Matching Items (9)
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- All Subjects: Water
- Creators: Westerhoff, Paul
- Member of: ASU Electronic Theses and Dissertations
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
Chloroform (CHCl3) is an important atmospheric pollutant by its direct health effects as well as by its contribution to photochemical smog formation. Chloroform outgassing from swimming pools is not typically considered a source of atmospheric CHCl3 because swimming pools are scarce compared to other sources. However, large urban areas in hot climates such as Phoenix, AZ contain a substantial amount of swimming pools, potentially resulting in significant atmospheric fluxes. In this study, CHCl3 formation potential (FP) from disinfection of swimming pools in Phoenix was investigated through laboratory experiments and annual CHCl3 emission fluxes from swimming pools were estimated based on the experimental data.
Swimming pool water (collected in June 2014 in Phoenix) and model contaminants (Pharmaceuticals and Personal Care Products (PPCPs), Endocrine Disrupting Compounds (EDCs), artificial sweeteners, and artificial human waste products) were chlorinated in controlled laboratory experiments. The CHCl3 production during chlorination was determined using Gas Chromatography-Mass Spectrometry (GC-MS) following solid-phase microextraction (SPME). Upon chlorination, all swimming pool water samples and contaminants produced measureable amounts of chloroform. Chlorination of swimming pool water produced 0.005-0.134 mol CHCl3/mol C and 0.004-0.062 mol CHCl3/mol Cl2 consumed. Chlorination of model contaminants produced 0.004-0.323 mol CHCl3/mol C and 0.001-0.247 mol CHCl3/mol Cl2 consumed. These numbers are comparable and indicate that the model contaminants react similarly to swimming pool water during chlorination. The CHCl3 flux from swimming pools in Phoenix was estimated at approximately 3.9-4.3 Gg/yr and was found to be largely dependent on water temperature and wind speed while air temperature had little effect. This preliminary estimate is orders of magnitude larger than previous estimates of anthropogenic emissions in Phoenix suggesting that swimming pools might be a significant source of atmospheric CHCl3 locally.
Swimming pool water (collected in June 2014 in Phoenix) and model contaminants (Pharmaceuticals and Personal Care Products (PPCPs), Endocrine Disrupting Compounds (EDCs), artificial sweeteners, and artificial human waste products) were chlorinated in controlled laboratory experiments. The CHCl3 production during chlorination was determined using Gas Chromatography-Mass Spectrometry (GC-MS) following solid-phase microextraction (SPME). Upon chlorination, all swimming pool water samples and contaminants produced measureable amounts of chloroform. Chlorination of swimming pool water produced 0.005-0.134 mol CHCl3/mol C and 0.004-0.062 mol CHCl3/mol Cl2 consumed. Chlorination of model contaminants produced 0.004-0.323 mol CHCl3/mol C and 0.001-0.247 mol CHCl3/mol Cl2 consumed. These numbers are comparable and indicate that the model contaminants react similarly to swimming pool water during chlorination. The CHCl3 flux from swimming pools in Phoenix was estimated at approximately 3.9-4.3 Gg/yr and was found to be largely dependent on water temperature and wind speed while air temperature had little effect. This preliminary estimate is orders of magnitude larger than previous estimates of anthropogenic emissions in Phoenix suggesting that swimming pools might be a significant source of atmospheric CHCl3 locally.
ContributorsRose, Christy J (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Hayes, Mark (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2014
Description
Filtration for microfluidic sample-collection devices is desirable for sample selection, concentration, preprocessing, and downstream manipulation, but microfabricating the required sub-micrometer filtration structure is an elaborate process. This thesis presents a simple method to fabricate polydimethylsiloxane (PDMS) devices with an integrated membrane filter that will sample, lyse, and extract the DNA from microorganisms in aqueous environments. An off-the-shelf membrane filter disc was embedded in a PDMS layer and sequentially bound with other PDMS channel layers. No leakage was observed during filtration. This device was validated by concentrating a large amount of cyanobacterium Synechocystis in simulated sample water with consistent performance across devices. After accumulating sufficient biomass on the filter, a sequential electrochemical lysing process was performed by applying 5VDC across the filter. This device was further evaluated by delivering several samples of differing concentrations of cyanobacterium Synechocystis then quantifying the DNA using real-time PCR. Lastly, an environmental sample was run through the device and the amount of photosynthetic microorganisms present in the water was determined. The major breakthroughs in this design are low energy demand, cheap materials, simple design, straightforward fabrication, and robust performance, together enabling wide-utility of similar chip-based devices for field-deployable operations in environmental micro-biotechnology.
