Matching Items (49)
Description
Harsh environments have conditions that make collecting scientific data difficult with existing commercial-off-the-shelf technology. Micro Electro Mechanical Systems (MEMS) technology is ideally suited for harsh environment characterization and operation due to the wide range of materials available and an incredible array of different sensing techniques while providing small device size, low power consumption, and robustness. There were two main objectives of the research conducted. The first objective was to design, fabricate, and test novel sensors that measure the amount of exposure to ionizing radiation for a wide range of applications including characterization of harsh environments. Two types of MEMS ionizing radiation dosimeters were developed. The first sensor was a passive radiation-sensitive capacitor-antenna design. The antenna's emitted frequency of peak-intensity changed as exposure time to radiation increased. The second sensor was a film bulk acoustic-wave resonator, whose resonant frequency decreased with increasing ionizing radiation exposure time. The second objective was to develop MEMS sensor systems that could be deployed to gather scientific data and to use that data to address the following research question: do temperature and/or conductivity predict the appearance of photosynthetic organisms in hot springs. To this end, temperature and electrical conductivity sensor arrays were designed and fabricated based on mature MEMS technology. Electronic circuits and the software interface to the electronics were developed for field data collection. The sensor arrays utilized in the hot springs yielded results that support the hypothesis that temperature plays a key role in determining where the photosynthetic organisms occur. Additionally, a cold-film fluidic flow sensor was developed, which is suitable for near-boiling temperature measurement. Future research should focus on (1) developing a MEMS pH sensor array with integrated temperature, conductivity, and flow sensors to provide multi-dimensional data for scientific study and (2) finding solutions to biofouling and self-calibration, which affects sensor performance over long-term deployment.
ContributorsOiler, Jonathon (Author) / Yu, Hongyu (Thesis advisor) / Anbar, Ariel (Committee member) / Hartnett, Hilairy (Committee member) / Scannapieco, Evan (Committee member) / Timmes, Francis (Committee member) / Arizona State University (Publisher)
Created2013
Description
This dissertation is presented in two sections. First, I explore two methods of using stable isotope analysis to trace environmental and biogeochemical processes. Second, I present two related studies investigating student understanding of the biogeochemical concepts that underlie part one. Fe and Hg are each biogeochemically important elements in their own way. Fe is a critical nutrient for phytoplankton, while Hg is detrimental to nearly all forms of life. Fe is often a limiting factor in marine phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown mineral dust, but other more soluble sources are more bioavailable. To look for evidence of these non-soil dust sources of Fe to the open ocean, I measured the isotopic composition of aerosol samples collected on Bermuda. I found clear evidence in the fine size fraction of a non-soil dust Fe source, which I conclude is most likely from biomass burning. Widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Isotope analysis would be a useful tool in quantifying this impact if the isotopic composition of Hg from CFL were known. My measurements show that CFL-Hg is isotopically fractionated, in a unique pattern, during normal operation. This fractionation is large and has a distinctive, mass-independent signature, such that CFL Hg can be uniquely identified from other sources. Misconceptions research in geology has been a very active area of research, but student thinking regarding the related field of biogeochemistry has not yet been studied in detail. From interviews with 40 undergraduates, I identified over 150 specific misconceptions. I also designed a multiple-choice survey (concept inventory) to measure understanding of these same biogeochemistry concepts. I present statistical evidence, based on the Rasch model, for the reliability and validity of this instrument. This instrument will allow teachers and researchers to easily quantify learning outcomes in biogeochemistry and will complement existing concept inventories in geology, chemistry, and biology.
ContributorsMead, Chris (Author) / Anbar, Ariel (Thesis advisor) / Semken, Steven (Committee member) / Shock, Everett (Committee member) / Herckes, Pierre (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2014
Description
Stable isotopes were measured in the groundwaters of the Salt River Valley basin in central Arizona to explore the utility of stable isotopes for sourcing recharge waters and engineering better well designs. Delta values for the sampled groundwaters range from -7.6‰ to -10‰ in 18O and -60‰ to -91‰ in D and display displacements off the global meteoric water line indicative of surficial evaporation during river transport into the area. Groundwater in the basin is all derived from top-down river recharge; there is no evidence of ancient playa waters even in the playa deposits. The Salt and Verde Rivers are the dominant source of groundwater for the East Salt River valley- the Agua Fria River also contributes significantly to the West Salt River Valley. Groundwater isotopic compositions are generally more depleted in 18O and D with depth, indicating past recharge in cooler climates, and vary within subsurface aquifer layers as sampled during well drilling. When isotopic data were evaluated together with geologic and chemical analyses and compared with data from the final well production water it was often possible to identify: 1) which horizons are the primary producers of groundwater flow and how that might change with time, 2) the chemical exchange of cations and anions via water-rock interaction during top-down mixing of recharge water with older waters, 3) how much well production might be lost if arsenic-contributing horizons were sealed off, and 4) the extent to which replacement wells tap different subsurface water sources. In addition to identifying sources of recharge, stable isotopes offer a new and powerful approach for engineering better and more productive water wells.
