Matching Items (8)
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- All Subjects: Water
- Creators: Halden, Rolf
- Creators: School of Earth and Space Exploration
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
Arsenic (As) and chromium (Cr) occur naturally in AZ surface and groundwaters, pose different health impacts, and exhibit different treatment efficacies. Hexavalent chromium (Cr(VI)) has newly recognized human health concerns, and State and Federal agencies are evaluating a low Cr(VI)-specific maximum contaminant level (MCL) for drinking water. Occurrence of Cr and As in municipal drinking waters and industrial cooling tower waters was quantified by grab samples and compared with sampling results obtained from a new passive sampler developed specifically for Cr(VI). Cr(VI) and As concentrations in groundwater used for cooling tower make-up water concentrations were ~3 ppb and ~4 ppb, respectively, and were concentrated significantly in blowdown water (~20 ppb and ~40 ppb). Based upon pending Cr(VI), As, and other metal regulations, these blowdown waters will need routine monitoring and treatment. Cr(VI) concentrations in a water treatment plant (WTP) raw and finished water samples varied from 0.5 and 2 ppb for grab samples collected every 4 hours for 7 consecutive days using an ISCO sampler. The development of an ion exchange (IX) based passive sampler was validated in the field at the WTP and yielded an average exposure within 1 standard deviation of ISCO sampler grab data. Sampling at both the WTP and cooling towers suggested sources of Cr(III) from treatment chemicals or wood preservatives may exist. Since both facilities use chlorine oxidants, I quantified the apparent (pH=5) second-order rate constant for aqueous chlorine (HOCl/OCl-) with Cr(III) to form Cr(VI) as 0.7 M-1s-1. Under typical conditions (2 ppb Cr(III) ; 2 mg/L Cl2) the half-life for the conversion of Cr(III) to the more toxic form Cr(VI) is 4.7 hours. The occurrence studies in AZ and CA show the Cr(VI) and As treatment of groundwaters will be required to meet stringent Cr(VI) regulations. IX technologies, both strong base anion (SBA) and weak base anion (WBA) resin types were screened (and compared) for Cr removal. The SBA IX process for As removal was optimized by utilizing a reactive iron coagulation and filtration (RCF) process to treat spent IX brine, which was then reused to for SBA resin regeneration.
ContributorsBowen, Alexandra (Author) / Paul, Westerhoff K. (Thesis advisor) / Hristovski, Kiril (Committee member) / Halden, Rolf (Committee member) / Arizona State University (Publisher)
Created2014
Description
Located in the Sunbelt of the Southwestern United States, Phoenix Arizona finds itself in one of the hottest, driest places in the world. Thankfully, Phoenix has the Salt River, Gila River, Verde River, and a vast aquifer to meet the water demands of the municipal, industrial, and agricultural sectors. However, rampant groundwater pumping and over-allocation of these water supplies based on unprecedented, high flows of the Colorado River have created challenges for water managers to ensure adequate water supply for the future. Combined with the current 17-year drought and the warming and drying projections of climate change, the future of water availability in Phoenix will depend on the strength of water management laws, educating the public, developing a strong sense of community, and using development to manage population and support sustainability. As the prevalence of agriculture declines in and around Phoenix, a substantial amount of water is saved. Instead of storing this saved water, Phoenix is using it to support further development. Despite uncertainty regarding the abundant and continuous availability of Phoenix's water resources, development has hardly slowed and barely shifted directions to support sustainability. Phoenix was made to grow until it legally cannot expand anymore. In order to develop solutions, we must first understand the push for development in water-stressed Phoenix, Arizona.
ContributorsVasquez, Brianna Nicole (Author) / Heimsath, Arjun (Thesis director) / Whipple, Kelin (Committee member) / School of Earth and Space Exploration (Contributor) / School of Art (Contributor) / School of Community Resources and Development (Contributor) / Barrett, The Honors College (Contributor)
Created2017-05
Description
Six high-production-volume neonicotinoids were traced through a municipal wastewater treatment plant (WWTP) and engineered wetland located downstream, in a study motivated by reports on these insecticides posing threats to non-target invertebrate species and potentially playing a role in the global honeybee colony collapse disorder. An array of automated samplers was deployed in a five-day monitoring campaign and resultant flow-weighted samples were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) using the isotope dilution method. Concentrations in WWTP influent and effluent were 54.7 ± 2.9 and 48.6 ± 2.7 ng/L for imidacloprid, respectively, and 3.7 ± 0.3 and 1.8 ± 0.1 ng/L for acetamiprid, respectively. A mass balance over the WWTP showed no (p=0.09, CI = 95%) removal of imidacloprid, and 56 ± 6% aqueous removal of acetamiprid. In the constructed wetland downstream, a lack of removal was noted for both imidacloprid (from 54.4 ± 3.4 ng/L to 49.9 ± 14.6 ng/L) and acetamiprid (from 2.00 ± 0.03 ng/L to 2.30 ± 0.21 ng/L). Clothianidin was detected only inconsistently in the WWTP and wetland (>2 to 288 ng/L; 60% detection frequency), whereas thiamethoxam (<10 ng/L), thiacloprid (<2 ng/L), and dinotefuran (<180 ng/L) were not detected at all. Thus, imidacloprid and acetamiprid were identified as recalcitrant sewage constituents (estimated U.S. WWTP discharge of 1920- 4780 kg/y) that persist during conventional wastewater treatment to enter U.S. surface waters at potentially harmful concentrations.