ContributorsLecluse, Aurelie (Author) / Meldrum, Deirdre (Thesis advisor) / Chao, Joseph (Thesis advisor) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2011
Description
Population growth and fresh water depletion challenge drinking water utilities. Surface water quality is impacted significantly by climate variability, human activities, and extreme events like natural disasters. Dissolved organic carbon (DOC) is an important water quality index and the precursor of disinfection by-products (DBPs) that varies with both hydrologic and anthropogenic factors. Granular activated carbon (GAC) is a best available technology for utilities to meet Stage 2 D/DBP rule compliance and to remove contaminants of emerging concern (CECs) (e.g., pharmaceutical, personal care products (PCPs), etc.). Utilities can operate GAC with more efficient and flexible strategies with the understanding of organic occurrence in source water and a model capable predicting DOC occurrence. In this dissertation, it was found that DOC loading significantly correlated with spring runoff and was intensified by dry-duration antecedent to first flush. Dynamic modeling based on reservoir management (e.g., pump-back operation) was established to simulate the DOC transport in the reservoir system. Additionally, summer water recreational activities were found to raise the level of PCPs, especially skin-applied products, in raw waters. GAC was examined in this dissertation for both carbonaceous and emerging nitrogenous DBP (N-DBP) precursors (i.e., dissolved organic nitrogen (DON)) removal. Based on the experimental findings, GAC preferentially removes UV254-absorbing material, and DOC is preferentially removed over DON which may be composed primarily of hydrophilic organic and results in the low affinity for adsorption by GAC. The presence of organic nitrogen can elevate the toxicity of DBPs by forming N-DBPs, and this could be a major drawback for facilities considering installation of a GAC adsorber owing to the poor removal efficiency of DON by GAC. A modeling approach was established for predicting DOC and DON breakthrough during GAC operation. However, installation of GAC adsorber is a burden for utilities with respect to operational and maintenance cost. It is common for utilities to regenerate saturated GAC in order to save the cost of purchasing fresh GAC. The traditional thermal regeneration technology for saturated GAC is an energy intensive process requiring high temperature of incineration. Additionally, small water treatment sites usually ship saturated GAC to specialized facilities for regeneration increasing the already significant carbon footprint of thermal regeneration. An innovative GAC regeneration technique was investigated in this dissertation for the feasibility as on-site water treatment process. Virgin GAC was first saturated by organic contaminant then regenerated in-situ by iron oxide nanocatalysts mixed with hydrogen peroxide. At least 70 % of adsorption capacity of GAC can be regenerated repeatedly for experiments using modeling compound (phenol) or natural organic matter (Suwannee River humic acid). The regeneration efficiency increases with increasing adsorbate concentration. Used-iron nanocatalysts can be recovered repeatedly without significant loss of catalytic ability. This in-situ regeneration technique provides cost and energy efficient solution for water utilities considering GAC installation. Overall, patterns were found for DOC and CEC variations in drinking water sources. Increasing concentrations of bulk (DOC and DON) and/or trace organics challenge GAC operation in utilities that have limited numbers of bed-volume treated before regeneration is required. In-situ regeneration using iron nanocatalysts and hydrogen peroxide provides utilities an alternative energy-efficient operation mode when considering installation of GAC adsorber.
