Doctor of Philosophy, The Ohio State University, 2024, Environmental Science

Historical and current anthropogenic activity combined with land turnovers and rampant vacancies have increased human exposure risk to contaminants. This exposure risk disproportionately affects lower income communities and can have detrimental impacts on human health, particularly children. A management solution is needed to address this widespread contamination of vacant lots. Additionally, federal and state regulators continue to lower residential soil Pb standards which will likely require new risk-based approaches to address urban soil Pb contamination. This dissertation examines three different amendment types (P amendments, Fe oxide containing amendments, and potassium permanganate (KMnO4)) for their ability to address urban Pb soil contamination and reduce human health exposure risk. Remediation strategies that can address both organic and inorganic pollutants are also needed. This is addressed in Chapter 3. This dissertation is written as a series of manuscripts to be submitted to the appropriate journals; this will be reflected by slight differences in formatting. In Chapter 1, readily available P sources (biosolids incinerator ash, poultry litter, biosolids compost, and triple super phosphate) of varying solubility were assessed as soil amendments to reduce Pb bioaccessibility and serve as an inexpensive remediation strategy for urban soil. Contaminated soil from Cleveland, OH was treated with the P soil amendments at a 1:5 Pb:P molar ratio and incubated for 3 months. A slurry analysis was also conducted to assess reduction in bioaccessible Pb independent of time. Pb bioaccessibility was evaluated using US EPA Method 1340 at pH 1.5 and the Physiologically Based Extraction Test (PBET). Treatments were largely found ineffective regardless of IVBA extraction method, incubation duration, slurry analyses, or P source. Method 1340 had one significant treatment (combined poultry litter and BIA) but only resulted in a 8% IVBA Pb reduction. The same treatmen (open full item for complete abstract)

Committee: Nicholas Basta (Advisor); Brian Lower (Committee Member); Steven Lower (Committee Member); Darryl Hood (Committee Member) Subjects: Environmental Science; Soil Sciences

Master of Science (MS), Bowling Green State University, 2021, Geology

Urban environments have a history of anthropogenic input of heavy metals to soils. Toledo, Ohio is an urban setting that has been altered through heavy industry and transportation dating back to the 1800s. Heavy metal contamination in soil has been shown to cause serious health effects in humans, such as brain damage, birth defects, cancer, and even death. A total of 137 Toledo soil samples were collected in collaboration with local Toledo schools, the Manos Community Garden, and a previous study completed by Stewart et al (2014). Stewart's study samples and the local Toledo schools' soil samples were collected by K-12 students through a hands-on citizen science project. The samples were analyzed to determine the concentrations of a series of heavy metals, including arsenic, cadmium, chromium, lead, nickel, and zinc. The results revealed multiple samples with elevated levels of all six focus metals greater than the Ohio EPA's soil background levels of the region. Two of these elements, arsenic and lead, had concentrations higher than the USEPA screening level for soils of this region in 73% and 7% of samples, respectively. Locations with elevated heavy metals concentrations in soils were mostly residential yards with older houses and within areas of high transportation. Therefore, the elevated levels of heavy metals were likely deposited from a legacy of human activities. Heavy metal predictive concentration maps of the Toledo, Ohio area were created to show possible areas of concern. The predictive maps showed a higher concentration of most elements in the Old West End area of Toledo. The findings were presented to the collaborating schools and in public forums to educate citizens about elevated heavy metal soil contamination in their area. They were given possible reasons for the contamination, explaining the harmful side effects of human activities on the soils. The health risks associated with the contamination were presented along with how to prevent health (open full item for complete abstract)

Committee: John Farver Dr. (Advisor); Jeffrey Snyder Dr. (Committee Member); Margaret Yacobucci Dr. (Committee Member) Subjects: Education; Geochemistry; Geology

