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A description of numerical and analytical work pertaining to models that describe the growth and progression of glioblastoma multiforme (GBM), an aggressive form of primary brain cancer. Two reaction-diffusion models are used: the Fisher-Kolmogorov-Petrovsky-Piskunov equation and a 2-population model that divides the tumor into actively proliferating and quiescent (or necrotic) cells. The numerical portion of this work (chapter 2) focuses on simulating GBM expansion in patients undergoing treatment for recurrence of tumor following initial surgery. The models are simulated on 3-dimensional brain geometries derived from magnetic resonance imaging (MRI) scans provided by the Barrow Neurological Institute. The study consists of 17 clinical time intervals across 10 patients that have been followed in detail, each of whom shows significant progression of tumor over a period of 1 to 3 months on sequential follow up scans. A Taguchi sampling design is implemented to estimate the variability of the predicted tumors to using 144 different choices of model parameters. In 9 cases, model parameters can be identified such that the simulated tumor contains at least 40 percent of the volume of the observed tumor. In the analytical portion of the paper (chapters 3 and 4), a positively invariant region for our 2-population model is identified. Then, a rigorous derivation of the critical patch size associated with the model is performed. The critical patch (KISS) size is the minimum habitat size needed for a population to survive in a region. Habitats larger than the critical patch size allow a population to persist, while smaller habitats lead to extinction. The critical patch size of the 2-population model is consistent with that of the Fisher-Kolmogorov-Petrovsky-Piskunov equation, one of the first reaction-diffusion models proposed for GBM. The critical patch size may indicate that GBM tumors have a minimum size depending on the location in the brain. A theoretical relationship between the size of a GBM tumor at steady-state and its maximum cell density is also derived, which has potential applications for patient-specific parameter estimation based on magnetic resonance imaging data.
ContributorsHarris, Duane C. (Author) / Kuang, Yang (Thesis advisor) / Kostelich, Eric J. (Thesis advisor) / Preul, Mark C. (Committee member) / Crook, Sharon (Committee member) / Gardner, Carl (Committee member) / Arizona State University (Publisher)
Created2023
Description
The measurement of the radiation and convection that the human body experiences are important for ensuring safety in extreme heat conditions. The radiation from the surroundings on the human body is most often measured using globe or cylindrical radiometers. The large errors stemming from differences in internal and exterior temperatures and indirect estimation of convection can be resolved by simultaneously using three cylindrical radiometers (1 cm diameter, 9 cm height) with varying surface properties and internal heating. With three surface balances, the three unknowns (heat transfer coefficient, shortwave, and longwave radiation) can be solved for directly. As compared to integral radiation measurement technique, however, the bottom mounting using a wooden-dowel of the three-cylinder radiometers resulted in underestimated the total absorbed radiation. This first part of this thesis focuses on reducing the size of the three-cylinder radiometers and an alternative mounting that resolves the prior issues. In particular, the heat transfer coefficient in laminar wind tunnel with wind speed of 0.25 to 5 m/s is measured for six polished, heated cylinders with diameter of 1 cm and height of 1.5 to 9 cm mounted using a wooden dowel. For cylinders with height of 6 cm and above, the heat transfer coefficients are independent of the height and agree with the Hilpert correlation for infinitely long cylinder. Subsequently, a side-mounting for heated 6 cm tall cylinder with top and bottom metallic caps is developed and tested within the wind tunnel. The heat transfer coefficient is shown to be independent of the flow-side mounting and in agreement with the Hilpert correlation.
The second part of this thesis explores feasibility of employing the three-cylinder concept to measuring all air-flow parameters relevant to human convection including mean wind speed, turbulence intensity and length scale. Heated cylinders with same surface properties but varying diameters are fabricated. Uniformity of their exterior temperature, which is fundamental to the three-cylinder anemometer concept, is tested during operation using infrared camera. To provide a lab-based method to measure convection from the cylinders in turbulent flow, several designs of turbulence-generating fractal grids are laser-cut and introduced into the wind tunnel.