ContributorsChiu, Chao-An (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2012
Description
Local municipalities in the Phoenix Metropolitan Area have voiced an interest in purchasing alternate source water with lower DBP precursors. Along the primary source is a hydroelectric dam in which water will be diverted from. This project is an assessment of optimizing the potential blends of source water to a water treatment plant in an effort to enable them to more readily meet DBP regulations. To perform this analysis existing water treatment models were used in conjunction with historic water quality sampling data to predict chemical usage necessary to meet DBP regulations. A retrospective analysis was performed for the summer months of 2007 regarding potential for the WTP to reduce cost through optimizing the source water by an average of 30% over the four-month period, accumulating to overall treatment savings of $154 per MG ($82 per AF).
ContributorsRice, Jacelyn (Author) / Westerhoff, Paul (Thesis advisor) / Fox, Peter (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2011
Description
To date, the production of algal biofuels is not economically sustainable due to the cost of production and the low cost of conventional fuels. As a result, interest has been shifting to high value products in the algae community to make up for the low economic potential of algal biofuels. The economic potential of high-value products does not however, eliminate the need to consider the environmental impacts. The majority of the environmental impacts associated with algal biofuels overlap with algal bioproducts in general (high-energy dewatering) due to the similarities in their production pathways. Selecting appropriate product sets is a critical step in the commercialization of algal biorefineries.
This thesis evaluates the potential of algae multiproduct biorefineries for the production of fuel and high-value products to be economically self-sufficient and still contribute to climate change mandates laid out by the government via the Energy Independence and Security Act (EISA) of 2007. This research demonstrates:
1) The environmental impacts of algal omega-3 fatty acid production can be lower than conventional omega-3 fatty acid production, depending on the dewatering strategy.
2) The production of high-value products can support biofuels with both products being sold at prices comparable to 2016 prices.
3) There is a tradeoff between revenue and fuel production
4) There is a tradeoff between the net energy ratio of the algal biorefinery and the economic viability due to the lower fuel production in a multi-product model that produces high-value products and diesel vs. the lower economic potential from a multi-product model that just produces diesel.
This work represents the first efforts to use life cycle assessment and techno-economic analysis to assess the economic and environmental sustainability of an existing pilot-scale biorefinery tasked with the production of high-value products and biofuels. This thesis also identifies improvements for multiproduct algal biorefineries that will achieve environmentally sustainable biofuel and products while maintaining economic viability.
This thesis evaluates the potential of algae multiproduct biorefineries for the production of fuel and high-value products to be economically self-sufficient and still contribute to climate change mandates laid out by the government via the Energy Independence and Security Act (EISA) of 2007. This research demonstrates:
1) The environmental impacts of algal omega-3 fatty acid production can be lower than conventional omega-3 fatty acid production, depending on the dewatering strategy.
2) The production of high-value products can support biofuels with both products being sold at prices comparable to 2016 prices.
3) There is a tradeoff between revenue and fuel production
4) There is a tradeoff between the net energy ratio of the algal biorefinery and the economic viability due to the lower fuel production in a multi-product model that produces high-value products and diesel vs. the lower economic potential from a multi-product model that just produces diesel.
This work represents the first efforts to use life cycle assessment and techno-economic analysis to assess the economic and environmental sustainability of an existing pilot-scale biorefinery tasked with the production of high-value products and biofuels. This thesis also identifies improvements for multiproduct algal biorefineries that will achieve environmentally sustainable biofuel and products while maintaining economic viability.
ContributorsBarr, William James (Author) / Landis, Amy E. (Thesis advisor) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Committee member) / Khanna, Vikas (Committee member) / Arizona State University (Publisher)
Created2016
Description
Several prominent research strategy organizations recommend applying life cycle assessment (LCA) early in the development of emerging technologies. For example, the US Environmental Protection Agency, the National Research Council, the Department of Energy, and the National Nanotechnology Initiative identify the potential for LCA to inform research and development (R&D) of photovoltaics and products containing engineered nanomaterials (ENMs). In this capacity, application of LCA to emerging technologies may contribute to the growing movement for responsible research and innovation (RRI). However, existing LCA practices are largely retrospective and ill-suited to support the objectives of RRI. For example, barriers related to data availability, rapid technology change, and isolation of environmental from technical research inhibit application of LCA to developing technologies. This dissertation focuses on development of anticipatory LCA tools that incorporate elements of technology forecasting, provide robust explorations of uncertainty, and engage diverse innovation actors in overcoming retrospective approaches to environmental assessment and improvement of emerging technologies. Chapter one contextualizes current LCA practices within the growing literature articulating RRI and identifies the optimal place in the stage gate innovation model to apply LCA. Chapter one concludes with a call to develop anticipatory LCA – building on the theory of anticipatory governance – as a series of methodological improvements that seek to align LCA practices with the objectives of RRI.