Master of Science (MS), Bowling Green State University, 2019, Geology

Blood lead levels (BLLs) in children of the Toledo, OH area have been elevated for decades, and numerous studies have linked the issue to soil contamination by lead (Pb) paint and leaded gasoline. Young children below the age of 4 years have proven the most susceptible to Pb poisoning due to their high Pb absorption rates and direct ingestion of Pb contaminated sources resulting from instinctive hand-to-mouth behaviors. This problem is significant because high BLLs can result in many pathological and developmental problems including irreversible fetal brain damage, brain damage to the developing prefrontal cortex, behavioral problems, violence, learning disabilities, and more. The objectives of this study were to determine the primary factors leading to Pb and other heavy metals contamination in community gardens located at or near contaminated soils in Toledo, OH. Given the rising popularity of urban community gardens, it is also important to understand the sustainability of current gardening practices for minimizing exposure to Pb. A total of 399 samples were collected across 27 community gardens, of which 218 including the soil profiles of 14 community gardens were analyzed for heavy metals using an ICP-OES. Soil profiles were collected down to 40 cm depth (or maximum achievable depth based on the presence of buried rubble from demolished structures, buried foundations, etc.), and subsampled at 5 cm intervals to observe its distribution with depth. Using historical maps such as the Sanborn Fire Insurance maps combined with measuring the distribution of lead within gardens across properties, it was found that drip zones, a 1-meter area of soil immediately surrounding structures containing lead paint, is the main predictor for high lead levels in community gardens. And given that many gardens are located at the sites of demolished structures, historical maps such as the Sanborn Fire Insurance maps proved critical for determining the locations of drip zones a (open full item for complete abstract)

Committee: John Farver Dr. (Advisor); Peter Gorsevski Dr. (Committee Member); Yuning Fu Dr. (Committee Member) Subjects: Environmental Geology; Environmental Science; Geology; Health Sciences; Soil Sciences

Master of Science (MS), Bowling Green State University, 2016, Geology

The oil and gas booms of the late 19th century left tens of thousands of wells in Wood County, Ohio abandoned and improperly capped. This allows hydrocarbons to seep into the surrounding soil. Detection of these wells proves difficult because many of the wells are buried and their locations lost. To be able to detect the oil wells over large areas, different remote sensing techniques can be used to detect changes in soil properties caused by the presence of hydrocarbons. However, the capability of this technology depends on spatial and spectral resolution of a sensor and in situ data are often necessary. In this study, in-situ hyperspectral reflectance data and thermal imaging are used in conjunction with clay mineral X-ray diffraction analysis to identify soil properties around abandoned wells located in an agricultural area in Wood County, Ohio. This study is confirmation of previous finding and it serves to indicate uncertainties related to a limited sampling effort, and to address the importance of field sampling strategies and adequate remote sensing techniques. Non-commercial satellite based remote sensors of medium, spatial resolution, such as Landsat, are inadequate for detection of the small abandoned wells in Wood County, Ohio. In situ hyperspectral reflectance measurements, used to simulate WorldView-3 spectral and spatial resolution, suggest that this high spatial resolution commercial satellite is optimal for detecting small abandoned oil wells. It is confirmed that a spectral band ratio in the spectral range between 2.185-2.225 µm and 2.295-2.365 µm (WorldView-3 shortwave bands 6 and 8, respectively) is effective. The clay mineral X-ray diffraction analysis suggests that these changes in the spectral information occur predominately due to the hydrocarbons; clay mineral content changes in the soil did not affect the soil spectral signature to a greater extent. Thermal imaging identified higher surface temperatures in soil with higher hydrocarbon content (open full item for complete abstract)

Committee: Anita Simic (Advisor); Jeff Snyder (Committee Member); John Farver (Committee Member) Subjects: Geology; Remote Sensing

