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Potential for Accumulation of Boron in Direct Potable Reuse

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This report analyzes the potential for accumulation of boron in direct potable reuse. Direct potable reuse treats water through desalination processes such as reverse osmosis or nanofiltration which can achieve rejection rates of salts sometimes above 90%. However, boron achieves

This report analyzes the potential for accumulation of boron in direct potable reuse. Direct potable reuse treats water through desalination processes such as reverse osmosis or nanofiltration which can achieve rejection rates of salts sometimes above 90%. However, boron achieves much lower rejection rates near 40%. Because of this low rejection rate, there is potential for boron to accumulate in the system to levels that are not recommended for potable human consumption of water. To analyze this issue a code was created that runs a steady state system that tracks the internal concentration, permeate concentration, wastewater concentration and reject concentration at various rejection rates, as well as all the flows. A series of flow and mass balances were performed through five different control volumes that denoted different stages in the water use. First was mixing of clean water with permeate; second, consumptive uses; third, addition of contaminant; fourth, wastewater treatment; fifth, advanced water treatments. The system cycled through each of these a number of times until steady state was reached. Utilities or cities considering employing direct potable reuse could utilize this model by estimating their consumption levels and input of contamination, and then seeing what percent rejection or inflow of makeup water they would need to obtain to keep boron levels at a low enough concentration to be fit for consumption. This code also provides options for analyzing spikes and recovery in the system due to spills, and evaporative uses such as cooling towers and their impact on the system.

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2017-12

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Examining Biofouling on Pristine and Aged Microplastics Exposed to Tempe Town Lake Water

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This study investigated the difference in biofilm growth between pristine polypropylene microplastics and aged polypropylene microplastics. The microplastics were added to Tempe Town Lake water for 4 weeks. Each week the microplastic biofilms were quantified. Comparing the total biofilm counts,

This study investigated the difference in biofilm growth between pristine polypropylene microplastics and aged polypropylene microplastics. The microplastics were added to Tempe Town Lake water for 4 weeks. Each week the microplastic biofilms were quantified. Comparing the total biofilm counts, the results showed that the aged microplastic biofilms were larger than the pristine each week. By week 3 the aged microplastic counts had almost doubled in size increasing from 324 to 626 Colony Forming Units per gram in just one week. There was a significant difference in the diversity found from week 1 to week 4. About 40% of the diversity for the pristine microplastic biofilm was seen as light-yellow dots and about 60% of these dots were seen on the aged microplastic biofilms in both weeks. As the microplastics were submerged in the lake water, new phenotypes emerged varying from week 1 to week 4 and from pristine to aged microplastic biofilms. Generally, it was found that as the microplastics stay in the environment there is more biofilm on the particles. The aged microplastics have a larger amount of biofouling, and the pristine microplastic biofilms were found to have more diversity of phenotypes.

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2021-05

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Graphene oxide mixed matrix membranes for improved desalination performance

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Reverse osmosis (RO) membranes are considered the most effective treatment to remove salt from water. Specifically, thin film composite (TFC) membranes are considered the gold standard for RO. Despite TFC membranes good performance, there are drawbacks to consider including: permeability-selectivity

Reverse osmosis (RO) membranes are considered the most effective treatment to remove salt from water. Specifically, thin film composite (TFC) membranes are considered the gold standard for RO. Despite TFC membranes good performance, there are drawbacks to consider including: permeability-selectivity tradeoff, chlorine damage, and biofouling potential. In order to counter these drawbacks, polyamide matrixes were embedded with various nanomaterials called mixed matrix membranes (MMMs) or thin film nanocomposites (TFNs). This research investigates the use of graphene oxide (GO) and reduced graphene oxide (RGO) into the polyamide matrix of a TFC membrane. GO and RGO have the potential to alter the permeability-selectivity trade off by offering nanochannels for water molecules to sieve through, protect polyamide from trace amounts of chlorine, as well as increase the hydrophilicity of the membrane thereby reducing biofouling potential. This project focuses on the impacts of GO on the permeability selectivity tradeoff. The hypothesis of this work is that the permeability and selectivity of GO can be tuned by controlling the oxidation level of the material. To test this hypothesis, a range of GO materials were produced in the lab using different graphite oxidation methods. The synthesized GOs were characterized by X-ray diffraction and X-ray photoelectron microscopy to show that the spacing is a function of the GO oxygen content. From these materials, two were selected due to their optimal sheet spacing between 3.4 and 7 angstroms and embedded into desalination MMM. This work reveals that the water permeability coefficient of MMM embedded with GO and RGO increased significantly; however, that the salt permeability coefficient of the membrane also increased. Future research directions are proposed to overcome this limitation.

