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- All Subjects: nanotechnology
- All Subjects: water treatment
- Creators: Westerhoff, Paul
Description
Much of Nepal lacks access to clean drinking water, and many water sources are contaminated with arsenic at concentrations above both World Health Organization and local Nepalese guidelines. While many water treatment technologies exist, it is necessary to identify those that are easily implementable in developing areas. One simple treatment that has gained popularity is biochar—a porous, carbon-based substance produced through pyrolysis of biomass in an oxygen-free environment. Arizona State University’s Engineering Projects in Community Service (EPICS) has partnered with communities in Nepal in an attempt to increase biochar production in the area, as it has several valuable applications including water treatment. Biochar’s arsenic adsorption capability will be investigated in this project with the goal of using the biochar that Nepalese communities produce to remove water contaminants. It has been found in scientific literature that biochar is effective in removing heavy metal contaminants from water with the addition of iron through surface activation. Thus, the specific goal of this research was to compare the arsenic adsorption disparity between raw biochar and iron-impregnated biochar. It was hypothesized that after numerous bed volumes pass through a water treatment column, iron from the source water will accumulate on the surface of raw biochar, mimicking the intentionally iron-impregnated biochar and further increasing contaminant uptake. It is thus an additional goal of this project to compare biochar loaded with iron through an iron-spiked water column and biochar impregnated with iron through surface oxidation. For this investigation, the biochar was crushed and sieved to a size between 90 and 100 micrometers. Two samples were prepared: raw biochar and oxidized biochar. The oxidized biochar was impregnated with iron through surface oxidation with potassium permanganate and iron loading. Then, X-ray fluorescence was used to compare the composition of the oxidized biochar with its raw counterpart, indicating approximately 0.5% iron in the raw and 1% iron in the oxidized biochar. The biochar samples were then added to batches of arsenic-spiked water at iron to arsenic concentration ratios of 20 mg/L:1 mg/L and 50 mg/L:1 mg/L to determine adsorption efficiency. Inductively coupled plasma mass spectrometry (ICP-MS) analysis indicated an 86% removal of arsenic using a 50:1 ratio of iron to arsenic (1.25 g biochar required in 40 mL solution), and 75% removal with a 20:1 ratio (0.5 g biochar required in 40 mL solution). Additional samples were then inserted into a column process apparatus for further adsorption analysis. Again, ICP-MS analysis was performed and the results showed that while both raw and treated biochars were capable of adsorbing arsenic, they were exhausted after less than 70 bed volumes (234 mL), with raw biochar lasting 60 bed volumes (201 mL) and oxidized about 70 bed volumes (234 mL). Further research should be conducted to investigate more affordable and less laboratory-intensive processes to prepare biochar for water treatment.
ContributorsLaird, Ashlyn (Author) / Schoepf, Jared (Thesis director) / Westerhoff, Paul (Committee member) / Chemical Engineering Program (Contributor) / School of International Letters and Cultures (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
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
As engineered nanomaterials (NMs) become used in industry and commerce their loading to sewage will increase. However, the fate of widely used NMs in wastewater treatment plants (WWTPs) remains poorly understood. In this research, sequencing batch reactors (SBRs) were operated with hydraulic (HRT) and sludge (SRT) retention times representative of full-scale biological WWTPs for several weeks. NM loadings at the higher range of expected environmental concentrations were selected. To achieve the pseudo-equilibrium state concentration of NMs in biomass, SBR experiments needed to operate for more than three times the SRT value, approximately 18 days. Under the conditions tested, NMs had negligible effects on ability of the wastewater bacteria to biodegrade organic material, as measured by chemical oxygen demand (COD). NM mass balance closure was achieved by measuring NMs in liquid effluent and waste biosolids. All NMs were well removed at the typical biomass concentration (1~2 gSS/L). However, carboxy-terminated polymer coated silver nanoparticles (fn-Ag) were removed less effectively (88% removal) than hydroxylated fullerenes (fullerols; >90% removal), nano TiO2 (>95% removal) or aqueous fullerenes (nC60; >95% removal). Although most NMs did not settle out of the feed solution without bacteria present, approximately 65% of the titanium dioxide was removed even in the absence of biomass simply due to self-aggregation and settling. Experiments conducted over 4 months with daily loadings of nC60 showed that nC60 removal from solution depends on the biomass concentration. Under conditions representative of most suspended growth biological WWTPs (e.g., activated sludge), most of the NMs will accumulate in biosolids rather than in liquid effluent discharged to surface waters. Significant fractions of fn-Ag were associated with colloidal material which suggests that efficient particle separation processes (sedimentation or filtration) could further improve removal of NM from effluent. As most NMs appear to accumulate in biosolids, future research should examine the fate of NMs during disposal of WWTP biosolids, which may occur through composting or anaerobic digestion and/or land application, incineration, or landfill disposal.