ContributorsGupta, Mahima (Author) / Rykaczewski, Konrad (Thesis advisor) / Pathikonda, Gokul (Thesis advisor) / Middel, Ariane (Committee member) / Arizona State University (Publisher)
Created2024
Description
Microplastics, plastics smaller than 5 mm, are an emerging concern worldwide due to their potential adverse effects on the environment and human health. Microplastics have the potential to biomagnify through the food chain, and are prone to adsorbing organic pollutants and heavy metals. Therefore, there is an urgent need to assess the extent of microplastic contamination in different environments. The occurrence of microplastics in the atmosphere of Tempe, AZ was investigated and results show concentrations as high as 1.1 microplastics/m3. The most abundant identified polymer was polyvinyl chloride. However, chemical characterization is fraught with challenges, with a majority of microplastics remaining chemically unidentified. Laboratory experiments simulating weathering of microplastics revealed that Raman spectra of microplastics change over time due to weathering processes. This work also studied the spatial variation of microplastics in soil in Phoenix and the surrounding areas of the Sonoran Desert, and microplastic abundances ranged from 122 to 1299 microplastics/kg with no clear trends between different locations, and substantial total deposition of microplastics occurring in the same location with resuspension and redistribution of deposited microplastics likely contributing to unclear spatial trends. Temporal variation of soil microplastics from 2005 to 2015 show a systematic increase in the abundance of microplastics. Polyethylene was prominent in all soil samples.
Further, recreational surface waters were investigated as a potential source of microplastics in aquatic environments. The temporal variation of microplastics in the Salt River, AZ over the course of one day depicted an increase of 8 times in microplastic concentration at peak activity time of 16:00 hr compared to 8:00 hr. Concurrently, microplastic concentrations in surface water samples from apartment community swimming pools in Tempe, AZ depicted substantial variability with concentrations as high as 254,574 MPs/m3. Polyester and Polyamide fibers were prevalent in surface water samples, indicating a release from synthetic fabrics. Finally, a method for distinguishing tire wear microplastics from soot in ambient aerosol samples was developed using Programmed Thermal Analysis, that allows for the quantification of Elemental Carbon. The method was successfully applied on urban aerosol samples with results depicting substantial fractions of tire wear in urban atmospheric environments.
ContributorsChandrakanthan, Kanchana (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2024
Description
The global increase in urbanization has raised questions about urban sustainability to which multiple research communities have entered. Those communities addressing interest in the urban heat island (UHI) effect and extreme temperatures include land system science, urban/landscape ecology, and urban climatology. General investigations of UHI have focused primarily on land surface and canopy layer air temperatures. The surface temperature is of prime importance to UHI studies because of its central rule in the surface energy balance, direct effects on air temperature, and outdoor thermal comfort. Focusing on the diurnal surface temperature variations in Phoenix, Arizona, especially on the cool (green space) island effect and the surface heat island effect, the dissertation develops three research papers that improve the integration among the abovementioned sub-fields. Specifically, these papers involve: (1) the quantification and modeling of the diurnal cooling benefits of green space; (2) the optimization of green space locations to reduce the surface heat island effect in daytime and nighttime; and, (3) an evaluation of the effects of vertical urban forms on land surface temperature using Google Street View. These works demonstrate that the pattern of new green spaces in central Phoenix could be optimized such that 96% of the maximum daytime and nighttime cooling benefits would be achieved, and that Google Street View data offers an alternative to other data, providing the vertical dimensions of land-cover for addressing surface temperature impacts, increasing the model accuracy over the use of horizontal land-cover data alone. Taken together, the dissertation points the way towards the integration of research directions to better understand the consequences of detailed land conditions on temperatures in urban areas, providing insights for urban designs to alleviate these extremes.
