Global shortages of urea and unsustainable production of synthetic urea have caused concerns over the future of food production, automobile operation, and other processes. Urine is a waste product that could supplement synthetic urea production. This study utilizes polyamide reverse osmosis (RO) and nanofiltration (NF) membranes in a cross-flow orientation to selectively recover urea from fresh human urine. Urea permeation experiments were conducted to determine the effects of urea stabilization via pH adjustment and membrane type on the production of a pure urea product. Fouling mitigation experiments were then conducted to determine the efficacy of microfiltration (MF) pretreatment on the reduction of the membrane fouling layer. The results showed that the NF90 membrane had advantageous performance to the BW30 RO and NF270 membranes, permeating 76% of the urea while rejecting 68% of the conductivity. Urine stabilization via acetic acid or sodium hydroxide addition did not inhibit membrane performance, signifying the use of pH 5 as a suitable pretreatment condition. Real fresh urine had higher rejection of constituents for NF90, suggesting the reduction of flux across the membrane due to interactions with organic material. MF pretreatment reduced foulant thickness and permeate flux loss but did not change the speciation of microorganisms. Finally, different urea-based products, such as fertilizers, biocement, and synthetic polymers, were suggested to show the potential of urine-recovered urea to reduce costs. The results from this work show the efficacy of using polyamide RO and NF membranes to supplement unsustainable synthetic production of urea with sustainably sourced urea from a waste product, human urine.

Existing water quality sensors in surface, environmental, and drinking water systems are not well suited for long-term, scalable use as they require calibration, replacement of reagents, and are subject to biofouling which degrades measurement accuracy. Microbial Potentiometric Sensors (MPSs) offer an alternative approach to water quality monitoring by monitoring a biofilm-mediated potentiometric response to diverse water quality parameters. MPS biofilms grow naturally on graphite electrodes in diverse aqueous systems, are regenerative, and their potentiometric response correlates with numerous water quality parameters. As such, the overarching hypothesis of this dissertation is that MPS signal can be used to assess water quality trends and that its signal is driven by biofilm vitality. To test this hypothesis, machine learning, statistical regression, and the use of more complex, impedimetric measurement techniques were explored to characterize water quality trends in diverse water systems. This was accomplished by completing three dissertation objectives: 1.) Assess whether Machine Learning/Artificial Intelligence (ML/AI) tools can be used to disaggregate various surface water quality parameter values from Open Circuit Potential (OCP) signals produced by MPSs; 2.) Determine whether residual free chlorine concentration in drinking water could be determined by monitoring MPSs; and 3.) Determine whether OCP and/or Electrochemical Impedance Spectroscopy (EIS)-derived impedance data from an MPS can be used to determine water quality trends while confirming its biological origins. The findings confirm the hypothesis by demonstrating that ML/AI can be used to disaggregate MPS signal and determine numerous water quality parameters, offering unique opportunities for real-time monitoring of aqueous environments. Additionally, MPSs are particularly useful in measuring free chlorine concentrations in drinking water distribution systems which offers opportunities for scalable, in-situ, continuous monitoring of chlorine throughout a distribution network. Finally, the findings demonstrate that coupling MPSs’ OCP signal with more advanced measurement techniques such as EIS can improve understanding of drinking water quality trends, however current open source, affordable technologies capable of conducting EIS are prone to high measurement noise and are not currently accurate enough to be used in drinking water systems.

