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Description
Plastic pollution has become a global threat to ecosystems worldwide, with microplastics now representing contaminants reported to occur in ambient air, fresh water, seawater, soils, fauna and people. Over time, larger macro-plastics are subject to weathering and fragmentation, resulting in smaller particles, termed ‘microplastics’ (measuring < 5 mm in diameter),

Plastic pollution has become a global threat to ecosystems worldwide, with microplastics now representing contaminants reported to occur in ambient air, fresh water, seawater, soils, fauna and people. Over time, larger macro-plastics are subject to weathering and fragmentation, resulting in smaller particles, termed ‘microplastics’ (measuring < 5 mm in diameter), which have been found to pollute virtually every marine and terrestrial ecosystem on the planet. This thesis explored the transfer of plastic pollutants from consumer products into the built water environment and ultimately into global aquatic and terrestrial ecosystems.

A literature review demonstrated that municipal sewage sludge produced by wastewater treatment plants around the world contains detectable quantities of microplastics. Application of sewage sludge on land was shown to represent a mechanism for transfer of microplastics from wastewater into terrestrial environments, with some countries reporting as high as 113 ± 57 microplastic particles per gram of dry sludge.

To address the notable shortcoming of inconsistent reporting practices for microplastic pollution, this thesis introduced a novel, online calculator that converts the number of plastic particles into the unambiguous metric of mass, thereby making global studies on microplastic pollution directly comparable.

This thesis concludes with an investigation of a previously unexplored and more personal source of plastic pollution, namely the disposal of single-use contact lenses and an assessment of the magnitude of this emerging source of environmental pollution. Using an online survey aimed at quantifying trends with the disposal of lenses in the US, it was discovered that 20 ± 0.8% of contact lens wearers flushed their used lenses down the drain, amounting to 44,000 ± 1,700 kg y-1 of lens dry mass discharged into US wastewater.

From the results it is concluded that conventional and medical microplastics represent a significant global source of pollution and a long-term threat to ecosystems around the world. Recommendations are provided on how to limit the entry of medical microplastics into the built water environment to limit damage to ecosystems worldwide.
ContributorsRolsky, Charles (Author) / Halden, Rolf (Thesis advisor) / Green, Matthew (Committee member) / Neuer, Susanne (Committee member) / Polidoro, Beth (Committee member) / Smith, Andrew (Committee member) / Arizona State University (Publisher)
Created2020
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Description
This dissertation aims at developing novel materials and processing routes using alkali activated aluminosilicate binders for porous (lightweight) geopolymer matrices and 3D-printing concrete applications. The major research objectives are executed in different stages. Stage 1 includes developing synthesis routes, microstructural characterization, and performance characterization of a family of economical, multifunctional

This dissertation aims at developing novel materials and processing routes using alkali activated aluminosilicate binders for porous (lightweight) geopolymer matrices and 3D-printing concrete applications. The major research objectives are executed in different stages. Stage 1 includes developing synthesis routes, microstructural characterization, and performance characterization of a family of economical, multifunctional porous ceramics developed through geopolymerization of an abundant volcanic tuff (aluminosilicate mineral) as the primary source material. Metakaolin, silica fume, alumina powder, and pure silicon powder are also used as additional ingredients when necessary and activated by potassium-based alkaline agents. In Stage 2, a processing route was developed to synthesize lightweight geopolymer matrices from fly ash through carbonate-based activation. Sodium carbonate (Na2CO3) was used in this study to produce controlled pores through the release of CO2 during the low-temperature decomposition of Na2CO3. Stage 3 focuses on 3D printing of binders using geopolymeric binders along with several OPC-based 3D printable binders. In Stage 4, synthesis and characterization of 3D-printable foamed fly ash-based geopolymer matrices for thermal insulation is the focus. A surfactant-based foaming process, multi-step mixing that ensures foam jamming transition and thus a dry foam, and microstructural packing to ensure adequate skeletal density are implemented to develop foamed suspensions amenable to 3D-printing. The last stage of this research develops 3D-printable alkali-activated ground granulated blast furnace slag mixture. Slag is used as the source of aluminosilicate and shows excellent mechanical properties when activated by highly alkaline activator (NaOH + sodium silicate solution). However, alkali activated slag sets and hardens rapidly which is undesirable for 3D printing. Thus, a novel mixing procedure is developed to significantly extend the setting time of slag activated with an alkaline activator to suit 3D printing applications without the use of any retarding admixtures. This dissertation, thus advances the field of sustainable and 3D-printable matrices and opens up a new avenue for faster and economical construction using specialized materials.
ContributorsAlghamdi, Hussam Suhail G (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Mobasher, Barzin (Committee member) / Abbaszadegan, Morteza (Committee member) / Bhate, Dhruv (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Engineered nanomaterials (ENMs) are added to numerous consumer products to enhance their effectiveness, whether it be for environmental remediation, mechanical properties, or as dietary supplements. Uses of ENMs include adding to enhance products, carbon for strength or dielectric properties, silver for antimicrobial properties, zinc oxide for UV sun-blocking properties, titanium