Doctor of Philosophy, The Ohio State University, 2014, Environmental Science

Increasing proportions of vacant land parcels in post-industrial cities is a growing concern due to decreasing land value and increasing maintenance externalities. Utilizing this urban vacant land for growing food crops can promote local self-reliance and access to healthy food; specifically in low income disadvantaged neighborhoods. However, impact of heavy metal contaminants on soil quality, is a major concern for urban agriculture. Additionally, health of vacant lot soil also depends on the structural bio-diversity of the below ground soil food web. Hence the specific objectives of this research were (i) to assess the level of soil heavy metal concentrations in two post-industrial cities and determine their potential human health risk (Chapter 2); (ii) to evaluate the relationship between heavy metal concentrations and the structure and function of the soil food web using nematodes as surrogates of soil microbial community (Chapter 3); (iii) to test a novel approach of transplantation of an intact soil core to reconstruct the structural complexity of a disturbed soil food web and restore its level of multi trophic interactions to a pre-disturbance level (Chapter 4) (iv) finally, to re-construct the soil food web in urban vacant lot using intact soil cores from relatively undisturbed forest soil, and assess the survival of the introduced nematode species under organic matter with different C:N ratios (Chapter 4) We determined the extent of soil Pb, Cd, Zn, As and Cr concentrations in 43 vacant lots in two disadvantaged neighborhoods in Hough (Cleveland) and Weinland Park (Columbus), Ohio. Results showed that compared to the Ecological Soil Screening levels (Eco SSL) for human ingestion of soil, only 6% of the lots in Weinland Park and 53% in Hough neighborhood had Pb concentrations above the Eco SSL of 400 mg Pb/kg soil. Also, all the studied sites exceeded the Eco SSL value of 0.4 mg As/kg soil; however, soil As concentration in 94% of the lots in Weinl (open full item for complete abstract)

Committee: Parwinder Grewal Dr. (Advisor); Larry Phelan Dr. (Committee Member); Nick Basta Dr. (Committee Member); Rafiq Islam Dr. (Committee Member) Subjects: Environmental Science

MS, Kent State University, 2021, College of Arts and Sciences / Department of Earth Sciences

Acid mine drainage (AMD) is one of the most serious environmental threats to water resources in the world. Mining operations create conditions that expose pyrite where it is susceptible to weathering by oxidative dissolution. Over time, soils develop from the mine spoil containing sulfide minerals and trace metals such as Fe, Mn, Zn, Al, Cu, and As. Adding alkalinity to the soil slows the oxidation rate of pyrite and promotes the precipitation of secondary minerals, particularly iron oxides, that may sorb metal ions and decrease porosity within the soil preventing further sulfide oxidation. This work is part of a recently completed pilot project which examined the efficacy of lime slurry as a non-point source treatment of pyrite-rich ~40-year-old mine spoil in the Huff Run Watershed (Mineral City, Ohio). In the current work, 12 thin sections prepared from two field sites (BP, an embankment located near a tributary to the Huff Run (subwatershed HR-25) with heavy understory vegetation and trees; and BY, a conical hill of mine spoil located northwest and upslope of the BP site with large trees, many dead or dying, but virtually no understory vegetation) collected along a depth profile and two laboratory columns of composite soils, which were either untreated or treated with a lime slurry. The impact of treatment on the formation and texture of secondary mineral coatings and trace metal sequestration was examined by Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS) element mapping. The image analysis software ImageJ was used to perform a quantitative analysis to determine the particle characteristics, surface area, coverage, and thickness of secondary mineral coatings and aggregates in the soils. Element correlation scatterplots created with the ScatterJn plugin were used to examine the association between trace metals and mineral surfaces. Results of this work show that lime addition significantly increased secondary coating coverage compar (open full item for complete abstract)

Committee: David Singer (Advisor); Jeremy Williams (Committee Member); Kuldeep Singh (Committee Member) Subjects: Geochemistry; Geology

MS, Kent State University, 2018, College of Arts and Sciences / Department of Earth Sciences