ContributorsSadaria, Akash Mahendra (Author) / Halden, Rolf (Thesis advisor) / Fox, Peter (Committee member) / Popat, Sudeep (Committee member) / Arizona State University (Publisher)
Created2015
Environmental releases of neonicotinoid and fipronil insecticides via U.S. wastewater infrastructure
Description
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.
ContributorsSadaria, Akash Mahendra (Author) / Halden, Rolf (Thesis advisor) / Fraser, Matthew (Committee member) / Perreault, Francois (Committee member) / Mascaro, Giuseppe (Committee member) / Arizona State University (Publisher)
Created2017
Description
The Star Planet Activity Research CubeSat (SPARCS) will be a 6U CubeSat devoted to photometric monitoring of M dwarfs in the far-ultraviolet (FUV) and near-ultraviolet (NUV) (160 and 280 nm respectively), measuring the time-dependent spectral slope, intensity and evolution of M dwarf stellar UV radiation. The delta-doped detectors baselined for SPARCS have demonstrated more than five times the in-band quantum efficiency of the detectors of GALEX. Given that red:UV photon emission from cool, low-mass stars can be million:one, UV observation of thes stars are susceptible to red light contamination. In addition to the high efficiency delta-doped detectors, SPARCS will include red-rejection filters to help minimize red leak. Even so, careful red-rejection and photometric calibration is needed. As was done for GALEX, white dwarfs are used for photometric calibration in the UV. We find that the use of white dwarfs to calibrate the observations of red stars leads to significant errors in the reported flux, due to the differences in white dwarf and red dwarf spectra. Here we discuss the planned SPARCS calibration model and the color correction, and demonstrate the importance of this correction when recording UV measurements of M stars taken by SPARCS.
ContributorsOsby, Ella (Author) / Shkolnik, Evgenya (Thesis director) / Ardila, David (Committee member) / School of Earth and Space Exploration (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
Gamma-ray bursts (GRBs) are a type of astrophysical transient resulting from the most energetic explosions known in the universe. The explosions occur in distant galaxies, and their bright initial emission may only last a few seconds. Colibri is a telescope being built at the San Pedro Martir Observatory in Baja, CA, MX with high sensitivity in order to study these events at a high redshift. Due to how quickly GRBs occur, it is essential to develop an image reduction pipeline that can quickly and accurately detect these events. Using existing image reduction software from Coatli, which was programmed and optimized for speed using python, numerous time trials were performed in order to determine if the pipeline meets the time requirements with various factors being adjusted. The goal of this experiment is for the telescope to respond to, capture, and reduce the images in under 3 minutes. It was determined that the reduction was optimized when the number of files to be reduced was set equal to 16 or higher by changing the batch number and the blank sky subtraction function was performed. As for the number of exposures, one can take up to four 30 second exposures or twenty 5 second exposures and reduce them in under 3 minutes.
ContributorsHeiligenstein, Wren (Author) / Butler, Nathaniel (Thesis director) / Jansen, Rolf (Committee member) / Dimitrova, Tzvetelina (Committee member) / Barrett, The Honors College (Contributor) / School of Earth and Space Exploration (Contributor)
Created2024-05
Description
Two large sectors of water consumption within cities are: city owned irrigated landscape (such as parks) and household consumption. A related, third sector of consumption that has very little research behind it is shared landscapes in residential communities. Neighborhood communities, including those with formal Homeowner’s Associations and informal Neighborhood Associations, have common landscapes they are responsible for up-keeping and irrigating. 208 neighborhood communities exist within the City of Tempe. Each year the city provides $30,000 in grant funding to these 208 neighborhoods to implement water conservation projects. This thesis focuses on ten neighborhoods who had applied and were granted funding to implement a conservation project between the years 2011 and 2016. My findings showed that this program has not been effective in reducing water consumption, wither due to the lack of implementation or the small-scale of the projects. From my research and synthesis, I suggest a layer of accountability be added to the program to ensure projects are effective and participants are implementing their projects and that the program is effective overall. This study provides the City of Tempe with relevant and viable information to aid management of water consumption and conservation within neighborhoods.
ContributorsApillanes, Sierra Caitlyn (Author) / Larson, Kelli (Thesis director) / Bomar, Melissa (Committee member) / School of Sustainability (Contributor, Contributor) / School of Earth and Space Exploration (Contributor) / Barrett, The Honors College (Contributor)
Created2019-05