Engineered nanomaterials (ENMs) are added to numerous consumer products to enhance their effectiveness, whether it be for environmental remediation, mechanical properties, or as dietary supplements. Uses of ENMs include adding to enhance products, carbon for strength or dielectric properties, silver for antimicrobial properties, zinc oxide for UV sun-blocking properties, titanium dioxide for photocatalysis, or silica for desiccant properties. However, concerns arise from ENM functional properties that can impact the environment and a lack of regulation regarding ENMs leads to potential public exposure to ENMs and results in ill-informed public or manufacturer perceptions of ENMs. My dissertation evaluates the environmental, human health, and societal impacts of using ENMs, with a focus on ionic silver and nanosilver, in consumer and industrial products. Reproducible experiments served as functional assays to assess ENM distributions among various environmental matrices. Functional assay results were visualized using radar plots and aid in a framework to estimate likely ENM disposition in the environment. To assess beneficial uses of ENMs, bromide ion removal from drinking waters to limit disinfection by-product formation was studied. Silver-enabled graphene oxide materials were capable of removing bromide from water, and exhibited less competition from background solutes (e.g. natural organic matter) when compared against solely ionic silver addition to water for bromide removal. To assess complex interactions of ENMs with the microbiome, batch experiments were performed using fecal samples spiked with ionic silver or commercial dietary silver nanoparticles. Dietary nanosilver and ionic silver exposures to the fecal microbiome for 24 hours reduce short chain fatty acid (SCFA) production and changes the relative abundance of the microbiota. To understand the social perceptions of ENMS, statistically rigorous surveys were conducted to assess related perceptions related to the use of ENMs in drinking water treatment devices the general public and, separately, industrial manufacturers. These stakeholders are influenced by costs and efficiency of the technologies, consumer concerns of the safety of technologies, and environmental health and safety of the technologies. This dissertation represents novel research that took an interdisciplinary approach, spanning from wet-lab engineering bench scale testing to social science survey assessments to better understand the environmental, human health, and societal impacts of using ENMs such as nanosilver and ionic silver in industrial processes and consumer products.
ContributorsKidd, Justin (Author) / Westerhoff, Paul (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Perreault, Francois (Committee member) / Maynard, Andrew (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Seeking to address sustainability issues associated with food waste (FW), and fat, oil, and grease (FOG) waste disposal, the City of Mesa commissioned the Biodesign Swette Center for Environmental Biotechnology (BSCEB) at Arizona State University (ASU) to study to the impact of implementing FW/FOG co-digestion at the wastewater treatment plant

Seeking to address sustainability issues associated with food waste (FW), and fat, oil, and grease (FOG) waste disposal, the City of Mesa commissioned the Biodesign Swette Center for Environmental Biotechnology (BSCEB) at Arizona State University (ASU) to study to the impact of implementing FW/FOG co-digestion at the wastewater treatment plant (WWTP). A key issue for the study was the “souring” of the anaerobic digesters (ADs), which means that the microorganism responsible for organic degradation were deactivated, causing failure of the AD. Several bench-scale reactors soured after the introduction of the FW/FOG feed streams. By comparing measurements from stable with measurements from the souring reactors, I identified two different circumstances responsible for souring events. One set of reactors soured rapidly after the introduction of FW/FOG due to the digester’s hydraulic retention times (HRT) becoming too short for stable operation. A second set of reactors soured after a long period of stability due to steady accumulation of fatty acids (FAs) that depleted bicarbonate alkalinity. FA accumulation was caused by the incomplete hydrolysis/fermentation of feedstock protein, leading to insufficient release of ammonium (NH4+). In contrast, carbohydrates were more rapidly hydrolyzed and fermented to FAs.