ContributorsZhang, Yujia (Author) / Turner, Billie (Thesis advisor) / Murray, Alan T. (Committee member) / Myint, Soe W (Committee member) / Middel, Ariane (Committee member) / Arizona State University (Publisher)
Created2018
Description
Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand these reactions, as well as how organic material is scavenged and deposited, so that climate and health effects can be fully assessed. Stable carbon isotopes have been used widely in studying gas- and particle-phase atmospheric chemistry. However, the processing of organic matter by fog has not yet been studied, even though stable isotopes can be used to track all aspects of atmospheric processing, from particle formation, particle scavenging, reactions that form secondary organic aerosol material, and particle deposition. Here, carbon isotope analysis is used for the first time to assess the processing of carbonaceous particles by fog.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
ContributorsNapolitano, Denise (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2018
Description
Urban-induced heating is a challenge to the livability and health of city dwellers. It is a complex issue that many cities are facing, and a more urgent hazard in hot urban deserts (HUDs) than elsewhere due to already high temperatures and aridity. The challenge compounds in the absence of more localized heat mitigation understanding. In addition, over-reliance on evidence from temperate regions is disconnected from the actualities of extreme bioclimatic dynamics found in HUDs. This dissertation is an integration of a series of studies that inform urban climate relationships specific to HUDs. This three-paper dissertation demonstrates heat mitigation aspirational goals from actualities, depicts local urban thermal drivers in Kuwait, and then tests morphological sensitivity of selected thermal modulation strategies in one neighborhood in Kuwait City.
The first paper is based on a systematic literature review where evidence from morphological mitigation strategies in HUDs were critically reviewed, synthesized and integrated. Metrics, measurements, and methods were extracted to examine the applicability of the different strategies, and a content synthesis identified the levels of strategy success. Collective challenges and uncertainties were interpreted to compare aspirational goals from actualities of morphological mitigation strategies.
The second paper unpacks the relationship of urban morphological attributes in influencing thermal conditions to assess latent magnitudes of heat amelioration strategies. Mindful of the challenges presented in the first study, a 92-day summer field-measurement campaign captured system dynamics of urban thermal stimuli within sub-diurnal phenomena. A composite data set of sub-hourly air temperature measurements with sub-meter morphological attributes was built, statistically analyzed, and modeled. Morphological mediation effects were found to vary hourly with different patterns under varying weather conditions in non-linear associations. Results suggest mitigation interventions be investigated and later tested on a site- use and time-use basis.
The third paper concludes with a simulation-based study to conform on the collective findings of the earlier studies. The microclimate model ENVI-met 4.4, combined with field measurements, was used to simulate the effect of rooftop shade-sails in cooling the near ground thermal environment. Results showed significant cooling effects and thus presented a novel shading approach that challenges orthodox mitigation strategies in HUDs.
The first paper is based on a systematic literature review where evidence from morphological mitigation strategies in HUDs were critically reviewed, synthesized and integrated. Metrics, measurements, and methods were extracted to examine the applicability of the different strategies, and a content synthesis identified the levels of strategy success. Collective challenges and uncertainties were interpreted to compare aspirational goals from actualities of morphological mitigation strategies.
The second paper unpacks the relationship of urban morphological attributes in influencing thermal conditions to assess latent magnitudes of heat amelioration strategies. Mindful of the challenges presented in the first study, a 92-day summer field-measurement campaign captured system dynamics of urban thermal stimuli within sub-diurnal phenomena. A composite data set of sub-hourly air temperature measurements with sub-meter morphological attributes was built, statistically analyzed, and modeled. Morphological mediation effects were found to vary hourly with different patterns under varying weather conditions in non-linear associations. Results suggest mitigation interventions be investigated and later tested on a site- use and time-use basis.
The third paper concludes with a simulation-based study to conform on the collective findings of the earlier studies. The microclimate model ENVI-met 4.4, combined with field measurements, was used to simulate the effect of rooftop shade-sails in cooling the near ground thermal environment. Results showed significant cooling effects and thus presented a novel shading approach that challenges orthodox mitigation strategies in HUDs.
ContributorsAlKhaled, Saud R A H (Author) / Coseo, Paul (Thesis advisor) / Brazel, Anthony (Thesis advisor) / Middel, Ariane (Committee member) / Cheng, Chingwen (Committee member) / Arizona State University (Publisher)
Created2019
Description
During summer 2014, a study was conducted as part of the Landscape Architecture Foundation Case Study Investigation to analyze features of three sustainably designed landscapes. Each project was located in a southwest desert city: Civic Space Park in Phoenix, AZ, the Pete V. Domenici US Courthouse Sustainable Landscape Retrofit in Albuquerque, NM, and George "Doc" Cavalliere Park in Scottsdale, AZ. The principal components of each case study were performance benefits that quantified ongoing ecosystem services. Performance benefits were developed from data provided by the designers and collected by the research team. The functionality of environmental, social, and economic sustainable features was evaluated. In southwest desert cities achieving performance benefits such as microclimate cooling often come at the cost of water conservation. In each of these projects such tradeoffs were balanced by prioritizing the project goals and constraints.