The waterways in the United States are polluted by agricultural, mining, and industrial activities. Recovery of valuable materials, such as energy and nutrients, from these waste streams can improve the economic and environmental sustainability of wastewater treatment. A number of state-of-the-art anaerobic bioreactors have promise for intensified anaerobic biological treatment and energy recovery, but they have drawbacks. The drawbacks should be overcome with a novel anaerobic biological wastewater treatment process: the anaerobic biofilm membrane bioreactor (AnBfMBR). This research works aims to advance key components of the AnBfMBR. The AnBfMBR is a hybrid suspended growth and biofilm reactor. The two main components of an AnBfMBR are plastic biofilm carriers and membranes. The plastic biofilm carriers provide the surface onto which the biofilms grow. Membranes provide liquid-solid separation, retention of suspended biomass, and a solids-free effluent. Introducing sufficient surface area promotes the biofilm accumulation of slow-growing methanogens that convert volatile fatty acids into methane gas. Biofilms growing on these surfaces will have a mixed culture that primarily consists of methanogens and inert particulate solids, but also includes some acetogens. Biomass that detaches from biofilms become a component of the suspended growth. A bench-scale AnBfMBR was designed by the AnBfMBR project team and constructed by SafBon Water Technology (SWT). The primary objective of this thesis project was to evaluate the ability of plastic biofilm carriers to minimize ceramic-membrane fouling in the AnBfMBR setting. A systematic analysis of mixing for the bench-scale AnBfMBR was also conducted with the plastic biofilm carriers. Experiments were conducted following a ‘run to failure’ method, in which the ceramic membranes provide filtration, and the time it takes to reach a ‘failure transmembrane pressure (TMP)’ was recorded. The experiments revealed two distinct trends. First, the time to failure TMP decreased as mixed liquor suspended solids concentration (MLSS) concentration increased. Second, increasing the carrier fill extend the time to failure, particularly for higher MLSS concentrations. Taken together, the experiments identified an optimized “sweet spot” for the AnBfMBR: an operating flux of 0.25-m/d, a failure TMP of 0.3-atm pressure, MLSS of 5,000 – 7,500 mg/L, and 40% carrier fill.

Glasses have many applications such as containers, substrates of displays, high strength fibers and portable electronic display panels. Their excellent mechanical properties such as high hardness, good forming ability and scratch resistance make glasses ideal for these applications. Many factors affect the selection of one glass over another for a given purpose such as cost, ingredients, scalability of manufacturing, etc. Typically, silicate based glasses are often selected because they satisfy most of the selection criteria. However, with the recent abundant use of these glasses in touch-based applications, understanding their abilities to dissipate energy due to surface contact loads has become increasingly desirable. The most common silicate glasses worldwide are glassy silica and soda lime. Calcium aluminosilicates are also gaining popularity due to their importance as substrates for display screens in electronic devices. The surface energy dissipation and strength of these glasses are based on several factors, but predominantly rely on ingredient composition and the so-called Indentation Size Effect (ISE), where the strength depends on the maximum surface force. Both the composition and ISE alter the strength and favored energy dissipation mechanisms of the glass. Unlocking the contribution of these mechanisms and elucidating their dependence on composition and force is the underlining goal of this thesis.Prior to cracking, silicate glasses can inelastically deform by shear and densification. However, the link between the mechanical properties, strength, glass structure and maximum force and the propensity by which either of these mechanisms are favored still remains unclear. In this study, the first aim is to elucidate the causes of the ISE and i explore the relationships between the ISE and the dissipation mechanisms, and identify what feature(s) of the glass can be used to infer their behavior. All glasses have shown a strong link between the ISE and shear flow and densification. Second, the link between composition and the dissipation mechanisms will be elucidated. This is accomplished by performing indentation tests coupled with an annealing method to independently quantify the amount of volume associated with each dissipation mechanism and elucidate relationships with ingredients and structure of the glasses. Some conclusions will then be presented that link all these behaviors together.