ContributorsWang, Yifei (Author) / Westerhoff, Paul (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Rittmann, Bruce (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2012
Description
Electrochemical technologies emerge as a feasible solution to monitor and treat pollutants. Although electrochemical technologies have garnered widespread attention, their commercial applications are still constrained by the use of expensive electrocatalysts, and the bulky and rigid plate design of electrodes that restricts electrochemical reactor design to systems with poor electrode surface/ volume treated ratios. By making electrodes flexible, more compact designs that maximize electrode surface per volume treated might become a reality. This dissertation encompasses the successful fabrication of flexible nanocomposite electrodes for electrocatalysis and electroanalysis applications.First, nano boron-doped diamond electrodes (BDD) were prepared as an inexpensive alternative to commercial boron-doped diamond electrodes. Comparative detailed surface and electrochemical characterization was conducted. Empirical study showed that replacing commercial BDD electrodes with nano-BDD electrodes can result in a cost reduction of roughly 1000x while maintaining the same electrochemical performance.
Next, self-standing electrodes were fabricated through the electropolymerization of conducing polymer, polypyrrole. Surface characterizations, such as SEM, FTIR and XPS proved the successful fabrication of these self-standing electrodes. High mechanical stability and bending flexibility demonstrated the ability to use these electrodes in different designs, such as roll-to-roll membranes. Electrochemical nitrite reduction was employed to demonstrate the viability of using self-standing nanocomposite electrodes for electrocatalytic applications reducing hazardous nitrogen oxyanions (i.e., nitrite) towards innocuous species such as nitrogen gas. A high faradaic efficiency of 78% was achieved, with high selectivity of 91% towards nitrogen gas.
To further enhance the conductivity and charge transfer properties of self-standing polypyrrole electrodes, three different nanoparticles, including copper (Cu), gold (Au), and platinum (Pt), were incorporated in the polypyrrole matrix. Effect of nanoparticle wt% and interaction between metal nanoparticles and polypyrrole matrix was investigated for electroanalytical applications, specifically dopamine sensing. Flexible nanocomposite electrodes showed outstanding performance as electrochemical sensors with PPy-Cu 120s exhibiting a low limit of detection (LOD) of 1.19 µM and PPy-Au 120s exhibiting a high linear range of 5 µM - 300 µM.
This dissertation outlines a method of fabricating self-standing electrodes and provides a pathway of using self-standing electrodes based on polypyrrole and polypyrrole-metal nanocomposites for various applications in wastewater treatment and electroanalytical sensing.
ContributorsBansal, Rishabh (Author) / Garcia-Segura, Sergio (Thesis advisor) / Westerhoff, Paul (Committee member) / Perreault, Francois (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2023
Description
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.
ContributorsHoogesteijn von Reitzenstein, Natalia Virginia (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Committee member) / Perreault, Francois (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2018
Description
Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential health concerns in case of exposure to popular FRs. Carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) have been studied and applied to polymer composites and electronics extensively due to their remarkable properties. Hence CNMs are considered as potential alternative materials that present high flame retardancy. In this research, different kinds of CNMs coatings on polyester fabric are produced and evaluated for their use as flame retardants. To monitor the mass loading of CNMs coated on the fabric, a two-step analytical method for quantifying CNMs embedded in polymer composites was developed. This method consisted of polymer dissolution process using organic solvents followed by subsequent programmed thermal analysis (PTA). This quantification technique was applicable to CNTs with and without high metal impurities in a broad range of polymers. Various types of CNMs were coated on polyester fabric and the efficacy of coatings as flame retardant was evaluated. The oxygen content of CNMs emerged as a critical parameter impacting flame retardancy with higher oxygen content resulting in less FR efficacy. The most performant nanomaterials, multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nantoubes (NH2-MWCNT) showed similar FR properties to current flame retardants with low mass loading (0.18 g/m2) and hence are promising alternatives that warrant further investigation. Chemical/physical modification of MWCNTs was conducted to produce well-dispersed MWCNT solutions without involving oxygen for uniform FR coating. The MWCNTs coating was studied to evaluate the durability of the coating and the impact on the efficacy during use phase by conducting mechanical abrasion and washing test. Approximately 50% and 40% of MWCNTs were released from 1 set of mechanical abrasion and washing test respectively. The losses during simulated usage impacted the flame retardancy negatively.
