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- Genre: Masters Thesis
- Member of: Theses and Dissertations
- Resource Type: Text
- Status: Published
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
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
Gold-silver alloy nanoparticles (NPs) capped with adenosine 5'-triphosphate were synthesized by borohydride reduction of dilute aqueous metal precursors. High-resolution transmission electron microscopy showed the as-synthesized particles to be spherical with average diameters ~4 nm. Optical properties were measured by UV-Visible spectroscopy (UV-Vis), and the formation of alloy NPs was verified across all gold:silver ratios by a linear shift in the plasmon band maxima against alloy composition. The molar absorptivities of the NPs decreased non-linearly with increasing gold content from 2.0 x 108 M-1 cm-1 (fÉmax = 404 nm) for pure silver to 4.1 x 107 M-1 cm-1 (fÉmax = 511 nm) for pure gold. The NPs were immobilized onto transparent indium-tin oxide composite electrodes using layer-by-layer (LbL) deposition with poly(diallyldimethylammonium) acting as a cationic binder. The UV-Vis absorbance of the LbL film was used to calculate the surface coverage of alloy NPs on the electrode. Typical preparations had average NP surface coverages of 2.8 x 10-13 mol NPs/cm2 (~5% of cubic closest packing) with saturated films reaching ~20% of ccp for single-layer preparations (1.0 ~ 10-12 mol NPs/cm2). X-ray photoelectron spectroscopy confirmed the presence of alloy NPs in the LbL film and showed silver enrichment of the NP surfaces by ~9%. Irreversible oxidative dissolution (dealloying) of the less noble silver atoms from the NPs on LbL electrodes was performed by cyclic voltammetry (CV) in sulfuric acid. Alloy NPs with higher gold content required larger overpotentials for silver dealloying. Dealloying of the more-noble gold atoms from the alloy NPs was also achieved by CV in sodium chloride. The silver was oxidized first to cohesive silver chloride, and then gold dealloyed to soluble HAuCl4- at higher potentials. Silver oxidation was inhibited during the first oxidative scan, but subsequent cycles showed typical, reversible silver-to-silver chloride voltammetry. The potentials for both silver oxidation and gold dealloying also shifted to more oxidizing potentials with increasing gold content, and both processes converged for alloy NPs with >60% gold content. Charge-mediated electrochemistry of silver NPs immobilized in LbL films, using Fc(meOH) as the charge carrier, showed that 67% of the NPs were electrochemically inactive.
ContributorsStarr, Christopher A (Author) / Buttry, Daniel A (Thesis advisor) / Petuskey, William (Committee member) / Jones, Anne (Committee member) / Arizona State University (Publisher)
Created2014
Description
Processed pyro-gel contains castor oil with solid component of boehmite (Al-OOH). The pyro-gel is synthesized by heat to convert boehmite to gamma-Al2O3 and to a certain extent alpha-Al2O3 nano-particles and castor oil into carbon residue. The effect of heat on pyro-gel is analyzed in a series of experiments using two burning chambers with the initial temperature as the main factor. The obtained temperature distribution profiles are studied and it is observed that the gel behaves very close to the theoretical prediction under heat. The carbon residue with Al2O3 is then processed for twelve hours and then analyzed to obtain the pore distribution of the Al2O3 nano-particles and the relation between the pore volume and the pre-heat temperature is analyzed. The obtained pore distribution shows the pore volume of Al2O3 nano-particles has direct relation to the pre-heat temperature. The experimental process involving the cylindrical reactor is simulated by using a finite rate chemistry eddy-dissipation model in a non-premixed and a porous mesh. The temperature distribution profile of the processed gel for both the meshes is obtained and a comparison is done with the data obtained in the experimental analysis. The temperature distribution obtained from the simulations show they follow a very similar profile to the temperature distribution obtained from experimental analysis, thus confirming the accuracy of both the models. The variation in numerical values between the experimental and simulation analysis is discussed. A physical model is proposed to determine the pore formation based on the temperature distribution obtained from experimental analysis and simulation.