The most important contribution of my research is that I identified several leading indicators of souring. In all cases of souring, the accumulation of soluble chemical oxygen demand (SCOD) was an early and easily quantified indicator. A shift in effluent FA concentrations from shorter to longer species also portended souring. A reduction in the yield of methane (CH4) per mass of volatile suspended solids removed (VSSR) also identified souring conditions, but its variability prevented the methane yield from providing advanced warning to allow intervention. For the rapidly soured reactors, reduced bicarbonate alkalinity was the most useful warning sign, and an increasing ratio of SCOD to bicarbonate alkalinity was the clearest sign of souring. Because I buffered the slow-souring reactors with calcium carbonate (CaCO3), I could not rely on bicarbonate alkalinity as an indicator, which put a premium on SCOD as the early warning. I implemented two buffering regimes and demonstrated that early and consistent buffering could lead to reactor recovery.
ContributorsKupferer III, Rick Anthony (Author) / Rittmann, Bruce E. (Thesis advisor) / Young, Michelle N (Committee member) / Torres, César I (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Eighty-two percent of the United States population reside in urban areas. The centralized treatment of the municipal wastewater produced by this population is a huge energy expenditure, up to three percent of the entire energy budget of the country. A portion of this energy is able to be recovered

Eighty-two percent of the United States population reside in urban areas. The centralized treatment of the municipal wastewater produced by this population is a huge energy expenditure, up to three percent of the entire energy budget of the country. A portion of this energy is able to be recovered through the process of anaerobic sludge digestion. Typically, this technology converts the solids separated and generated during the wastewater treatment process into methane, a combustible gas that may be burned to generate electricity. Designing and optimizing anaerobic digestion systems requires the measurement of degradation rates for waste-specific kinetic parameters. In this work, I discuss the ways these kinetic parameters are typically measured. I recommend and demonstrate improvements to these commonly used measuring techniques. I provide experimental results of batch kinetic experiments exploring the effect of sludge pretreatment, a process designed to facilitate rapid breakdown of recalcitrant solids, on energy recovery rates. I explore the use of microbial electrochemical cells, an alternative energy recovery technology able to produce electricity directly from sludge digestion, as precise reporters of degradation kinetics. Finally, I examine a fundamental kinetic limitation of microbial electrochemical cells, acidification of the anode respiring biofilm, to improve their performance as kinetic sensors or energy recovery technologies.
ContributorsHart, Steven Gregg (Author) / Torres, César I (Thesis advisor) / Parameswaran, Prathap (Committee member) / Rittmann, Bruce E. (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are detected ubiquitously in the aquatic environment, biota, and humans. Human exposure and adverse health of PFAS through consuming impacted drinking water is getting regulatory attention. Adsorption using granular activated carbon (GAC) and ion exchange resin (IX) has

Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are detected ubiquitously in the aquatic environment, biota, and humans. Human exposure and adverse health of PFAS through consuming impacted drinking water is getting regulatory attention. Adsorption using granular activated carbon (GAC) and ion exchange resin (IX) has proved to be efficient in removing PFAS from water. There is a need to study the effectiveness of commercially available sorbents in PFAS removal at the pilot-scale with real PFAS contaminated water, which would aid in efficient full-scale plant design. Additionally, there is also a need to have validated bench-scale testing techniques to aid municipalities and researchers in selecting or comparing adsorbents to remove PFAS. Rapid Small-Scale Column Tests (RSSCTs) are bench-scale testing to assess media performance and operational life to remove trace organics but have not been validated for PFAS. Different design considerations exist for RSSCTs, which rely upon either proportional diffusivity (PD) or constant diffusivity (CD) dimensionless scaling relationships.

This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs.
ContributorsVenkatesh, Krishishvar (Author) / Westerhoff, Paul (Thesis advisor) / Sinha, Shahnawaz (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Earthquake-induced soil liquefaction poses a significant global threat, especially to vulnerable populations. There are no existing cost-effective techniques for mitigation of liquefaction under or around existing infrastructure. Microbially Induced Desaturation and Precipitation (MIDP) via denitrification is a potentially sustainable, non-disruptive bio-based ground improvement technique under existing structures. MIDP