ContributorsNosaka, Takayuki (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Wang, Qing Hua (Committee member) / Arizona State University (Publisher)
Created2018
Description
Over the past decade, there has been a revival in applied algal research and attempts at commercialization. However, the main limitation in algal commercialization is the process of cultivation, which is one of the main cost and energy burdens in producing biomass that is economically feasible for different products. There are several parameters that must be considered when growing algae, including the type of growth system and operating mode, preferred organism(s), and many other criteria that affect the process of algal cultivation. The purpose of this dissertation was to assess key variables that affect algal productivity and to improve outdoor algal cultivation procedures. The effect of reducing or eliminating aeration of algal cultures at night, in flat panel photobioreactors (panels), was investigated to assess the reduction of energy consumption at night. The lack of aeration at night resulted in anoxic conditions, which significantly reduced lipid accumulation and productivity, but did not affect log phase biomass productivity. In addition, the reduction in aeration resulted in lower pH values, which prevented ammonia volatility and toxicity. Raceways are operated at deeper cultivation depths, which limit culture density and light exposure. Experimentation was accomplished to determine the effects of decreasing cultivation depth, which resulted in increased lipid accumulation and lipid productivity, but did not significantly affect biomass productivity. A comparison of semi-continuous cultivation of algae in raceways and panels in side-by-side experiments showed that panels provided better temperature control and higher levels of mixing, which resulted in higher biomass productivity. In addition, sub-optimal morning temperatures in raceways compared to panels were a significant factor in reducing algae biomass productivity. The results from this research indicate that increasing lipid productivity and biomass productivity cannot be completed simultaneously. Therefore, the desired product will determine if lipid or biomass productivity is more crucial, which also dictates whether the system should be operated in batch mode to either allow lipid accumulation or in semi-continuous mode to allow high biomass productivity. This work is a critical step in improving algal cultivation by understanding key variables that limit biomass and lipid productivity.
ContributorsEustance, Everett (Author) / Sommerfeld, Milton R (Thesis advisor) / Fox, Peter (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2015
Description
Photosynthesis converts sunlight to biomass at a global scale. Among the photosynthetic organisms, cyanobacteria provide an excellent model to study how photosynthesis can become a practical platform of large-scale biotechnology. One novel approach involves metabolically engineering the cyanobacterium Synechocystis sp. PCC 6803 to excrete laurate, which is harvested directly.
This work begins by defining a working window of light intensity (LI). Wild-type and laurate-excreting Synechocystis required an LI of at least 5 µE/m2-s to sustain themselves, but are photo-inhibited by LI of 346 to 598 µE/m2-s.
Fixing electrons into valuable organic products, e.g., biomass and excreted laurate, is critical to success. Wild-type Synechocystis channeled 75% to 84% of its fixed electrons to biomass; laurate-excreting Synechocystis fixed 64 to 69% as biomass and 6.6% to 10% as laurate. This means that 16 to 30% of the electrons were diverted to non-valuable soluble products, and the trend was accentuated with higher LI.
How the Ci concentration depended on the pH and the nitrogen source was quantified by the proton condition and experimentally validated. Nitrate increased, ammonium decreased, but ammonium nitrate stabilized alkalinity and Ci. This finding provides a mechanistically sound tool to manage Ci and pH independently.
Independent evaluation pH and Ci on the growth kinetics of Synechocystis showed that pH 8.5 supported the fastest maximum specific growth rate (µmax): 2.4/day and 1.7/day, respectively, for the wild type and modified strains with LI of 202 µE/m2-s. Half-maximum-rate concentrations (KCi) were less than 0.1 mM, meaning that Synechocystis should attain its µmax with a modest Ci concentration (≥1.0 mM).
Biomass grown with day-night cycles had a night endogenous decay rate of 0.05-1.0/day, with decay being faster with higher LI and the beginning of dark periods. Supplying light at a fraction of daylight reduced dark decay rate and improved overall biomass productivity.
This dissertation systematically evaluates and synthesizes fundamental growth factors of cyanobacteria: light, inorganic carbon (Ci), and pH. LI remains the most critical growth condition to promote biomass productivity and desired forms of biomass, while Ci and pH now can be managed to support optimal productivity.
