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Description
Zero-Valent Metals (ZVM) are highly reactive materials and have been proved to be effective in contaminant reduction in soils and groundwater remediation. In fact, zero-Valent Iron (ZVI) has proven to be very effective in removing, particularly chlorinated organics, heavy metals, and odorous sulfides. Addition of ZVI has also been proved

Zero-Valent Metals (ZVM) are highly reactive materials and have been proved to be effective in contaminant reduction in soils and groundwater remediation. In fact, zero-Valent Iron (ZVI) has proven to be very effective in removing, particularly chlorinated organics, heavy metals, and odorous sulfides. Addition of ZVI has also been proved in enhancing the methane gas generation in anaerobic digestion of activated sludge. However, no studies have been conducted regarding the effect of ZVM stimulation to Municipal Solid Waste (MSW) degradation. Therefore, a collaborative study was developed to manipulate microbial activity in the landfill bioreactors to favor methane production by adding ZVMs. This study focuses on evaluating the effects of added ZVM on the leachate generated from replicated lab scale landfill bioreactors. The specific objective was to investigate the effects of ZVMs addition on the organic and inorganic pollutants in leachate. The hypothesis here evaluated was that adding ZVM including ZVI and Zero Valent Manganese (ZVMn) will enhance the removal rates of the organic pollutants present in the leachate, likely by a putative higher rate of microbial metabolism. Test with six (4.23 gallons) bioreactors assembled with MSW collected from the Salt River Landfill and Southwest Regional Landfill showed that under 5 grams /liter of ZVI and 0.625 grams/liter of ZVMn additions, no significant difference was observed in the pH and temperature data of the leachate generated from these reactors. The conductivity data suggested the steady rise across all reactors over the period of time. The removal efficiency of sCOD was highest (27.112 mg/lit/day) for the reactors added with ZVMn at the end of 150 days for bottom layer, however the removal rate was highest (16.955 mg/lit/day) for ZVI after the end of 150 days of the middle layer. Similar trends in the results was observed in TC analysis. HPLC study indicated the dominance of the concentration of heptanoate and isovalerate were leachate generated from the bottom layer across all reactors. Heptanoate continued to dominate in the ZVMn added leachate even after middle layer injection. IC analysis concluded the chloride was dominant in the leachate generated from all the reactors and there was a steady increase in the chloride content over the period of time. Along with chloride, fluoride, bromide, nitrate, nitrite, phosphate and sulfate were also detected in considerable concentrations. In the summary, the addition of the zero valent metals has proved to be efficient in removal of the organics present in the leachate.
ContributorsPandit, Gandhar Abhay (Author) / Cadillo – Quiroz, Hinsby (Thesis advisor) / Olson, Larry (Thesis advisor) / Boyer, Treavor (Committee member) / Arizona State University (Publisher)
Created2019
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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
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

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.
ContributorsRanjbari, Kiarash (Author) / Perreault, Francois (Thesis advisor) / Abbaszadegan, Morteza (Committee member) / Islam, Mohammed R (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Nearly 2.1 billion people around the world to date do not have access to safe drinking water. This study proposes a compact (2-L) upflow photoreactor that uses widely available photocatalysts material, such as titanium dioxide (TiO2) or hexagonal boron nitrate (hBN), to oxidize toxic micropollutants. Photocatalysts, such as TiO2, can

Nearly 2.1 billion people around the world to date do not have access to safe drinking water. This study proposes a compact (2-L) upflow photoreactor that uses widely available photocatalysts material, such as titanium dioxide (TiO2) or hexagonal boron nitrate (hBN), to oxidize toxic micropollutants. Photocatalysts, such as TiO2, can create powerful hydroxyl radicals (OH•) under UV irradiation to oxidize and disinfect water with various toxic pollutants present in untreated waters. The study assesses this along with few other photoreactors in terms of their performance with an indicator dye, such as methyl orange (MO), para-chlorobenzoic acid (pCBA), as an intermediate of pesticides, and perfluorooctanoic acid (PFOA), part of the per- and polyfluoroalkyl substances (PFAS), a highly persistent organic contaminant in water. This study also describes the various stages of evolution of this 2-L photoreactor, first using TiO2 coated sand in maintaining a uniform (photocatalyst) bed in suspension along with few other modifications that resulted in a photoreactor with a 3 to 4-fold increase in contact time, is discussed. The final stage of this upflow photoreactor modification resulted in the direct use of photocatalysts as a slurry, which was critical, especially for hBN, which cannot be coated onto the sand particles. During this modification and assessment, a smaller bench-top photoreactor (i.e., collimated beam) was also built and tested. It was primarily used in screening various photocatalysts and operational conditions before assessment at this upflow photoreactor and also at a commercial photoreactor (Purifics Photo-Cat) of a larger scale. Thus, the overall goal of this study is to compare a few of these photoreactors of different designs and scales. This includes a collimated beam (at bench-scale), upflow photoreactor (at testbed scale), and a commercial photoreactor, Photo-Cat (at pilot-scale). This study also discusses the performance of these photoreactors under different operating conditions, which includes evaluating two different photocatalyst types (TiO2 and hBN), variable loading rates, applied UV doses, environment pH, and supplemental peroxide addition (as AOP) and with corresponding EEO values.
ContributorsCao, Jiefei (Author) / Sinha, Shahnawaz (Thesis advisor) / Westerhoff, Paul (Committee member) / Ersan, Mahmut (Committee member) / Arizona State University (Publisher)
Created2021
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Description
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

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.
ContributorsCrane, Lucas Christopher (Author) / Boyer, Treavor H (Thesis advisor) / Perreault, Francois (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2022