Matching Items (3)
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- All Subjects: Nanoparticles
- Genre: Doctoral Dissertation
- Creators: Emady, Heather
Description
As the use of engineered nanomaterials (ENMs) in consumer products becomes more common, the amount of ENMs entering wastewater treatment plants (WWTPs) increases. Investigating the fate of ENMs in WWTPs is critical for risk assessment and pollution control. The objectives of this dissertation were to (1) quantify and characterize titanium (Ti) in full-scale wastewater treatment plants, (2) quantify sorption of different ENMs to wastewater biomass in laboratory-scale batch reactors, (3) evaluate the use of a standard, soluble-pollutant sorption test method for quantifying ENM interaction with wastewater biomass, and (4) develop a mechanistic model of a biological wastewater treatment reactor to serve as the basis for modeling nanomaterial fate in WWTPs. Using titanium (Ti) as a model material for the fate of ENMs in WWTPs, Ti concentrations were measured in 10 municipal WWTPs. Ti concentrations in pant influent ranged from 181 to 3000 µg/L, and more than 96% of Ti was removed, with effluent Ti concentrations being less than 25 µg/L. Ti removed from wastewater accumulated in solids at concentrations ranging from 1 to 6 µg Ti/mg solids. Using transmission electron microscopy, spherical titanium oxide nanoparticles with diameters ranging from 4 to 30 nm were found in WWTP effluents, evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems. Batch experiments were conducted to quantify sorption of different ENM types to activated sludge. Percentages of sorption to 400 mg TSS/L biomass ranged from about 10 to 90%, depending on the ENM material and functionalization. Natural organic matter, surfactants, and proteins had a stabilizing effect on most of the ENMs tested. The United States Environmental Protection Agency's standard sorption testing method (OPPTS 835.1110) used for soluble compounds was found to be inapplicable to ENMs, as freeze-dried activated sludge transforms ENMs into stable particles in suspension. In conjunction with experiments, we created a mechanistic model of the microbiological processes in membrane bioreactors to predict MBR, extended and modified this model to predict the fate of soluble micropollutants, and then discussed how the micropollutant fate model could be used to predict the fate of nanomaterials in wastewater treatment plants.
ContributorsKiser, Mehlika Ayla (Author) / Westerhoff, Paul K (Thesis advisor) / Rittmann, Bruce E. (Committee member) / Hristovski, Kiril D (Committee member) / Arizona State University (Publisher)
Created2011
Description
A comprehensive and systematic investigation on the diffusion and phase behaviors of nanoparticles and macromolecules in two component liquid-liquid systems via Molecule Dynamic (MD) simulations is presented in this dissertation.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
ContributorsGao, Wei (Author) / Dai, Lenore (Thesis advisor) / Jiao, Yang (Committee member) / Liu, Yongming (Committee member) / Green, Matthew (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2017
Description
The applications utilizing nanoparticles have grown in both industrial and academic areas because of the very large surface area to volume ratios of these particles. One of the best ways to process and control these nanoparticles is fluidization. In this work, a new microjet and vibration assisted (MVA) fluidized bed system was developed in order to fluidize nanoparticles. The system was tested and the parameters optimized using two commercially available TiO2 nanoparticles: P25 and P90. The fluidization quality was assessed by determining the non-dimensional bed height as well as the non-dimensional pressure drop. The non-dimensional bed height for the nanosized TiO2 in the MVA system optimized at about 5 and 7 for P25 and P90 TiO2, respectively, at a resonance frequency of 50 Hz. The non-dimensional pressure drop was also determined and showed that the MVA system exhibited a lower minimum fluidization velocity for both of the TiO2 types as compared to fluidization that employed only vibration assistance. Additional experiments were performed with the MVA to characterize the synergistic effects of vibrational intensity and gas velocity on the TiO2 P25 and P90 fluidized bed heights. Mathematical relationships were developed to correlate vibrational intensity, gas velocity, and fluidized bed height in the MVA. The non-dimensional bed height in the MVA system is comparable to previously published P25 TiO2 fluidization work that employed an alcohol in order to minimize the electrostatic attractions within the bed. However, the MVA system achieved similar results without the addition of a chemical, thereby expanding the potential chemical reaction engineering and environmental remediation opportunities for fluidized nanoparticle systems.
In order to aid future scaling up of the MVA process, the agglomerate size distribution in the MVA system was predicted by utilizing a force balance model coupled with a two-fluid model (TFM) simulation. The particle agglomerate size that was predicted using the computer simulation was validated with experimental data and found to be in good agreement.
Lastly, in order to demonstrate the utility of the MVA system in an air revitalization application, the capture of CO2 was examined. CO2 breakthrough time and adsorption capacities were tested in the MVA system and compared to a vibrating fluidized bed (VFB) system. Experimental results showed that the improved fluidity in the MVA system enhanced CO2 adsorption capacity.
In order to aid future scaling up of the MVA process, the agglomerate size distribution in the MVA system was predicted by utilizing a force balance model coupled with a two-fluid model (TFM) simulation. The particle agglomerate size that was predicted using the computer simulation was validated with experimental data and found to be in good agreement.
Lastly, in order to demonstrate the utility of the MVA system in an air revitalization application, the capture of CO2 was examined. CO2 breakthrough time and adsorption capacities were tested in the MVA system and compared to a vibrating fluidized bed (VFB) system. Experimental results showed that the improved fluidity in the MVA system enhanced CO2 adsorption capacity.
ContributorsAn, Keju (Author) / Andino, Jean (Thesis advisor) / Phelan, Patrick (Thesis advisor) / Adrian, Ronald (Committee member) / Emady, Heather (Committee member) / Kasbaoui, Mohamed (Committee member) / Arizona State University (Publisher)
Created2019