer.
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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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    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.
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    Arsenic release to the environment from hydrocarbon production, storage, transportation, use and waste management
    Schreiber, Madeline E.; Cozzarelli, Isabelle M. (2021-06-05)
    Arsenic (As) is a toxic trace element with many sources, including hydrocarbons such as oil, natural gas, oil sands, and oil- and gas-bearing shales. Arsenic from these hydrocarbon sources can be released to the environment through human activities of hydrocarbon production, storage, transportation and use. In addition, accidental release of hydrocarbons to aquifers with naturally occurring (geogenic) As can induce mobilization of As to groundwater through biogeochemical reactions triggered by hydrocarbon biodegradation. In this paper, we review the occurrence of As in different hydrocarbons and the release of As from these sources into the environment. We also examine the occurrence of As in wastes from hydrocarbon production, including produced water and sludge. Last, we discuss the potential for As release related to waste management, including accidental or intentional releases, and recycling and reuse of these wastes.
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    Arsenic transport in groundwater, surface water, and the hyporheic zone of a mine-influenced stream-aquifer system
    Brown, Brendan (Virginia Tech, 2005-12-12)
    We investigated the transport of dissolved arsenic in groundwater, surface water and the hyporheic zone in a stream-aquifer system influenced by an abandoned arsenopyrite mine. Mine tailing piles consisting of a host of arsenic-bearing minerals including arsenopyrite and scorodite remain adjacent to the stream and represent a continuous source of arsenic. Arsenic loads from the stream, springs, and groundwater were quantified at the study reach on nine dates from January to August 2005 and a mass-balance approach was used to determine hyporheic retention. Arsenic loading from the groundwater was the dominate source of arsenic to the stream, while loads from springs represented a substantial proportion of the total arsenic load during spring. Arsenic loads in surface and groundwater were significantly elevated during summer. Elevated temperatures during summer may lead to increased arsenic loading by increasing dissolution rate of arsenic source minerals and/or increases in microbially-mediated dissolution processes. The hyporheic zone was shown to be retaining arsenic in the upstream-most sub-reach. Retention most likely occurs through the sorption of dissolved arsenic onto hyporheic sediments. In downstream sub-reaches, hyporheic sediments are derived from mine-tailing piles which have high arsenic content. The hyporheic zone in these sub-reaches was shown to be releasing dissolved arsenic. The historic influence of mining activity has resulted in multiple sources of arsenic to the stream which has increased arsenic contamination of the surface waters.
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    Assessing landscape and seasonal controls on CO2 fluxes in a karst sinkhole
    Thompson, Taryn Karie (Virginia Tech, 2022-01-06)
    Karst landscapes can serve as carbon sinks when carbon dioxide (CO2) reacts with water to form carbonic acid, which then weathers carbonate rocks. However, CO2 can also move through the subsurface via gas diffusion, a process that is not well-understood in karst systems. This study focused on quantifying CO2 diffusion within a karst sinkhole. The objectives of this study were to: 1) identify the depth of the zero-flux plane (i.e., depths of local maximum CO2 concentrations), analyze the distributions of concentration gradients, and investigate the validity of a uniform concentration gradient throughout the profile; and 2) assess the influences of vertical position and seasonality on CO2 fluxes within this sinkhole. The study site contained three locations within the sinkhole, including shoulder, backslope, and toeslope locations. Each location had three soil CO2 and three soil water content/temperature sensors placed at 20, 40, and 60 cm depths. Zero-flux planes were seldom detectable during the warm season (April-September) but were frequently found near the surface (20 or 40 cm) during the cool season (October-March). The common assumption of a uniform concentration gradient was often invalid based on relative concentrations between sensor pairs. As for the second objective, CO2 fluxes generally followed a trend of upward fluxes in warmer months that was partially offset by downward fluxes during the cooler months. These study results provide new insight into CO2 dynamics in a karst system, and suggest that subsurface processes such as chemical weathering and cave ventilation affect the direction and magnitude of CO2 fluxes.
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    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.
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    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.
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    Beneficial Reuse of Dredged Materials in Upland Environments
    Haus, Nicholas Wes (Virginia Tech, 2011-12-13)
    Sediments excavated from dredging operations are known as dredged materials. Beneficial reuse of dredged materials in confined utilization facilities (CUFs) is a new approach that has the potential to productively utilize large quantities of dredged materials. However, several factors can inhibit the use of dredged materials in CUFs. In this study, high levels of salts and polycyclic aromatic hydrocarbons (PAHs) were investigated. In the first part of this study, 176,000 m3 of saline dredged materials was placed into a CUF. In less than 4 years, most of the dredged materials had developed horizonation and converted to Inceptisols. The formation of pedogenic Bg horizons in these soils occurred after a polygonal prism network had developed which partially disintegrated into a blocky structured, oxidized horizon with an abundance of redoximorphic features. During the study period, the soil chemistry of the weathering dredged materials shifted from Na-dominated to Ca and Mg-dominated system, allowing plant invasion. In the second part of the study, a bench-scale greenhouse bioremediation experiment was conducted to test the effectiveness of biosolids, compost, and straw at enhancing PAH degradation. Initial concentrations of PAHs decreased significantly after 150 days using standard methods of extraction. However, at 327 days the concentrations of many PAHs, especially those with higher molecular weights, had rebounded close to initial levels. This indicates that PAH bioremediation studies using organic matter additions and conducted using standard methods of extraction need to be carried out longer periods of time or that extraction methods need to be improved.
