Theses and Dissertations from UMD
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New submissions to the thesis/dissertation collections are added automatically as they are received from the Graduate School. Currently, the Graduate School deposits all theses and dissertations from a given semester after the official graduation date. This means that there may be up to a 4 month delay in the appearance of a give thesis/dissertation in DRUM
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Item PREVENTION AND TREATMENT OF PERSISTENT ORGANIC POLLUTANTS IN STORMWATER AND SEDIMENT(2023) Yuan, Chen; Kjellerup, Birthe V; Davis, Allen P; Civil Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Polycyclic aromatic hydrocarbons (PAHs) and Polychlorinated biphenyls (PCBs) are two groups of persistent organic pollutants (POPs) with toxicity, carcinogenicity, and teratogenicity. Those compounds are harmful to human health and wildlife. Stormwater is one of the important sources of PAHs and PCBs to aquatic environments. Stormwater control measures (SCMs) have already been used to remove PAHs and PCBs from stormwater, however traditional SCMs can remove PAHs and PCBs in the particle phase, but there still are dissolved PAHs and PCBs in the outflow of SCMs. This study focused on reducing the influence of PAHs and PCBs in stormwater on the environment by 1) improve the treatment performance by adding a polishing treatment procedure after traditional SCMs, and remove the PAHs and PCBs accumulated in the polishing treatment media by bioaugmentation of Pseudomonas putida ATCC 17484 and Paraburkholderia xenovorans LB400 and 2) dechlorination of PCBs in the sediment of aquatic environments by biofilm Dehalobium chlorocoercia DF1 inoculum. The results of polishing treatment showed that all black carbon materials, namely biochar, granular activated carbon (GAC), and regenerated GAC (RAC), were effective to remove dissolved PAHs with removal > 95%. However, all materials had lower removal efficiency on PCBs with removal > 84%, By the comparation of cost and lifetime under the condition that 50% polishing media are used in the polishing treatment facility. RAC which has a lifetime>147 years based on the precipitation of Maryland and Washington and cost <3.79 $-m3-yr-1, was the best material for polishing treatment. Results of treatment train with a traditional SCM media column and polishing treatment column indicated that average removal of PAHs can be improved from 94.56% of BSM columns to 99.61% of polishing treatment columns, and removal of PCBs can be improved from 84.61% to 95.16%. Results of bioaugmentation of polishing treatment media showed no biodegradation took place in the mesocosms with polishing media. However, the liquid mesocosms showed P.putida degraded 97.9% of pyrene. The bacteria colony on plates after the biodegradation experiment showed that there were less P.putida and P.xenovorans colony of polishing media mesocosms than liquid mesocosms. Therefore, the limitation of biodegradation of polishing media mesocosms may cause by the limited bioavailability and less active inoculated bacteria. The results of dechlorination by Dehalobium chlorocoercia DF1 biofilm shows that there were native bacteria, such as Gemmatimonadetes, Actinobacteria, Proteobacteria and Firmicutes in the sediment that can dechlorinate PCBs. The three treated mesocosm groups (addition of biochar, bioaugmentation with DF1 biofilm and liquid DF1 culture) all can improve dechlorination, of 28.09%, 21.30%, and 17.10%, respectively. Those three groups had dechlorination extent higher than negative control (4.60%), and abiotic control (-1.02%). The microbial community analysis indicated that biofilm inoculation improved abundance of DF1 and had a more stable influence on the community than liquid inoculation. Overall, biofilm inoculation and addition of biochar dechlorinate PCBs in sediment efficiently, and polishing treatment is an efficient approach to improve traditional SCMs, while treating the polishing media with bioaugmentation need further study.Item Interactions and Treatment of Metals in Urban Stormwater(2023) Croft, Kristen; Kjellerup, Birthe V; Davis, Allen P; Civil Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Increasing urbanization and a changing climate will only exacerbate the magnitude of pollution entering our waterways, threatening our drinking water source and aquatic ecosystems. Urban stormwater contains a cornucopia of pollutants that pose direct