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2017

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Comparison of four methods to assess silver release from nano impregnated reverse osmosis membranes

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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,

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.

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2017

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Passive and active surfaces to reduce fouling of membranes and membane modules

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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

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.

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2019

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Controlling Silver Release from Antibacterial Surface Coatings on Stainless Steel for Biofouling Control

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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

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.

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Date Created
2021

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Electrospun polymeric nanocomposites for aqueous inorganic and organic pollutant removal

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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

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.

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Date Created
2018

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Immobilization of T4 on modified silica particles

Description

Bacteriophage provide high specificity to bacteria; receiving interest in various applications and have been used as target recognition tools in designing bioactive surfaces. Several current immobilization strategies to detect and capture bacteriophage require non-deliverable bioactive substrates or modifying the chemistry

Bacteriophage provide high specificity to bacteria; receiving interest in various applications and have been used as target recognition tools in designing bioactive surfaces. Several current immobilization strategies to detect and capture bacteriophage require non-deliverable bioactive substrates or modifying the chemistry of the phage, procedures that are labor intensive and can damage the integrity of the virus. The aim of this research was to develop the framework to physisorb and chemisorb T4 coliphage on varied sized functionalized silica particles while retaining its infectivity. First, silica surface modification, silanization, altered pristine silica colloids to positively, amine coated silica. The phages remain infective to their host bacteria while adsorbed on the surface of the silica particles. It is reported that the number of infective phage bound to the silica is enhanced by the immobilization method. It was determined that covalent attachment yielded 106 PFU/ml while electrostatic attachment resulted in 105 PFU/ml.

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Date Created
2017

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Environmental releases of neonicotinoid and fipronil insecticides via U.S. wastewater infrastructure

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This dissertation is focused on environmental releases from U.S. wastewater infrastructure of recently introduced, mass-produced insecticides, namely neonicotinoids as well as fipronil and its major degradates (sulfone, sulfide, amide, and desulfinyl derivatives), jointly known as fiproles. Both groups of compounds

This dissertation is focused on environmental releases from U.S. wastewater infrastructure of recently introduced, mass-produced insecticides, namely neonicotinoids as well as fipronil and its major degradates (sulfone, sulfide, amide, and desulfinyl derivatives), jointly known as fiproles. Both groups of compounds recently have caught the attention of regulatory agencies worldwide due to their toxic effects on pollinators and on aquatic invertebrates at very low, part-per-trillion levels (Chapter 1). Mass balance studies conducted for 13 U.S. wastewater treatment plants (WWTPs) showed ubiquitous occurrence (3-666 ng/L) and persistence of neonicotinoids (Chapter 2). For the years 2001 through 2016, a longitudinal nationwide study was conducted on the occurrence of fiproles, via analysis of sludge as well as raw and treated wastewater samples. Sludge analysis revealed ubiquitous fiprole occurrence since 2001 (0.2-385 µg/kg dry weight) and a significant increase (2.4±0.3-fold; p<0.005) to elevated levels found both in 2006/7 and 2015/6. This study established a marked persistence of fiproles during both wastewater and sludge treatment, while also identifying non-agricultural uses as a major source of fiprole loading to wastewater (Chapter 3). Eight WWTPs were monitored in Northern California to assess pesticide inputs into San Francisco Bay from wastewater discharge. Per-capita-contaminant-loading calculations identified flea and tick control agents for use on pets as a previously underappreciated source term dominating the mass loading of insecticides to WWTPs in sewage and to the Bay in treated wastewater (Chapter 4). A nationwide assessment of fipronil emissions revealed that pet products, while representing only 22±7% of total fipronil usage (2011-2015), accounted for 86±5% of the mass loading to U.S. surface waters (Chapter 5). In summary, the root cause for considerable annual discharges into U.S. surface waters of the neonicotinoid imidacloprid (3,700-5,500 kg/y) and of fipronil related compounds (1,600-2,400 kg/y) is domestic rather than agricultural insecticide use. Reclaimed effluent from U.S. WWTPs contained insecticide levels that exceed toxicity benchmarks for sensitive aquatic invertebrates in 83% of cases for imidacloprid and in 67% of cases for fipronil. Recommendations are provided on how to limit toxic inputs in the future.

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2017

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Water quality and thermal stratification of Cragin Reservoir: current and future impact of forest fires

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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.

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.

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Date Created
2018