During summer 2015, a study was conducted to characterize effects of tree species and shade structures on outdoor human thermal comfort under hot, arid conditions. Motivating the research was the hypothesis that tree species and shade structures will vary in their capacity to improve thermal comfort due to their respective abilities to attenuate solar radiation. Micrometeorological data was collected in full sun and under shade of six landscape tree species and park ramadas in Phoenix, AZ during pre-monsoon summer afternoons. The six landscape tree species included: Arizona ash (Fraxinus velutina Torr.), Mexican palo verde (Parkinsonia aculeata L.), Aleppo pine (Pinus halepensis Mill.), South American mesquite (Prosopis spp. L.), Texas live oak (Quercus virginiana for. fusiformis Mill.), and Chinese elm (Ulmus parvifolia Jacq.). Results showed that the tree species and ramadas were not similarly effective at improving thermal comfort, represented by physiologically equivalent temperature (PET). The difference between PET in full sun and under shade was greater under Fraxinus and Quercus than under Parkinsonia, Prosopis, and ramadas by 2.9-4.3 °C. Radiation was a significant driver of PET (p<0.0001, R2=0.69) and with the exception of ramadas, lower radiation corresponded with lower PET. Variations observed in this study suggest selecting trees or structures that attenuate the most solar radiation is a potential strategy for optimizing PET.
During summer 2015, a study was conducted to characterize effects of tree species and shade structures on outdoor human thermal comfort under hot, arid conditions. Motivating the research was the hypothesis that tree species and shade structures will vary in their capacity to improve thermal comfort due to their respective abilities to attenuate solar radiation. Micrometeorological data was collected in full sun and under shade of six landscape tree species and park ramadas in Phoenix, AZ during pre-monsoon summer afternoons. The six landscape tree species included: Arizona ash (Fraxinus velutina Torr.), Mexican palo verde (Parkinsonia aculeata L.), Aleppo pine (Pinus halepensis Mill.), South American mesquite (Prosopis spp. L.), Texas live oak (Quercus virginiana for. fusiformis Mill.), and Chinese elm (Ulmus parvifolia Jacq.). Results showed that the tree species and ramadas were not similarly effective at improving thermal comfort, represented by physiologically equivalent temperature (PET). The difference between PET in full sun and under shade was greater under Fraxinus and Quercus than under Parkinsonia, Prosopis, and ramadas by 2.9-4.3 °C. Radiation was a significant driver of PET (p<0.0001, R2=0.69) and with the exception of ramadas, lower radiation corresponded with lower PET. Variations observed in this study suggest selecting trees or structures that attenuate the most solar radiation is a potential strategy for optimizing PET.
ContributorsColter, Kaylee (Author) / Martin, Chris (Thesis advisor) / Coseo, Paul (Committee member) / Middel, Ariane (Committee member) / Arizona State University (Publisher)
Created2016
Description
Chemical and physical interactions of flowing ice and rock have inexorably shaped planetary surfaces. Weathering in glacial environments is a significant link in biogeochemical cycles – carbon and strontium – on Earth, and may have once played an important role in altering Mars’ surface. Despite growing recognition of the importance of low-temperature chemical weathering, these processes are still not well understood. Debris-coated glaciers are also present on Mars, emphasizing the need to study ice-related processes in the evolution of planetary surfaces. During Earth’s history, subglacial environments are thought to have sheltered communities of microorganisms from extreme climate variations. On Amazonian Mars, glaciers such as lobate debris aprons (LDA) could have hosted chemolithotrophic communities, making Mars’ present glaciers candidates for life preservation. This study characterizes glacial processes on both Earth and Mars.
Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.
Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.
I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.
Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.