ContributorsSagi, Varun (Author) / Lee, Taewoo (Thesis advisor) / Phelan, Patrick (Committee member) / Chen, Kangping (Committee member) / Arizona State University (Publisher)
Created2010
Description
Atmospheric particulate matter has a substantial impact on global climate due to its ability to absorb/scatter solar radiation and act as cloud condensation nuclei (CCN). Yet, little is known about marine aerosol, in particular, the carbonaceous fraction. In the present work, particulate matter was collected, using High Volume (HiVol) samplers, onto quartz fiber substrates during a series of research cruises on the Atlantic Ocean. Samples were collected on board the R/V Endeavor on West–East (March–April, 2006) and East–West (June–July, 2006) transects in the North Atlantic, as well as on the R/V Polarstern during a North–South (October–November, 2005) transect along the western coast of Europe and Africa. The aerosol total carbon (TC) concentrations for the West–East (Narragansett, RI, USA to Nice, France) and East–West (Heraklion, Crete, Greece to Narragansett, RI, USA) transects were generally low over the open ocean (0.36±0.14 μg C/m3) and increased as the ship approached coastal areas (2.18±1.37 μg C/m3), due to increased terrestrial/anthropogenic aerosol inputs. The TC for the North–South transect samples decreased in the southern hemisphere with the exception of samples collected near the 15th parallel where calculations indicate the air mass back trajectories originated from the continent. Seasonal variation in organic carbon (OC) was seen in the northern hemisphere open ocean samples with average values of 0.45 μg/m3 and 0.26 μg/m3 for spring and summer, respectively. These low summer time values are consistent with SeaWiFS satellite images that show decreasing chlorophyll a concentration (a proxy for phytoplankton biomass) in the summer. There is also a statistically significant (p<0.05) decline in surface water fluorescence in the summer. Moreover, examination of water–soluble organic carbon (WSOC) shows that the summer aerosol samples appear to have a higher fraction of the lower molecular weight material, indicating that the samples may be more oxidized (aged). The seasonal variation in aerosol content seen during the two 2006 cruises is evidence that a primary biological marine source is a significant contributor to the carbonaceous particulate in the marine atmosphere and is consistent with previous studies of clean marine air masses.
ContributorsHill, Hansina Rae (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2011
Description
The work described in the thesis involves the synthesis of a molecular triad which is designed to undergo proton coupled electron transfer (PCET) upon irradiation with light. Photoinduced PCET is an important process that many organisms use and the elucidation of its mechanism will allow further understanding of this process and its potential applications. The target compound designed for PCET studies consists of a porphyrin chromophore (also a primary electron donor), covalently linked to a phenol-imidazole (secondary electron donor), and a C60 (primary electron acceptor). The phenol-imidazole moiety of this system is modeled after the TyrZ His-190 residues in the reaction center of Photosystem II (PS II). These residues participate in an intermolecular H-bond between the phenol side chain of TyrZ and the imidazole side chain of His-190. The phenol side chain of TyrZ is the electron transfer mediator between the oxygen evolving complex (OEC) and P680 (primary electron donor) in PSII. During electron transfer from TyrZ to P680*+, the phenolic proton of TyrZ becomes highly acidic (pKa~-2) and the hydrogen is preferentially transferred to the relatively basic imidazole of His-190 through a pre-existing hydrogen bond. This PCET process avoids a charged intermediate, on TyrZ, and results in a neutral phenolic radical (TyrZ*). The current research consists of building a molecular triad, which can mimic the photoinduced PCET process of PSII. The following, documents the synthetic progress in the synthesis of a molecular triad designed to investigate the mechanism of PCET as well as gain further insight on how this process can be applied in artificial photosynthetic devices.
ContributorsPatterson, Dustin (Author) / Moore, Ana L (Thesis advisor) / Gust, Devens (Committee member) / Skibo, Edward B (Committee member) / Arizona State University (Publisher)
Created2011
Description
Alkali treated aluminosilicate (geopolymer) was functionalized by surfactant to increase the hydrophobicity for making Pickering emulsion for the first part of this work. In the first part of this study, alkali treated metakaolin was functionalized with cetyltrimethylammonium bromide ((C16H33)N(CH3)3Br, CTAB). The electrostatic interaction between this quaternary ammonium and the surface of the aluminosilicate which has negative charge has taken place. The particles then were used to prepare Pickering emulsion. The resulting stable dispersions, obtained very fast at very simple conditions with low ratio of aluminosilicate to liquid phase. In the second part, the interaction between geopolymer and glycerol was studied to see the covalent grafting of the geopolymer for making geopolymer composite. The composite material would be the basis material to be used as support catalyst, thin coating reagent and flame retardant material and so on, Variety of techniques, Thermogravimetric (TGA), Particle-induced X-ray emission (PIXE), FTIR, Solid state NMR, Powder X-ray diffraction (PXRD), BET surface area, Elemental analysis (CHN), TEM, SEM and Optical microscopy were used to characterize the functionalized geopolymer.