toxicity risks (e.g., metals, organics, pathogens) and indirect adverse effects (e.g., sediments, nutrients) to aquatic life. Metals, specifically copper (Cu) and zinc (Zn), are both ubiquitous in the urban environment and detrimental to aquatic ecosystems at low concentrations (approximately 10 ppb). Targeting this growing source of pollution upstream is critical in providing necessary environmental protections, especially as the intensifying effects of climate change and urbanization are imminent. This leads to the main research question – how can Cu and Zn loads in stormwater be reduced to protect aquatic ecosystems?Bioretention is a stormwater control measure (SCM) that mimics natural systems to take advantage of the natural filtering processes. In addition to hydrologic benefits, bioretention provides removal of particulate matter (PM) through filtration and sedimentation, and potential removal of dissolved constituents through chemical and biological processes. Studies including characterization of stormwater, road-deposited sediments (RDS), and performance of a mature bioretention cell were performed to determine treatability, mobility, and bioavailability of Cu and Zn in stormwater and through bioretention treatment. Both metals accumulated in the finest (<25 μm) fraction of RDS samples, however particulate bound (PB) Zn concentrations were enriched in stormwater compared to finer fractions of RDS, while PB-Cu was not. This indicated that PB-Zn is more mobile than PB-Cu, likely due to different sources of these metals in urban environments. The PM and PB metal loads were reduced by 82% and 83%, respectively, showing that mature bioretention cells are effective at reducing PM and PB contaminant loads. However, dissolved constituents were essentially unchanged through bioretention treatment, and concentrations of dissolved metals were measured at levels that potentially cause aquatic toxicity. Thus, alternative media amendments were investigated for further reduction of dissolved metal contents. Black carbon (BC) media including biochar, granular activated carbon (GAC), regenerated activated carbon (RAC), and a natural mineral sorbent, clinoptilolite zeolite, were tested in continuous columns, and in up-scaled modular treatment columns. The four tested BC media performed similarly for Cu and Zn removal, with Zn having an earlier breakthrough compared to Cu. This technology is predicted to provide reduction of dissolved Cu for up to 60 years with current rainfall predictions. Modular treatment columns showed that traditional bioretention soil media (BSM) provided effective removal of dissolved Zn (71%) and ineffective removal of Cu (17%). The subsequent BC polishing module was effective for Cu removal (40%), and zeolite showed potential for Zn removal. Overall, dissolved metals in stormwater are the most mobile, bioavailable, and difficult to remove through traditional filtration-based SCMs. This research has shown that fresh BSM can provide effective removal of dissolved Zn, and BC amendments are a potential solution for removal of dissolved Cu in stormwater. Refreshing the top few centimeters of an existing bioretention with fresh BSM can provide treatment of dissolved Zn. Retrofitting bioretention to include a polishing module either layered or in series with a mix of BC and zeolite can further reduce dissolved Cu and Zn loads in stormwater.Item REMOVAL OF STORMWATER DISSOLVED ORGANIC NITROGEN MODEL COMPOUNDS THROUGH ADSORPTION AND BIOTRANSFORMATION(2019) Mohtadi, Mehrdad; Davis, Allen P.; Civil Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Bioretention systems are stormwater control measures designed to reduce nitrogen and phosphorus transferred by stormwater to water resources. They are, however, not effectively designed to remove dissolved organic nitrogen (DON). This study concentrated on improvement of bioretention design to remove stormwater DON. Batch adsorption of eight organic nitrogenous compounds onto several adsorbents showed that coal activated carbon (AC) could be a reliable adsorbent for removal of organic nitrogenous compounds such as pyrrole and N-acetyl-D-glucosamine (NAG). The adsorption capacity of pyrrole and NAG on coal AC were 0.4 mg N/g (at equilibrium concentration, Ce = 0.02 mg N/L) and 0.71 mg N/g (at Ce = 1 mg N/L), respectively. These eight nitrogenous compounds were also tested for continuous column adsorption on a media mixture of coal AC + quartz sand, and only pyrrole showed an appreciable adsorption