I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
ContributorsRutledge, Alicia Marie (Author) / Christensen, Philip R. (Thesis advisor) / Shock, Everett (Committee member) / Clarke, Amanda (Committee member) / Sharp, Thomas (Committee member) / Whipple, Kelin (Committee member) / Arizona State University (Publisher)
Created2015
Description
Natural variations in 238U/235U of marine carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ~7.5 and ~ 8.5 to study possible U isotope fractionation during incorporation into these minerals.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
ContributorsChen, Xinming (Author) / Anbar, Ariel (Thesis advisor) / Herckes, Pierre (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2015
Description
The discovery and development of novel antibacterial agents is essential to address the rising health concern over antibiotic resistant bacteria. This research investigated the antibacterial activity of a natural clay deposit near Crater Lake, Oregon, that is effective at killing antibiotic resistant human pathogens. The primary rock types in the deposit are andesitic pyroclastic materials, which have been hydrothermally altered into argillic clay zones. High-sulfidation (acidic) alteration produced clay zones with elevated pyrite (18%), illite-smectite (I-S) (70% illite), elemental sulfur, kaolinite and carbonates. Low-sulfidation alteration at neutral pH generated clay zones with lower pyrite concentrations pyrite (4-6%), the mixed-layered I-S clay rectorite (R1, I-S) and quartz.
Antibacterial susceptibility testing reveals that hydrated clays containing pyrite and I-S are effective at killing (100%) of the model pathogens tested (E. coli and S. epidermidis) when pH (< 4.2) and Eh (> 450 mV) promote pyrite oxidation and mineral dissolution, releasing > 1 mM concentrations of Fe2+, Fe3+ and Al3+. However, certain oxidized clay zones containing no pyrite still inhibited bacterial growth. These clays buffered solutions to low pH (< 4.7) and oxidizing Eh (> 400 mV) conditions, releasing lower amounts (< 1 mM) of Fe and Al. The presence of carbonate in the clays eliminated antibacterial activity due to increases in pH, which lower pyrite oxidation and mineral dissolution rates.
The antibacterial mechanism of these natural clays was explored using metal toxicity and genetic assays, along with advanced bioimaging techniques. Antibacterial clays provide a continuous reservoir of Fe2+, Fe3+ and Al3+ that synergistically attack pathogens while generating hydrogen peroxide (H2O¬2). Results show that dissolved Fe2+ and Al3+ are adsorbed to bacterial envelopes, causing protein misfolding and oxidation in the outer membrane. Only Fe2+ is taken up by the cells, generating oxidative stress that damages DNA and proteins. Excess Fe2+ oxidizes inside the cell and precipitates Fe3+-oxides, marking the sites of hydroxyl radical (•OH) generation. Recognition of this novel geochemical antibacterial process should inform designs of new mineral based antibacterial agents and could provide a new economic industry for such clays.
Antibacterial susceptibility testing reveals that hydrated clays containing pyrite and I-S are effective at killing (100%) of the model pathogens tested (E. coli and S. epidermidis) when pH (< 4.2) and Eh (> 450 mV) promote pyrite oxidation and mineral dissolution, releasing > 1 mM concentrations of Fe2+, Fe3+ and Al3+. However, certain oxidized clay zones containing no pyrite still inhibited bacterial growth. These clays buffered solutions to low pH (< 4.7) and oxidizing Eh (> 400 mV) conditions, releasing lower amounts (< 1 mM) of Fe and Al. The presence of carbonate in the clays eliminated antibacterial activity due to increases in pH, which lower pyrite oxidation and mineral dissolution rates.
The antibacterial mechanism of these natural clays was explored using metal toxicity and genetic assays, along with advanced bioimaging techniques. Antibacterial clays provide a continuous reservoir of Fe2+, Fe3+ and Al3+ that synergistically attack pathogens while generating hydrogen peroxide (H2O¬2). Results show that dissolved Fe2+ and Al3+ are adsorbed to bacterial envelopes, causing protein misfolding and oxidation in the outer membrane. Only Fe2+ is taken up by the cells, generating oxidative stress that damages DNA and proteins. Excess Fe2+ oxidizes inside the cell and precipitates Fe3+-oxides, marking the sites of hydroxyl radical (•OH) generation. Recognition of this novel geochemical antibacterial process should inform designs of new mineral based antibacterial agents and could provide a new economic industry for such clays.
ContributorsMorrison, Keith D (Author) / Williams, Lynda B (Thesis advisor) / Williams, Stanley N (Thesis advisor) / Misra, Rajeev (Committee member) / Shock, Everett (Committee member) / Anbar, Ariel (Committee member) / Arizona State University (Publisher)
Created2015