ContributorsMesgar, Milad (Author) / Seo, Dong-Kuyn (Thesis advisor) / Petuskey, William (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2012
Description
Polydimethyl siloxane is a commonly used fabrication material for microfluidic devices. However, its hydrophobic nature and protein adsorption on the surface restricts its use for microfluidic applications. Also, it is critical to control the electroosmotic flow for electrophoretic and dielectrophoretic manipulations. Therefore, surface modification of PDMS is essential to make it well suited for bioanalytical applications. In this project, the role of polyethylene oxide copolymers F108 and PLL-PEG has been investigated to modify the surface properties of PDMS using physisorption method. Measuring electroosmotic flow and adsorption studies tested the quality and the long-term stability of the modified PDMS surface. Static and dynamic coating strategies were used to modify the PDMS surface. In static coating, the PDMS surface was incubated with the coating agent prior to the measurements. For dynamic coating, the coating agent was always present in the solution throughout the experiment. F108 and PLL-PEG were equally effective to prevent the protein adsorption under both strategies. However, dynamic coating was more time saving. Furthermore, effective reduction of EOF was observed with F108 coating agent under dynamic conditions and with PLL-PEG coating agent under static conditions. Moreover, PLL-PEG dynamic coatings exhibited reversal of EOF. These important findings could be used to manipulate EOF and suggest optimal coating agent and strategies for PDMS surface treatment by the physisorption method.
ContributorsManchanda, Shikha (Author) / Ros, Alexandra (Thesis advisor) / Hayes, Mark (Committee member) / Liu, Yan (Committee member) / Arizona State University (Publisher)
Created2012
Description
Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface.
ContributorsShah, QuratulAin Jawed (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2012
Description
With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts chemical energy into electrical energy. Proton exchange membrane fuel cells (PEMFCs) are a highly researched energy source for automotive and stationary power applications. In order to produce the power required to meet Department of Energy requirements, platinum (Pt) must be used as a catalyst material in PEMFCs. Platinum, however, is very expensive and extensive research is being conducted to develop ways to reduce the amount of platinum used in PEMFCs. In the current study, three catalyst synthesis techniques were investigated and evaluated on their effectiveness to produce platinum-on copper (Pt@Cu) core-shell nanocatalyst on multi-walled carbon nanotube (MWCNT) support material. These three methods were direct deposition method, two-phase surfactant method, and single-phase surfactant method, in which direct deposition did not use a surfactant for particle size control and the surfactant methods did. The catalyst materials synthesized were evaluated by visual inspection and fuel cell performance. Samples which produced high fuel cell power output were evaluated using transmission electron microscopy (TEM) imaging. After evaluation, it was concluded that the direct deposition technique was effective in synthesizing Pt@Cu core-shell nanocatalyst on MWCNTs support when a rinsing process was used before adding platinum. The peak power density achieved by the rinsed core-shell catalyst was 618 mW.cm-2 , 13 percent greater than that of commercial platinum-carbon (Pt/C) catalyst. Transmission electron microscopy imaging revealed the core-shell catalyst contained Pt shells and platinum-copper alloy cores. Rinsing with deionized (DI) water was shown to be a crucial step in core-shell catalyst deposition as it reduced the number of platinum colloids on the carbon nanotube surface. After evaluation, it was concluded that the two-phase surfactant and single-phase surfactant synthesis methods were not effective at producing core-shell nanocatalyst with the parameters investigated.
ContributorsAdame, Anthony (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Peng, Xihong (Committee member) / Tamizhmani, Govindasamy (Committee member) / Arizona State University (Publisher)
Created2012