performance; the breakthrough and exhaustion depths for pyrrole were 88 and 499 m, respectively, at the fixed superficial velocity of 61 cm/h and influent DON concentration of 1 mg N/L. Pyrrole adsorption was also minimally affected by superficial velocity (DON removal efficiency stayed > 91% for all tested superficial velocities, 7 to 489 cm/h). Because the adsorption process was successful for removal of only one (pyrrole) out of eight examined compounds, biological treatment was also investigated for removal of organic nitrogenous compounds. Biotransformation alongside adsorption demonstrated benefits such as ammonification of bio-recalcitrant organic nitrogen compounds, e.g., pyrrole, and bioregeneration of the adsorbent (coal AC). According to the results, ammonifiction might be considered as a possible reliable mechanism for stormwater DON removal at low temperatures > 4°C. Under intermittent wetting/draining conditions, the effluent DON was less than 0.1 mg N/L after the applied depth of 48 m, indicating that DON was successfully removed through simultaneous adsorption/ammonification, although generated ammonium in the effluent must be properly addressed. Overall, based on the results from the current study, some DON types were strongly adsorbed by adsorbents, e.g., adsorption of pyrrole on coal AC, some were more bioavailable, e.g., ammonification of leucine, and some were barely adsorbable and bioavailable, e.g., Aldrich humic acid on coal AC. Accordingly, both adsorption and biotransformation should be considered to enhance stormwater DON removal as much as possible.Item UNDERSTANDING THE SURFACE CHEMISTRY OF GAS PHASE ORGANOPHOSPHORUS CHEMICAL WARFARE AGENTS WITH SORBENT MATERIALS(2019) Holdren, Scott; Zachariah, Michael R.; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Chemical warfare agents (CWAs) pose a serious threat to civilians and warfighters due to their high toxicity and usage in recent attacks. Although existing filtration media (ASZM-TEDA) used in gas mask devices absorbs and decomposes a wide spectrum of CWAs, the filtration performance of this material can be compromised in the battlefield due to poorly understood mechanisms. The high toxicity of CWAs remains a barrier for most research institutions to study these compounds experimentally which hinders the search for improved filtration materials. To overcome this issue, studies are performed using relatively benign simulant compounds that have similar adsorption and decomposition properties as toxic CWAs. In this work, a report of experimental findings will be presented regarding how dimethyl methylphosphonate (DMMP), an organophosphorus CWA simulant, will adsorb and decompose on components that makeup ASZM-TEDA. The work presented in this dissertation deconstructs the components that makeup ASZM-TEDA in order to identify the role of specific metal oxides and the carbon support. This approach was facilitated using different analytical techniques including TGA, FTIR spectroscopy, and DFT modeling to gain a molecular understanding of how DMMP interacts with porous carbon (Chapter 3) and metal oxide nanoparticles/surfaces (Chapters 4 and 5). Lastly, a new method is described (Chapter 6) that overcomes many of the difficulties encountered in conventional measurements that monitor gas phase DMMP adsorption/desorption processes on sorbent materials. This method can be used to obtain reliable quantitative measurements and parameters (e.g. adsorption capacities, ∆Hads, and kads) of low vapor pressure adsorbate/sorbent systems making it particularly useful for CWAs/CWA simulants and new filtration materials (e.g. DMMP and porous carbon).Item Synthesis of Novel Co-Polymers Using Ionizing Radiation Grafting Methods for the Extraction of Uranium from Seawater(2017) Dietz, Travis Cameron; Al-Sheikhly, Mohamad I; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)The world’s oceans contain a relatively uniform uranium concentration of 3 μg/L. While this is an exceedingly small concentration, the quantity of uranium throughout the oceans is about 1000 times higher than the quantity in known terrestrial deposits. To take advantage of this immense resource, radiation grafting techniques were used to attach uranium-chelating monomers to durable polymer substrates. Three novel, uranium extracting co-polymer systems have been fabricated through this process and characterized. Three different compound classes were explored for their ability to extract uranium, specifically