Iodine and silver ions (Ag+), added as silver fluoride (AgF) or silver nitrate (AgNO3), are currently being used as a biocide to control the spread of bacteria in the water storage tanks of the International Space Station (ISS). Due to the complications of the iodine system, NASA is interested to completely replace iodine with silver and apply it as an antibacterial surface coating on stainless steel (SS) surfaces for biofouling control in extended space missions. However, Ag+ is highly soluble and rapidly dissolves in water, as a result, the coated surface loses its antibacterial properties. The dissolution of NPs into Ag+ and subsequent solubilization reduces its effectivity or extended period application. This study focuses on the in-situ nucleation of silver nanoparticles (AgNP) on stainless steel followed by their partial passivation by the formation of a low solubility silver sulfide (Ag2S), silver bromide (AgBr), and silver iodide (AgI) shell with various concentrations for an increased long-term biofouling performance and a slower silver release over time. Antibacterial activity was evaluated using Pseudomonas aeruginosa. The highest bacterial inactivation (up to 75%) occurred with sulfidized AgNPs as opposed to bromidized (up to 50%) and iodized NPs (up to 60%). Surface analysis by scanning electron microscopy (SEM) showed considerably fewer particles on AgBr and AgI compared to Ag2S-coated samples. Silver iodide was not tested in additional experiments due to its drawbacks and its poor antibacterial performance compared to sulfidized samples. Compared to pristine AgNPs, Ag release from both sulfidized and bromidized NPs was significantly low (16% vs 6% or less) depending on the extent of sulfidation or bromidation. Experiments were also carried out to investigate the effect of passivation on biofilm formation. Biofilm growth was smaller on surfaces treated with 10-3 M Na2S and 10-3 M NaBr compared to the surface of pristine AgNPs. Overall, sulfidation appears to be the most effective option to control biofilm formation on stainless steel. However, future research is needed to verify the effectiveness of sulfidized AgNPs on other metals including Inconel 718 and Titanium 6Al-4V used in the spacecraft potable water systems.

This dissertation focuses on the structure-function relationships of nanomaterials (NMs) and some of their applications in environmental engineering. The aim is to investigate NMs of different surface chemistries and assess their interactions with biological models, evaluate the weathering impact and degradation parameters to improve polymer coatings, test their efficiency for contaminant removal and provide further understanding in the safe design of nanomaterials. Nanoecotoxicological risk assessment currently suffers from a lack of testing procedures adapted to nanomaterials. Graphene oxide (GO) is a carbon nanomaterial (CNM) that consists of a single layer of carbon atoms arranged in a hexagonal network. It is decorated with a high density of oxygen functional groups including epoxide and hydroxyl moieties on the basal planes and carboxylic and carbonyl groups at the edges. The changes in surface chemistry give GO unique properties that can be tailored for a function. Additionally, because of its simple synthesis and flexible chemistry, GO has been a popular building block of many composite CNMs. In environmental engineering, specifically, water treatment, GO has been studied by itself or as a composite for pollutant removal, biofouling reduction, and as an antimicrobial agent, just to name a few. Like GO, silver (Ag) is another NM widely used in water treatment for its biocidal properties. Despite the recent growth in this field, a fundamental understanding of the function-structure relationships in NMs is still progressing. Through a systematic set of experiments, the structure-properties-function and structure-properties-hazard relationships were investigated. These relationships can be used to establish guidelines to engineer “safe-by-design” functional nanomaterials, where materials are tailored to enhance their function while minimizing their inherent biological or environmental hazard.

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.

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.

To successfully launch and maintain a long-term colony on Mars, Martian agricultural systems need to be capable of sustaining human life without requiring expensive deliveries from Earth. There is a need for more studies on this topic to make this a feasible mission. This thesis aims to study from a high level one such agricultural system, specifically examining the requirements and flow of Nitrogen, Phosphorus and Potassium required to sustain a given human colony size. We developed a Microsoft Excel based model that relates human nutritional needs to the amount available in food crops and in turn the amount of Martian soil required for agriculture. The model works by inputting the number of humans, and then utilizing the built-in calculations and datasets to determine how much of each nutrient is needed to meet all nutritional needs of the colony. Using that information, it calculates the amount of plants needed to supply the nutrition and then calculates the amount of nutrients that would be taken from the soil. It compares the Martian regolith to the nutrient uptake, accounting for inedible biomass from the plants and human waste that can be added to the regolith. Any deficiencies are used to determine if and how much fertilizer should be added to the system initially and over time. Using the total amount of plants and the number of harvests, the amount of Martian land required for sustaining the colony is computed. These results can be used as a building block to enable the successful design of an agricultural system on Mars.