Chapter two provides a framework for anticipatory LCA, identifies where research from multiple disciplines informs LCA practice, and builds off the recommendations presented in the preceding chapter. Chapter two focuses on crystalline and thin film photovoltaics (PV) to illustrate the novel framework, in part because PV is an environmentally motivated technology undergoing extensive R&D efforts and rapid increases in scale of deployment. The chapter concludes with a series of research recommendations that seek to direct PV research agenda towards pathways with the greatest potential for environmental improvement.
Similar to PV, engineered nanomaterials (ENMs) are an emerging technology with numerous potential applications, are the subject of active R&D efforts, and are characterized by high uncertainty regarding potential environmental implications. Chapter three introduces a Monte Carlo impact assessment tool based on the toxicity impact assessment model USEtox and demonstrates stochastic characterization factor (CF) development to prioritize risk research with the greatest potential to improve certainty in CFs. The case study explores a hypothetical decision in which personal care product developers are interested in replacing the conventional antioxidant niacinamide with the novel ENM C60, but face high data uncertainty, are unsure regarding potential ecotoxicity impacts associated with this substitution, and do not know what future risk-relevant experiments to invest in that most efficiently improve certainty in the comparison. Results suggest experiments that elucidate C60 partitioning to suspended solids should be prioritized over parameters with little influence on results. This dissertation demonstrates a novel anticipatory approach to exploration of uncertainty in environmental models that can create new, actionable knowledge with potential to guide future research and development decisions.
Chapter two provides a framework for anticipatory LCA, identifies where research from multiple disciplines informs LCA practice, and builds off the recommendations presented in the preceding chapter. Chapter two focuses on crystalline and thin film photovoltaics (PV) to illustrate the novel framework, in part because PV is an environmentally motivated technology undergoing extensive R&D efforts and rapid increases in scale of deployment. The chapter concludes with a series of research recommendations that seek to direct PV research agenda towards pathways with the greatest potential for environmental improvement.
Similar to PV, engineered nanomaterials (ENMs) are an emerging technology with numerous potential applications, are the subject of active R&D efforts, and are characterized by high uncertainty regarding potential environmental implications. Chapter three introduces a Monte Carlo impact assessment tool based on the toxicity impact assessment model USEtox and demonstrates stochastic characterization factor (CF) development to prioritize risk research with the greatest potential to improve certainty in CFs. The case study explores a hypothetical decision in which personal care product developers are interested in replacing the conventional antioxidant niacinamide with the novel ENM C60, but face high data uncertainty, are unsure regarding potential ecotoxicity impacts associated with this substitution, and do not know what future risk-relevant experiments to invest in that most efficiently improve certainty in the comparison. Results suggest experiments that elucidate C60 partitioning to suspended solids should be prioritized over parameters with little influence on results. This dissertation demonstrates a novel anticipatory approach to exploration of uncertainty in environmental models that can create new, actionable knowledge with potential to guide future research and development decisions.