The surface mining of coal leaves behind an abundance of surface waste material called coal mine spoil. Prior to the enactment of the Clean Water Act in 1972 and the Surface Mining Control and Reclamation Act of 1977, mine spoils and their associated mines were often left abandoned after production ceased. Active and abandoned mines are primary producers of acidic and sulfur-rich wastewater in the United States and it is estimated that it will cost $32-$72 billion dollars to remediate waters impacted by acid mine drainage (AMD). Once exposed to the surface, pyrite within these mine waste soils will begin to oxidize, releasing metals and acidity which can leach into nearby surface and groundwater systems. This work explores the efficacy of applying lime slurry, a potential low-cost approach, to coal mine spoil in order to determine mineralogical and geochemical factors controlling neutralization of acidity and sequestration of dissolved metals. Joint field and laboratory studies were conducted in order to determine the chemical and physical interactions that take place between a lime-slurry and coal mine spoil- and AMD impacted soils. The field portion of this study consisted of monitoring the changes in near surface water and solid phase composition of two coal spoil-dominated hillslopes which were treated with lime slurry. Parallel laboratory column experiments simulated rainwater passing through treated and untreated mine spoil in a controlled setting. Changes in solid phase composition during treatment were determined by X-ray diffraction (XRD) and X-ray fluorescence (XRF). Porewater composition was determined by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), Ion Chromatography (IC), and Total Organic Carbon (TOC). The results from the field pilot project are ambiguous and difficult to separate from natural processes. Porewater composition showed little response of pH or electrical conductivity (EC) to lime treatment, in contrast porewater an (open full item for complete abstract)

Committee: David Singer (Advisor); Elizabeth Herndon (Committee Member); Jeremy Williams (Committee Member) Subjects: Environmental Geology; Geochemistry; Geology

MS, University of Cincinnati, 2005, Arts and Sciences : Biological Sciences

The effects of trees on microbial degradation of PAHs are largely unknown. An experimental soil was spiked with 3 model PAHs (phenanthrene, anthracene, and pyrene) and planted with six tree species. PAH dissipation and mineralization in planted and unplanted soils was monitored for up to 15 months. Initial, year long studies revealed that planting effects were negligible and that rapid PAH dissipation was due to high microbial activity and bioavailability. Further experimentation showed that microbial communities respond differently to two seasonally variable sources of root-derived carbon (root exudation and root mortality/decay). Also, soil nutrient amendments reduced pyrene mineralization in root zone soils. While the ‘rhizosphere effect' was supported by one-time mineralization studies, long term PAH dissipation did not vary according to proximity to roots. Seasonal variation in rhizosphere dynamics may reduce or negate the effect of trees on long term PAH dissipation in the rhizosphere.

Committee: Jodi Shann (Advisor) Subjects:

Doctor of Philosophy, The Ohio State University, 2002, Geological Sciences

This study investigates various aspects of in situ chemical oxidation (ISCO) schemes based on MnO4-. Batch experiments show that the interaction between MnO4-, and sediment solids will not only consume the reactant, but also can release toxic metals into ground water. Various column and flow tank experiments were conducted to examine the capacity and efficiency of the oxidation scheme. Oxidation was capable of destroying chlorinated ethylenes in aqueous phase. MnO4- oxidation performs better in removal of residual DNAPL than pooled DNAPL. In zones of high NAPL saturation, Mn oxide precipitates causing pore plugging and permeability reduction. These changes potentially could cause the remedial action to fail. In an effort to mitigate the precipitation, experiments have been carried out to investigate possibilities of delaying the formation of colloidal Mn oxide and to remove the precipitates once formed. The investigation begins with the identification of the Mn oxide mineral structure and the determination of the chemical properties of the solid. Phosphate ion was added to the reaction in an attempt to slowdown colloidal formation due to its high charge and the tendency to sorb on surfaces. The results indicate that the presence of phosphate ion can lower the rate of colloid formation. However, the magnitude of effects due to the addition of phosphate is limited by the ionic strength increase and the pzc (point of zero charge) of the mineral. The dissolution kinetics of birnessite was evaluated using solutions of citric acid, oxalic acid, and EDTA. The results showed that the addition of an organic acid could greatly increase the dissolution rate of birnessite. The dissolution mechanism involves proton and ligand-promoted dissolution and reductive dissolution. A permanganate reactive barrier system (PRBS) was designed and a proof-of-concept experiment was carried out in the laboratory. The experiment demonstrated how the PRBS could delivery MnO4- at a stable, consta (open full item for complete abstract)

Committee: Franklin Schwartz (Advisor) Subjects: