This dissertation investigates the mechanisms that lead to fouling, as well as how an understanding of how these mechanisms can be leveraged to mitigate fouling.

To limit fouling on feed spacers, various coatings were applied. The results showed silver-coated biocidal spacers outperformed other spacers by all measures. The control polypropylene spacers performed in-line with, or better than, the other coatings. Polypropylene’s relative anti-adhesiveness is due to its surface free energy (SFE; 30.0 +/- 2.8 mN/m), which, according to previously generated models, is near the ideal SFE for resisting adhesion of bacteria and organics (~25 mN/m).

Previous research has indicated that electrochemical surfaces can be used to remove biofilms. To better elucidate the conditions and kinetics of biofilm removal, optical coherence tomography microscopy was used to visualize the biofouling and subsequent cleaning of the surface. The 50.0 mA cm-2 and 87.5 mA cm-2 current densities proved most effective in removing the biofilm. The 50.0 mA cm-2 condition offers the best balance between performance and energy use for anodic operation.

To test the potential to incorporate electrochemical coatings into infrastructure, membranes were coated with carbon nanotubes (CNTs), rendering the membranes electrochemically active. These membranes were biofouled and subsequently cleaned via electrochemical reactions. P. aeruginosa was given 72h to develop a biofilm on the CNT-coated membranes in a synthetic medium simulating desalination brines. Cathodic reactions, which generate H2 gas, produce vigorous bubbling at a current density of 12.5 mA cm-2 and higher, leading to a rapid and complete displacement of the biofilm from the CNT-functionalized membrane surface. In comparison, anodic reactions were unable to disperse the biofilms from the surface at similar current densities.

The scaling behavior of a nanophotonics-enabled solar membrane distillation (NESMD) system was investigated. The results showed the NESMD system to be resistant to scaling. The system operated without any decline in flux up to concentrations 6x higher than the initial salt concentration (8,439 mg/L), whereas in traditional membrane distillation (MD), flux essentially stopped at a salt concentration factor of 2x. Microscope and analytical analyses showed more fouling on the membranes from the MD system.

Zwitterionic polymers, due to their supurior capability of electrostatically induced hydration, have been considered as effective functionalities to alleviate bio-fouling of reverse osmosis (RO) membranes. Bulk modification of polysulfone-based matrices to improve hydrophilicity, on the other hand, is favored due to the high membrane performance, processibility, and intrinsic chlorine resistance. Here a novel synthetic method was demonstrated to prepare zwitterionic poly(arylene ether sulfone) (PAES) copolymers, which was blended with native polysulfone (PSf) to fabricate free-standing asymmetric membranes via non-solvent induced phase separation process. Both the porosity of the support layer and surface hydrophilicity increased drastically due to the incorporation of zwitterion functionalities in the rigid polysulfone matrix. The water permeance and antifouling ability of the blend membranes were both remarkably improved to 2.5 Lm−2 h−1 bar−1 and 94% of flux recovery ratio, respectively, while salt rejection remained at a high level (98%) even under the high exposure to chlorine (8,000 ppm•h). Besides the preliminary blended membrane design, for the future membrane property enhancement, this dissertation also focused on polymer structure optimizations via elucidating the fundamentals from two perspectives: 1). Synthetic reaction kinetics and mechanisms on polycondensation of PAES. Interestingly, in combination of experiments and the computational calculations by density functional theory (DFT) methods in this work, only the aryl chlorides (ArCl) monomer follows the classical second-order reaction kinetics of aromatic nucleophilic substitution (SNAr) mechanism, while the kinetics of the aryl fluorides (ArF) reaction fit a third-order rate law. The third order reaction behavior of the ArF monomer is attributed to the activation of the carbon-fluorine bond by two potassium cations (at least one bounded to phenolate), which associate as a strong three-body complex. This complex acts as the predominant reactant during the attack by the nucleophile. 2). Optimized copolymer structures were developed for controlled high molecular weight (Mw ~ 65 kDa) and zwitterionic charge content (0~100 mol%), via off-set stoichiometry during polycondensations, following with thiol-ene click reaction and ring-opening of sultone to introduce the sulfobetaine functional groups. The structure-property-morphology relationships were elucidated for better understanding atomic-level features in the charged polymers for future high-performance desalination applications.

In order to produce efficient reverse osmosis membranes, it is necessary to minimize the effects of outside factors on the membrane surface that can reduce the flux of water through the membrane. One such problem is fouling. Fouling happens when particles are deposited on the membrane surface, blocking water flow through the membrane. Over time, the collection of foulants will prevent water through the membrane, increasing the amount of energy required in the system. Microgel, a heat-responsive colloidal gel, shows promise as an anti-foulant coating as it possesses functional groups similar to the membrane and compatible with common foulants and changes volume due to temperature differences. By coating the membrane with the microgel, foulants will attach to the functional groups of the microgel instead of those of the membrane Our hypothesis is that the change in volume of the microgel with different temperatures will help reduce and remove foulants. By functionalizing the surface of the membrane and the microgel, the microgel can covalently bond to the membrane surface and avoid detachment under reverse osmosis conditions. Microgel-coated reverse osmosis membranes have been fluorescently fouled to measure the decrease in foulants with heated crossflow under fluorescent microscopy. This process has shown a 50% decrease in fluorescence on the surface of the membrane indicating a decrease in foulants due to the presence of microgel. Under cross-flow conditions with a low flow rate, the microgel remains on the functionalized membrane for 8 hours with similar anti-fouling performance as the dip-coating process.

C.C. Cragin Reservoir’s location in the Coconino National Forest, Arizona makes it prone to wild fire. This study focused on the potential impacts of such a wild fire on the reservoir’s annual thermal stratification cycle impacts and water quality. The annual thermal stratification cycle impacted the reservoir’s water quality by increasing hypolimnion concentrations of magnesium, iron, turbidity, and specific ultraviolet absorbance (SUVA) values, as well as resulting in the hypolimnion having decreased dissolved oxygen concentrations during stratified months. The scarification process did not affect the dissolved organic carbon (DOC) concentrations in the reservoir or the total/dissolved nitrogen and phosphorous concentrations. Some general water quality trends that emerged were that phosphorous was the limiting nutrient, secchi disk depth and chlorophyll a concentration are inversely related, and no metals were found to be in concentrations that would violate an EPA drinking water maximum contaminant level (MCL). A carbon mass model was developed and parameterized using DOC measurements, and then using historic reservoir storage and weather data, the model simulated DOC concentrations in the reservoir following four hypothetical wild fire events. The model simulated varying initial reservoir storage volumes, initial flush volumes, and flush DOC concentrations, resulting in reservoir DOC concentrations varying from 17.41 mg/L to 8.82 mg/L.

Electrospinning is a means of fabricating micron-scale diameter fiber networks with enmeshed nanomaterials. Polymeric nanocomposites for water treatment require the manipulation of fiber morphology to expose nanomaterial surface area while anchoring the nanomaterials and maintaining fiber integrity; that is the overarching goal of this dissertation. The first investigation studied the effect of metal oxide nanomaterial loadings on electrospinning process parameters such as critical voltage, viscosity, fiber diameter, and nanomaterial distribution. Increases in nanomaterial loading below 5% (w/v) were not found to affect critical voltage or fiber diameter. Nanomaterial dispersion was conserved throughout the process. Arsenic adsorption tests determined that the fibers were non-porous. Next, the morphologies of fibers made with carbonaceous materials and the effect of final fiber assembly on adsorption kinetics of a model organic contaminant (phenanthrene, PNT) was investigated. Superfine powdered activated carbon (SPAC), C60 fullerenes, multi-walled carbon nanotubes, and graphene platelets were added to PS and electrospun. SPAC maintained its internal pore structure and created porous fibers which had 30% greater PNT sorption than PS alone and a sevenfold increase in surface area. Carbon-based nanomaterial-PS fibers were thicker but less capacious than neat polystyrene electrospun fibers. The surface areas of the carbonaceous nanomaterial-polystyrene composites decreased compared to neat PS, and PNT adsorption experiments yielded decreased capacity for two out of three carbonaceous nanomaterials. Finally, the morphology and arsenic adsorption capacity of a porous TiO2-PS porous fiber was investigated. Porous fiber was made using polyvinylpyrrolidone (PVP) as a porogen. PVP, PS, and TiO2 were co-spun and the PVP was subsequently eliminated, leaving behind a porous fiber morphology which increased the surface area of the fiber sevenfold and exposed the nanoscale TiO2 enmeshed inside the PS. TiO2-PS fibers had comparable arsenic adsorption performance to non-embedded TiO2 despite containing less TiO2 mass. The use of a sacrificial polymer as a porogen facilitates the creation of a fiber morphology which provides access points between the target pollutant in an aqueous matrix and the sorptive nanomaterials enmeshed inside the fiber while anchoring the nanomaterials, thus preventing release.

Nitrate contamination to groundwater and surface water is a serious problem in areas with high agricultural production due to over application of fertilizers. There is a need for alternative technologies to reduce nutrient runoff without compromising yield. Carbon nanoparticles have adsorptive properties and have shown to improve germination and yield of a variety of crops. Graphite nanoparticles (CNP) were studied under a variety of different fertilizer conditions to grow lettuce for the three seasons of summer, fall, and winter. The aim of this thesis was to quantify the effect of CNPs on nitrate leaching and lettuce growth. This was accomplished by measuring the lettuce leaf yield, formulating a nutrient balance using the leachate, plant tissue, and soil data, and changing the hydraulic conductivity of the soil to assess the effect on nutrient mobility. summer and fall experiments used Arizona soil with different amounts of nitrogen, phosphorus, and potassium (NPK) fertilizer being applied to the soil with and without CNPs. The winter experiments used three different soil blends of Arizona soil, Arizona soil blended with 30% sand, and Arizona soil blended with 70% sand with a constant fertilizer treatment of 30% NPK with and without CNPs. The results showed that the 70% NPK with CNP treatment was best at reducing the amount of nitrate leached while having little to no compromise in yield. The winter experiments showed that the effectiveness of CNPs in reducing nitrate leaching and enhancing yield, improved with the higher the hydraulic conductivity of the soil.

Consumers purchase point-of-use (POU) devices to further improve the quality of water provided by the tap. As awareness increases of harmful contaminants, an emerging market of advanced POU with claims of removing beyond what a typical activated carbon filter is capable of, such as heavy metals. This research compares four commercially available pitcher filters; two that claim to remove arsenic and hexavalent chromium and two without such claims. Arsenate (As (V)) and hexavalent chromium (Cr (VI)) co-occur in natural geologic formations and are known to have harmful effects on humans when ingested. Pitcher filters Epic Water Filter and Aquagear had claims of removing both As (V) and Cr (VI) up to 99% with a capacity of nearly 200 gallons. In contrast, pitcher filters Brita and Pur had no claims for removal of As(V) and Cr(VI) with a 40-gallon lifespan. A series of experiments were conducted to first determine the efficiency of each filter, then to add the ability or improve removal of As(V) and Cr(VI) in one filter for future design implementations. Experiment 1 was conducted by treating 100 gallons of spiked tap water (50 ppb for As (V) and 100 ppb for Cr (VI)) with each filter. All four pitcher filters showed low performance, resulting in Pur with the lowest removal percentage of 2% and Aquagear with the highest percentage 16% for As (V). For Cr (VI) Pur performed the worst with a removal of 5% and Brita had the best performance of 15%. The functionality of Brita was improved by embedding a selective ion exchange media, which when nanotized successfully removed Cr (VI) in previous studies. The optimal mass of resin to add to the pitcher was experimentally determined as 18.9 grams through Experiment 2. Finally, Experiment 3 compared an alternative placement of the resin material using the same 18.9 grams. The performance in Experiment 3 was significantly worse than Experiment 2. The final recommendation for future design implementation was to add 18.9 grams of SIR-700 resin below the filter media for optimum performance. Overall, the results demonstrate the limited removal of As(V) and Cr(VI) by the four commercial pitcher filters and show that by adding selective ion exchange media, the POUs can be nano-enabled to effectively remove As(V) and Cr(VI) from water.

Drinking water filtration using reverse osmosis (RO) membranes effectively removes salts and most other inorganic, organic, and microbial pollutants. RO technologies are utilized at both the municipal and residential scale. The formation of biofilms on RO membranes reduces water flux and increases energy consumption. The research conducted for this thesis involves In-Situ coating of silver, a known biocide, on the surface of RO membranes. This research was adapted from a protocol developed for coating flat sheet membranes with silver nanoparticles, and scaled up into spiral-wound membranes that are commonly used at the residential scale in point-of-use (POU) filtration systems. Performance analyses of the silver-coated spiral-wound were conducted in a mobile drinking water treatment system fitted with two POU units for comparison. Five month-long analyses were performed, including a deployment of the mobile system. In addition to flux, salt rejection, and other water quality analyses, additional membrane characterization tests were conducted on pristine and silver-coated membranes.