This work begins by defining a working window of light intensity (LI). Wild-type and laurate-excreting Synechocystis required an LI of at least 5 µE/m2-s to sustain themselves, but are photo-inhibited by LI of 346 to 598 µE/m2-s.
Fixing electrons into valuable organic products, e.g., biomass and excreted laurate, is critical to success. Wild-type Synechocystis channeled 75% to 84% of its fixed electrons to biomass; laurate-excreting Synechocystis fixed 64 to 69% as biomass and 6.6% to 10% as laurate. This means that 16 to 30% of the electrons were diverted to non-valuable soluble products, and the trend was accentuated with higher LI.
How the Ci concentration depended on the pH and the nitrogen source was quantified by the proton condition and experimentally validated. Nitrate increased, ammonium decreased, but ammonium nitrate stabilized alkalinity and Ci. This finding provides a mechanistically sound tool to manage Ci and pH independently.
Independent evaluation pH and Ci on the growth kinetics of Synechocystis showed that pH 8.5 supported the fastest maximum specific growth rate (µmax): 2.4/day and 1.7/day, respectively, for the wild type and modified strains with LI of 202 µE/m2-s. Half-maximum-rate concentrations (KCi) were less than 0.1 mM, meaning that Synechocystis should attain its µmax with a modest Ci concentration (≥1.0 mM).
Biomass grown with day-night cycles had a night endogenous decay rate of 0.05-1.0/day, with decay being faster with higher LI and the beginning of dark periods. Supplying light at a fraction of daylight reduced dark decay rate and improved overall biomass productivity.
This dissertation systematically evaluates and synthesizes fundamental growth factors of cyanobacteria: light, inorganic carbon (Ci), and pH. LI remains the most critical growth condition to promote biomass productivity and desired forms of biomass, while Ci and pH now can be managed to support optimal productivity.
ContributorsNguyen, Binh Thanh (Author) / Rittmann, Bruce E. (Thesis advisor) / Krajmalnik-Brown, Rosa (Committee member) / Westerhoff, Paul (Committee member) / Arizona State University (Publisher)
Created2015
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
Description
Granular activated carbon (GAC) is effectively used to remove natural organic matter (NOM) and to assist in the removal of disinfection byproducts (DBPs) and their precursors. However, operation of GAC is cost- and labor-intensive due to frequent media replacement. Optimizing the use of GAC is necessary to ensure treatment efficiency while reducing costs. This dissertation presents four strategies to reduce improve GAC usage while reducing formation of DBPs. The first part of this work adopts Rapid Small Scale Tests (RSSCTs) to evaluate removal of molecular weight fractions of NOM, characterized using size exclusion chromatography (SECDOC). Total trihalomethanes (TTHM), haloacetic acids (HAA5) and haloacetonitriles (HAN) formation were quantified after treatment with GAC. Low MW NOM was removed preferentially in the early bed volumes, up until exhaustion of available adsorption sites. DBP formation potential lowered with DOC removal. Chlorination prior to GAC is investigated in the second part of this work as a strategy to increase removal of NOM and DBP precursors. Results showed lower TTHM formation in the effluent of the GAC treatment when pre-chlorination was adopted, meaning this strategy could help optimize and extend the bed life if GAC filters. The third part of this work investigates in-situ GAC regeneration as an alternative to recover adsorption capacity of field-spent GAC that could potentially offer new modes of operation for water treatment facilities while savng costs with reactivation of spent GAC in an external facility. Field-spent GACs were treated with different oxidant solutions and recovery in adsorption capacity was evaluated for NOM and for two micro pollutants. Recovery of GAC adsorption capacity was not satisfactory for most of conditions evaluated. This indicates that in-situ GAC regeneration could be more effective when the adsorbates are present at high concentrations. Lastly, this work investigates the impact of low molecular weight polyDADMAC on N-nitrosodimethylamine (NDMA) formation. Water treatment facilities rely on polyDADMAC as a coagulant aid to comply with NOM removal and turbidity requirements. Since polymer-derived NDMA precursors are not removed by GAC, it is essential to optimize the use and synthesis of polyDADMAC to reduce NDMA precursors during water treatment.
ContributorsFischer, Natalia (Author) / Westerhoff, Paul (Thesis advisor) / Hristovski, Kiril (Committee member) / Fox, Peter (Committee member) / Arizona State University (Publisher)
Created2017