Earthquake-induced soil liquefaction poses a significant global threat, especially to vulnerable populations. There are no existing cost-effective techniques for mitigation of liquefaction under or around existing infrastructure. Microbially Induced Desaturation and Precipitation (MIDP) via denitrification is a potentially sustainable, non-disruptive bio-based ground improvement technique under existing structures. MIDP has been shown to reduce liquefaction triggering potential under lab conditions in two ways: 1) biogenic gas desaturation in the short-term (treatment within hours to days) and 2) calcium carbonate precipitation and soil strengthening in the long-term (treatment within weeks to months). However, these experiments have not considered MIDP behavior under field stresses and pressures, nor have they considered challenges from process inhibition or microbial competition that may be encountered when upscaled to field applications. This study presents results from centrifuge experiments and simplified modeling to explore scaling effects on biogenic gas formation, distribution, and retention when simulating field pressures and stresses. Experimental results from the centrifuge demonstrated MIDP’s potential to mitigate the potential liquefaction triggering through desaturation. This study also includes the development of a biogeochemical model to explore the impact of water constituents, process inhibition, and alternative biochemical metabolisms on MIDP and the subsequent impact of MIDP on the surrounding environment. The model was used to explore MIDP behavior when varying the source-water used as the substrate recipe solute (i.e., groundwater and seawater) and when varying the electron donor (i.e., acetate, glucose, and molasses) in different substrate recipes. The predicted products and by-products were compared for cases when desaturation was the targeted improvement mechanism and for the case when precipitation was the primary targeted ground improvement mechanism. From these modeling exercises, MIDP can be applied in all tested natural environments and adjusting the substrate recipe may be able to mitigate unwanted long-term environmental impacts. A preliminary techno-economic analysis using information gained from the modeling exercises was performed, which demonstrated MIDP’s potential as a cost-effective technique compared to currently used ground improvement techniques, which can be costly, impractical, and unsustainable. The findings from this study are critical to develop treatment MIDP plans for potential field trials to maximize treatment effectiveness, promote sustainability and cost-effectiveness, and limit unwanted by-products.
ContributorsHall, Caitlyn Anne (Author) / Rittmann, Bruce E. (Thesis advisor) / Kavazanjian, Edward (Thesis advisor) / van Paassen, Leon A. (Committee member) / DeJong, Jason T. (Committee member) / Arizona State University (Publisher)
Created2021
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Description
This dissertation investigated the use of membrane processes to selectively separate and concentrate nitrogen in human urine. The targeted nitrogen species to be recovered were urea from fresh human urine and unionized ammonia from hydrolyzed human urine. Chapter 1 investigated a novel two-step process of forward osmosis (FO) and membrane

This dissertation investigated the use of membrane processes to selectively separate and concentrate nitrogen in human urine. The targeted nitrogen species to be recovered were urea from fresh human urine and unionized ammonia from hydrolyzed human urine. Chapter 1 investigated a novel two-step process of forward osmosis (FO) and membrane distillation (MD) to recover the urea in fresh human urine. Specifically, FO was used to selectively separate urea from the other components in urine and MD was used to concentrate the separated urea. The combined process was able to produce a product solution that had an average urea concentration that is 45–68% of the urea concentration found in the fresh urine with greater than 90% rejection of total organic carbon (TOC).Chapter 2 determined the transport behavior of low molecular weight neutral nitrogen compounds in order to maximize ammonia recovery from real hydrolyzed human urine by FO. Novel strategic pH manipulation between the feed and the draw solution allowed for up to 86% recovery of ammonia by keeping the draw solution pH <6.5 and the feed solution pH >11. An economic analysis showed that ammonia recovery by FO has the potential to be much more economically favorable compared to ammonia air stripping or ion exchange if the proper draw solute is chosen. Chapter 3 investigated the dead-end rejection of urea in fresh urine at varying pH and the rejection of unionized ammonia and the ammonium ion in hydrolyzed urine by reverse osmosis (RO), nanofiltration (NF), and microfiltration (MF). When these different membrane separation processes were compared, NF is found to be a promising technology to recover up to 90% of ammonia from hydrolyzed urine with a high rejection of salts and organics. Chapter 4 investigated the use of the RO and NF to recover ammonia from hydrolyzed human urine in a cross-flow system where both rejection and fouling experiments were performed. For both RO and NF, ammonia rejection was found to be 0% while still achieving high rejection of TOC and salts, and MF pretreatment greatly reduced the extent of fouling on the membrane surface.
ContributorsRay, Hannah (Author) / Boyer, Treavor H (Thesis advisor) / Perreault, Francois (Committee member) / Sinha, Shahnawaz (Committee member) / Arizona State University (Publisher)
Created2020
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Description
Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals used for a wide variety of products and industrial processes, including being an essential class of chemicals in the fabrication of semiconductors. Proven concerns related to bioaccumulation and toxicity across multiple species have resulted in health advisory and regulatory initiatives for PFAS