For flat sheet membranes coated with silver, the surface charge remained negative and contact angle remained below 90. Scaling up to spiral-wound RO membrane configuration was successful, with an average silver-loading of 1.93 g-Ag/cm2. Results showed the flux of water through the membrane ranged from 8 to 13 liters/m2*hr. (LMH) operating at 25% recovery during long-term of operation. The flux was initially decreased due to the silver coating, but no statistically significant differences were observed after 14 days of operation (P < 0.05). The salt rejection was also not effected due to the silver coating (P < 0.05). While 98% of silver was released during long-term studies, the silver release from the spiral-wound membrane was consistently below the secondary MCL of 100 ppb established by the EPA, and was consistently below 5 ppb after two hours of operation. Microbial assays in the form of heterotrophic plate counts suggested there was no statistically significant difference in the prevention of biofouling formation due to the silver coating (P < 0.05). In addition to performance tests and membrane characterizations, a remote data acquisition system was configured to remotely monitor performance and water quality parameters in the mobile system.

With the application of reverse osmosis (RO) membranes in the wastewater treatment and seawater desalination, the limitation of flux and fouling problems of RO have gained more attention from researchers. Because of the tunable structure and physicochemical properties of nanomaterials, it is a suitable material that can be used to incorporate with RO to change the membrane performances. Silver is biocidal, which has been used in a variety of consumer products. Recent studies showed that fabricating silver nanoparticles (AgNPs) on membrane surfaces can mitigate the biofouling problem on the membrane. Studies have shown that Ag released from the membrane in the form of either Ag ions or AgNP will accelerate the antimicrobial activity of the membrane. However, the silver release from the membrane will lower the silver loading on the membrane, which will eventually shorten the antimicrobial activity lifetime of the membrane. Therefore, the silver leaching amount is a crucial parameter that needs to be determined for every type of Ag composite membrane.

This study is attempting to compare four different silver leaching test methods, to study the silver leaching potential of the silver impregnated membranes, conducting the advantages and disadvantages of the leaching methods. An In-situ reduction Ag loaded RO membrane was examined in this study. A custom waterjet test was established to create a high-velocity water flow to test the silver leaching from the nanocomposite membrane in a relative extreme environment. The batch leaching test was examined as the most common leaching test method for the silver composite membrane. The cross-flow filtration and dead-end test were also examined to compare the silver leaching amounts.

The silver coated membrane used in this experiment has an initial silver loading of 2.0± 0.51 ug/cm2. The mass balance was conducted for all of the leaching tests. For the batch test, water jet test, and dead-end filtration, the mass balances are all within 100±25%, which is acceptable in this experiment because of the variance of the initial silver loading on the membranes. A bad silver mass balance was observed at cross-flow filtration. Both of AgNP and Ag ions leached in the solution was examined in this experiment. The concentration of total silver leaching into solutions from the four leaching tests are all below the Secondary Drinking Water Standard for silver which is 100 ppb. The cross-flow test is the most aggressive leaching method, which has more than 80% of silver leached from the membrane after 50 hours of the test. The water jet (54 ± 6.9% of silver remaining) can cause higher silver leaching than batch test (85 ± 1.2% of silver remaining) in one-hour, and it can also cause both AgNP and Ag ions leaching from the membrane, which is closer to the leaching condition in the cross-flow test.

The purpose of this research was to produce reduced graphene oxides for the fabrication of desalination membranes. Graphene has typically been considered a way to create more energy efficient desalination membranes. However, graphene is expensive and unstable, while graphene oxide has similar properties, but is less expensive and more stable. Graphene oxide membranes have the potential to perform above the permeability-selectivity tradeoff that is typical in membranes through size-based exclusion. Reduction through heat or Vitamin C reduces the size of graphene oxide nanochannels so salt and organic materials can be rejected in higher numbers. Both reduced and unreduced graphene oxide membranes were created and evaluated by their ability to filter dye and salt in a pressurized membrane cell. The permeability and rejection of the graphene oxide membrane is found to be dependent on the oxidation level of the graphene oxide material and the concentration on the graphene oxide on the membrane. Unreduced graphene oxide membranes were created in three concentrations: 7.37, 14.74, and 29.47 μg/cm2. As graphene oxide concentration increased, dye rejection and salt rejection increased, while water flux decreased. Graphene oxide was reduced in solution using Vitamin C and was used to create a 14.74 μg/cm2 membrane. The reduction resulted in an increase in salt rejection from 12.59% to 100%, an increase in dye rejection from 30.44% to 100%, and a decrease in water flux from 9.502 to 0.198 L/(hr*m2*bar). Future research should focus on creating membranes using different methods of synthesizing graphene oxide from graphene and creating a reduced graphene oxide membrane with a higher water flux.