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    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.
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    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.
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    Catchment Structure Regulates Hydrodynamic Drivers of Chemical Weathering in Shallow Forest Soils
    Pennino, Amanda (Virginia Tech, 2023-06-12)
    Determining where, when, and how subsurface flow affects soil processes and the resulting arrangement of soil development along flow paths is challenging. While hydrologic regime and soil solution acidity are known to influence weathering rates and soil transformation processes, an integrated understanding of these factors together is still lacking. This dissertation explores the effects of subsurface flow on the mobility and distribution of dissolved organic carbon (DOC) and base cations to explain spatial patterns in chemical weathering in a forested headwater catchment. In the first chapter, relationships between hydrologic behavior, fluxes of weathered elements, and the extent of soil elemental loss across landscape positions are established. The second chapter investigates what specific groundwater behavior best explains spatial patterns in solution DOC concentrations during storm events. Lastly, in the third chapter, near surface saturation dynamics are examined to determine when and where DOC mobilization might be enhanced by subsurface flow. Results show that weathering extent was greatest in the upper reaches of the catchment, where O horizon saturation frequency and DOC concentrations are highest. Annual base cation fluxes, which were also greatest in these positions, could indicate where weathering is likely still enhanced. Additionally, while O horizon saturation occurred across the catchment, spatial differences in DOC concentrations suggest there are other sources of acidity to groundwater solutions other than just leaching from O horizons. Shallow organic soils, near bedrock outcrops at the top of the catchment is likely this additional C source, in which drainage water is transported downslope to nearby mineral soils when water tables are high and hydrologic connectivity between soils is increased. Spring and fall storm events were identified as times when groundwater most frequently reached O horizons during the snow-free year, providing insight into the timing of these processes throughout the year. This dissertation highlights how catchment structure mediates DOC flushing events, which in turn, influences the spatial architecture of soil development and chemical weathering processes across the landscape.
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    Characterization and modeling of land subsidence due to groundwater withdrawals from the confined aquifers of the Virginia Coastal Plain
    Pope, Jason Philip (Virginia Tech, 2002-05-16)
    Measurement and analysis of aquifer-system compaction have been used to characterize aquifer and confining unit properties when other techniques such as flow modeling have been ineffective at adequately quantifying storage properties or matching historical water levels in environments experiencing land subsidence. In the southeastern Coastal Plain of Virginia, high-sensitivity borehole pipe extensometers were used to measure 24.2 mm of total compaction at Franklin from 1979 to 1995 (an average of 1.5 mm/yr) and 50.2 mm of total compaction at Suffolk from 1982 to 1995 (an average of 3.7 mm/yr). Analysis of the extensometer data reveals that the small rates of aquifer-system compaction appear to be correlated with withdrawals of water from confined aquifers. One-dimensional vertical compaction modeling indicates that the measured compaction is the result of nonrecoverable hydrodynamic consolidation of the fine-grained confining units and interbeds as well as recoverable compaction and expansion of coarse-grained aquifer units. The modeling results also provide useful information about specific storage and vertical hydraulic conductivity of individual hydrogeologic units. The results of this study enhance the understanding of the complex Coastal Plain aquifer system and will be useful in future modeling and management of ground water in this region.
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    Characterization of a hydraulically induced bedrock fracture
    Brandon, Ryan (Virginia Tech, 2014-09-17)
    Hydraulic fracturing is a controversial practice because of concerns about environmental impacts due to its widespread use in recovering unconventional petroleum and natural gas deposits. However, water-only hydraulic fracturing has been used safely and successfully for many years to increase the permeability of aquifers used for drinking and irrigation water supply. This process extends and widens existing bedrock fractures, allowing groundwater storage to increase. Researchers have studied the behavior of fractured-rock aquifers for decades, but little has been published on the hydraulic and mechanical properties of hydraulically enhanced fractures. In this study, a multi-faceted approach consisting of aquifer and tracer testing is used to estimate the transmissivity and storage coefficient of a hydraulically induced fracture and observe its behavior as a contaminant flow pathway. The results of the aquifer tests indicated a decrease in both the transmissivity and storage coefficient of the fracture of three orders of magnitude after cessation of pumping. The aquifer temporarily experienced incomplete recovery following pumping tests, likely due to slow recharge. After complete recovery occurred, subsequent tests showed that these hydraulic properties returned to their original values, indicating elastic compression of the fracture during periods of applied stress. The results of the tracer test indicated rapid, uniform, one-dimensional flow through the fracture, with average fluid velocity approaching 1 km/day in an induced steady flow field of 6 x 10-5 m3/s (1 gal/min) and a fracture volume of 0.238 m3 (63 gal). The complex heterogeneity of fractured-rock aquifers necessitates the use of multiple lines of testing in order to arrive at a detailed description of the behavior of these systems. This study demonstrates one effective method of investigating a single fracture that can uncover information about the behavior of a hydraulically enhanced aquifer that is otherwise difficult to obtain.