phosphates, oxalates, and azos. These classes displayed characteristics that provide advantages to the technology over state-of-the-art systems. For the phosphates and oxalates, monomers of these classes containing allyl groups were radiation grafted onto a polymer in a single step. For the azos, a chemical precursor containing a vinyl group was initially radiation grafted to a polymer. The azo compound was then chemically attached to the functionalized polymer surface. For effective seawater deployment, a polymer substrate was chosen as an inexpensive, reusable platform for extraction. While different fabric substrates were tested, high surface area (14 m^2/g) nylon 6 fabric was chosen for its durability and its capacity for radiation grafting. Direct and indirect radiation induced graft polymerization methods were used in this work. For direct grafting, the nylon 6 fabric was immersed in the monomer solution and irradiated. However, for indirect grafting, only the fabric was irradiated followed by the immediate introduction of the monomer solution. All of these experiments were conducted under anaerobic conditions to prevent the reaction of oxygen with the radiolytically-produced, carbon-centered free radicals. The grafted fabrics were characterized for attachment of the monomer and their ability to extract uranium. The degree of surface grafting was determined through attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy, among other techniques. Electron paramagnetic resonance spectroscopy was used to determine radical decay kinetics in the polymer substrate. Pulse radiolysis was used to elucidate the polymerization reaction kinetics of certain monomers. These fabrics were then exposed to uranium-doped seawater solutions and the extraction capacities of the grafted materials were determined.Item Effect of Surfactants on Drop Size Distributions in a Batch, Rotor-Stator Mixer(2004-12-17) Padron, Gustavo A.; Calabrese, Richard V; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Surfactants are often required to stabilize liquid-liquid dispersions produced by rotor-stator mixers. Since drops are deformed rapidly due to the high power input of these devices, the dynamic interfacial properties governed by the surfactant adsorption rate have a significant effect on the resulting drop size. The objective of this work is to develop a fundamental link between surfactant adsorption dynamics, interfacial properties, and turbulent emulsification processes in rotor-stator mixers. The mean drop size and drop size distributions (DSD) of dilute dispersions produced by a batch rotor-stator mixer were studied. Silicone oils of various viscosities were dispersed in aqueous nonionic surfactant and aqueous methanol solutions. The aqueous methanol (clean) systems allowed comparison of surfactant-laden to surfactant-free systems with similar equilibrium interfacial tensions. The DSD were measured via a video microscopy/automated image analysis technique. The equilibrium interfacial tension of clean and surfactant systems was measured, via a pendant drop technique, as a function of methanol and surfactant concentration, respectively. The dynamic surface tension of surfactant solutions was similarly measured. By fitting the data to the Langmuir adsorption isotherm and a long time approximation to the Ward Tordai equation, the adsorption parameters and surfactant diffusivities were obtained. This information, with an estimate of the drop deformation timescale, allowed estimation of the surface dilational modulus (Esd). This is a measure of the Marangoni stresses acting on the drop' surface due to interfacial tension gradients. Trends observed in the mean drop size and DSD experimental results are explained in terms of the interfacial and rheological properties. Below the CMC, Esd peaks and the drop size increases with concentration, despite a decrease in equilibrium interfacial tension. Above the CMC, Marangoni stresses are small but the presence of the surfactant still modifies the rheology of the interface, increasing the effective viscosity of the drops. A comprehensive set of mechanistic models for drop size in turbulent flows was developed and modified to partially account for the effect of surfactants via an appropriately defined effective viscosity. Various model choices were systematically fit to the drop size data to select the most appropriate mechanistic correlation. Normalized experimental DSD data collapsed to a single log-normal volume distribution.