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals used for a wide variety of products and industrial processes, including being an essential class of chemicals in the fabrication of semiconductors. Proven concerns related to bioaccumulation and toxicity across multiple species have resulted in health advisory and regulatory initiatives for PFAS in drinking and wastewaters. Among impacted users of PFAS, the semiconductor industry is in urgent need of technologies to remove PFAS from water. Specifically, they prefer technologies capable of mineralizing PFAS into inorganic fluoride (F-). The goal of this thesis is to compare the effectiveness of photo- versus electrocatalytic treatment in benchtop reactor systems PFAS in industrial wastewater before selecting one technology to investigate comprehensively. First, a model wastewater was developed based upon semiconductor samples to represent water matrices near where PFAS are used and the aggregate Fab effluent, which were then used in batch catalytic experiments. Second, batch experiments with homogenous photocatalysis (UV/SO32-) were found to be more energy-intensive than heterogeneous catalysis using boron-doped diamond (BDD) electrodes, and the latter approach was then studied in-depth. During electrocatalysis, longer chain PFAS (C8; PFOA & PFOS) were observed to degrade faster than C6 and C4 PFAS. This study is the first to report near-complete defluorination of not only C8- and C6- PFAS, but also C4-PFAS, in model wastewaters using BDD electrocatalysis, and the first to report such degradation in real Fab wastewater effluents. Based upon differences in PFAS degradation rates observed in single-solute systems containing only C4 PFAS versus multi-solute systems including C4, C6, and C8 PFAS, it was concluded that the surfactant properties of the longer-chain PFAS created surface films on the BDD electrode surface which synergistically enhanced removal of shorter-chain PFAS. The results from batch experiments that serve as the basis of this thesis will be used to assess the chemical byproducts and their associated bioaccumulation and toxicity. This thesis was aimed at developing an efficient method for the degradation of perfluoroalkyl substances from industrial process waters at realistic concentrations.
ContributorsNienhauser, Alec Brockway (Author) / Westerhoff, Paul (Thesis advisor) / Garcia-Segura, Sergi (Committee member) / Thomas, Marylaura (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2021
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Description
This dissertation focused on the implementation of urine diversion systems in commercial and institutional buildings in the United States with a focus on control of the urea hydrolysis reaction. Urine diversion is the process by which urine is separately collected at the source in order to realize system benefits, including

This dissertation focused on the implementation of urine diversion systems in commercial and institutional buildings in the United States with a focus on control of the urea hydrolysis reaction. Urine diversion is the process by which urine is separately collected at the source in order to realize system benefits, including water conservation, nutrient recovery, and pharmaceutical removal. Urine diversion systems depend greatly on the functionality of nonwater urinals and urine diverting toilets, which are needed to collect undiluted urine. However, the urea hydrolysis reaction creates conditions that lead to precipitation in the fixtures due to the increase in pH from 6 to 9 as ammonia and bicarbonate are produced. Chapter 2 and Chapter 3 describes the creation and use of a cyber-physical system (CPS) to monitor and control urea hydrolysis in the urinal testbed. Two control logics were used to control urea hydrolysis in realistic restroom conditions. In the experiments, acid was added to inhibit urea hydrolysis during periods of high and low building occupancy. These results were able to show that acid should be added based on the restroom use in order to efficiently inhibit urea hydrolysis. Chapter 4 advanced the results from Chapter 3 by testing the acid addition control logics in a real restroom with the urinal-on-wheels. The results showed that adding acid during periods of high building occupancy equated to the least amount of acid added and allowed for urea hydrolysis inhibition. This study also analyzed the bacterial communities of the collected urine and found that acid addition changed the structure of the bacterial communities. Chapter 5 showed an example of the capabilities of a CPS when implemented in CI buildings. The study used data mining methods to predict chlorine residuals in premise plumbing in a CI green building. The results showed that advance modeling methods were able to model the system better than traditional methods. These results show that CPS technology can be used to illuminate systems and can provide information needed to understand conditions within CI buildings.
ContributorsSaetta, Daniella (Author) / Boyer, Treavor H (Thesis advisor) / Hamilton, Kerry (Committee member) / Ross, Heather M. (Committee member) / Boscovic, Dragan (Committee member) / Arizona State University (Publisher)
Created2021