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- Creators: Westerhoff, Paul
- Resource Type: Text
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
Contamination of drinking water supplies from oxo-anion pollutants necessitates treatment prior to potable use. This dissertation aims to inform and improve light delivery (emission spectra, radiant intensity, reactor configuration) in order to enhance the photocatalytic reduction of hexavalent chromium (Cr(VI)) and nitrate, two common oxo-anions in drinking water, and photocatalytic oxidation of two model organic pollutants (methylene blue, (MB) and para-chlorobenzoic acid (pCBA)). By varying the photon fluence dose, two metrics (contaminant quantum yield (Φ), and electrical energy per order (EEO)) were used to assess photocatalytic reactor performance. A detailed literature review and experimental results demonstrated how different irradiance sources with variable intensity and emission spectra synergistically enhanced contaminant removal by a coupled photolytic/photocatalytic reaction mechanism. Cr(VI) was photocatalytically reduced on TiO2 and formed Cr(OH)3(s) in a large-scale slurry reactor, but Cr(III) was then photolyzed and reformed Cr(VI). UV light also led to photo-aggregation of TiO2 which improved its recovery by the ceramic membrane within the reactor. For nitrate reduction, light source emission spectra and fluence dose delineate the preferred pathways as intermediates were reduced via wavelength-dependent mechanisms. HONO was identified as a key nitrate reduction intermediate, which was reduced photocatalytically (UV wavelengths) and/or readily photolyzed at 365nm, to yield nitrogen gases. Photocatalytic nitrate reduction efficiency was higher for discrete wavelength irradiation than polychromatic irradiation. Light delivery through aqueous media to the catalyst surface limits efficiency of slurry-based photocatalysts because absorption and scattering of light in nanomaterial slurries decreases effective photon transmittance and minimizes photolytic reactions. The use of optical fibers coupled to light emitting diodes (OF-LED) with immobilized catalyst demonstrated higher performance compared to slurry systems. OF-LED increased Φ for MB degradation by increasing direct photon delivery to the photocatalyst. Design of OF-LED reactors using bundled optical fibers demonstrated photocatalytic pCBA removal with high Φ and reduced EEO due to increased surface area and catalytic sites compared to single OF/LED couples. This work advances light delivery as well as the suspension and attachment of nanoparticles in photocatalytic water treatment for selective transformation of oxo-anions and organic compounds to innocuous species.
ContributorsTugaoen, Heather O'Neal (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Thesis advisor) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2017
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 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
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 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