ContributorsWender, Ben A. (Author) / Seager, Thomas (Thesis advisor) / Guston, David (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2016
Description
Due to the use of fertilizers, concentrations of harmful nitrate have increased in groundwater and surface waters globally in the last century. Water treatment plants primarily use separation techniques for nitrate treatment, but these technologies create a high nitrate concentration brine that is costly to dispose of. This dissertation focuses on catalytic hydrogenation, an emerging technology capable of reducing nitrate to nitrogen gas using hydrogen gas (H2). This technology reduces nitrate at rates >95% and is an improvement over technologies used at water treatment plants, because the nitrate is chemically transformed with harmless byproducts and no nitrate brine. The goal of this dissertation is to upgrade the maturity of catalytic nitrate hydrogenation systems by overcoming several barriers hindering the scale-up of this technology. Objective 1 is to compare different methods of attaching the bimetallic catalyst to a hollow-fiber membrane surface to find a method that results in 1) minimized catalyst loss, and 2) repeatable nitrate removal over several cycles. Results showed that the In-Situ MCfR-H2 deposition was successful in reducing nitrate at a rate of 1.1 min-1gPd-1 and lost less than 0.05% of attached Pd and In cumulatively over three nitrate treatment cycles. Objective 2 is to synthesize catalyst-films with varied In3+ precursor decorated over a Pd0 surface to show the technology can 1) reliably synthesize In-Pd catalyst-films with varied bimetallic ratios, and 2) optimize nitrate removal activity by varying In-Pd ratio. Results showed that nitrate removal activity was optimized with a rate constant of 0.190 mg*min-1L-1 using a catalyst-film with a 0.045 In-Pd ratio. Objective 3 is to perform nitrate reduction in a continuous flow reactor for two months to determine if nitrate removal activity can be sustained over extended operation and identify methods to overcome catalyst deactivation. Results showed that a combination of increased hydraulic residence time and reduced pH was successful in increasing the nitrate removal and decreasing harmful nitrite byproduct selectivity to 0%. These objectives increased the technology readiness of this technology by enabling the reuse of the catalyst, maximizing nitrate reduction activity, and achieving long-term nitrate removal.
ContributorsLevi, Juliana (Author) / Westerhoff, Paul (Thesis advisor) / Rittmann, Bruce (Thesis advisor) / Garcia-Segura, Sergi (Committee member) / Wong, Michael (Committee member) / Lind Thomas, Mary Laura (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2023
Description
Ion exchange sorbents embedded with metal oxide nanoparticles can have high affinity and high capacity to simultaneously remove multiple oxygenated anion contaminants from drinking water. This research pursued answering the question, “Can synthesis methods of nano-composite sorbents be improved to increase sustainability and feasibility to remove hexavalent chromium and arsenic simultaneously from groundwater compared to existing sorbents?” Preliminary nano-composite sorbents outperformed existing sorbents in equilibrium tests, but struggled in packed bed applications and at low influent concentrations. The synthesis process was then tailored for weak base anion exchange (WBAX) while comparing titanium dioxide against iron hydroxide nanoparticles (Ti-WBAX and Fe-WBAX, respectively). Increasing metal precursor concentration increased the metal content of the created sorbents, but pollutant removal performance and usable surface area declined due to pore blockage and nanoparticle agglomeration. An acid-post rinse was required for Fe-WBAX to restore chromium removal capacity. Anticipatory life cycle assessment identified critical design constraints to improve environmental and human health performance like minimizing oven heating time, improving pollutant removal capacity, and efficiently reusing metal precursor solution. The life cycle environmental impact of Ti-WBAX was lower than Fe-WBAX as well as a mixed bed of WBAX and granular ferric hydroxide for all studied categories. A separate life cycle assessment found the total number of cancer and non-cancer cases prevented by drinking safer water outweighed those created by manufacture and use of water treatment materials and energy. However, treatment relocated who bore the health risk, concentrated it in a sub-population, and changed the primary manifestation from cancer to non-cancer disease. This tradeoff was partially mitigated by avoiding use of pH control chemicals. When properly synthesized, Fe-WBAX and Ti-WBAX sorbents maintained chromium removal capacity while significantly increasing arsenic removal capacity compared to the parent resin. The hybrid sorbent performance was demonstrated in packed beds using a challenging water matrix and low pollutant influent conditions. Breakthrough curves hint that the hexavalent chromium is removed by anion exchange and the arsenic is removed by metal oxide sorption. Overall, the hybrid nano-sorbent synthesis methods increased sustainability, improved sorbent characteristics, and increased simultaneous removal of chromium and arsenic for drinking water.
ContributorsGifford, James McKay (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Thesis advisor) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2016