ContributorsBond, Angela Nicole (Author) / Knauth, Paul (Thesis advisor) / Hartnett, Hilairy (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2010
Description
Carbonaceous chondrites (CCs) present a unique opportunity for learning about the earliest organic chemistry that took place in our Solar System. The complex and diverse suite of meteoritic organic material is the result of multiple settings and physicochemical processes, including aqueous and thermal alteration. Though meteorites often inform origin-of-life discussions because they could have seeded early Earth with significant amounts of water and pre-biotic, organic material, their record of abiotic, aqueous, and organic geochemistry is of interest as well.
CC materials previously resided on asteroidal parent bodies, relic planetesimals of Solar System formation which never accreted enough material to develop long-lived, large-scale geological processes. These bodies were large enough, however, to experience some degree of heating due to the decay of radiogenic isotopes, and the meteorite record suggests the existence of 100-150 parent bodies which experienced varying degrees of thermal and aqueous alteration for the first several 10 Myr of Solar System history.
The first chapter of this dissertation reviews literature addressing aqueous alteration as an essential participant in parent body geochemistry, organic synthesis, or both (though papers which address both are rare). The second chapter is a published organic analysis of the soluble organic material of Bells, an unclassified type 2 chondrite. Analytical approaches to assess terrestrial contamination of meteorite samples are also reviewed in the first chapter to allow introduction in chapter 3 of kinetic modeling which rules out certain cases of contamination and constrains the timing of thermal and aqueous alteration. This is the first known application of isoleucine epimerization for either of these purposes. Chapter 4 is a kinetic study of D-allo-isoleucine epimerization to establish its behavior in systems with large, relative abundances of alloisoleucine to isoleucine. Previous epimerization studies for paleontological or geological purposes began with L-isoleucine, the only protein amino acid of the four isoleucine stereoisomers.
Kinetic model calculations using isoleucine stereoisomer abundances from 7 CR chondrites constrain the total duration of the amino acids' residence in the aqueous phase. The comparatively short timescales produced by the presented modeling elicit hypotheses for protection or transport of the amino acids within the CR parent body.
CC materials previously resided on asteroidal parent bodies, relic planetesimals of Solar System formation which never accreted enough material to develop long-lived, large-scale geological processes. These bodies were large enough, however, to experience some degree of heating due to the decay of radiogenic isotopes, and the meteorite record suggests the existence of 100-150 parent bodies which experienced varying degrees of thermal and aqueous alteration for the first several 10 Myr of Solar System history.
The first chapter of this dissertation reviews literature addressing aqueous alteration as an essential participant in parent body geochemistry, organic synthesis, or both (though papers which address both are rare). The second chapter is a published organic analysis of the soluble organic material of Bells, an unclassified type 2 chondrite. Analytical approaches to assess terrestrial contamination of meteorite samples are also reviewed in the first chapter to allow introduction in chapter 3 of kinetic modeling which rules out certain cases of contamination and constrains the timing of thermal and aqueous alteration. This is the first known application of isoleucine epimerization for either of these purposes. Chapter 4 is a kinetic study of D-allo-isoleucine epimerization to establish its behavior in systems with large, relative abundances of alloisoleucine to isoleucine. Previous epimerization studies for paleontological or geological purposes began with L-isoleucine, the only protein amino acid of the four isoleucine stereoisomers.
Kinetic model calculations using isoleucine stereoisomer abundances from 7 CR chondrites constrain the total duration of the amino acids' residence in the aqueous phase. The comparatively short timescales produced by the presented modeling elicit hypotheses for protection or transport of the amino acids within the CR parent body.
ContributorsMonroe, Adam Alexander (Author) / Pizzarello, Sandra (Thesis advisor) / Williams, Peter (Thesis advisor) / Anbar, Ariel D (Committee member) / Shock, Everett L (Committee member) / Arizona State University (Publisher)
Created2014
Description
The hydrothermal chemistry of organic compounds influences many critical geological processes, including the formation of oil and gas reservoirs, the degradation and transport of organic matter in sedimentary basins, metabolic cycles in the deep subsurface biosphere, and possibly prebiotic organic synthesis related to the origin of life. In most previous studies of hydrothermal organic reactions the emphasis has been mainly on determining reaction product distributions, studies that provide detailed mechanistic information or direct evidence for specific reaction intermediates are rare. To develop a better understanding, I performed hydrothermal experiments with model ketone compound dibenzylketone (DBK), which serves as a quite useful tool to probe the bond breaking and forming processes in hydrothermal geochemical transformations. A careful study of reaction kinetics and products of DBK in Chapter 2 of this dissertation reveals reversible and irreversible reaction pathways, and provides evidence for competing ionic and radical reaction mechanisms. The majority of the observed products result from homolytic carbon-carbon and carbon-hydrogen bond cleavage and secondary coupling reactions of the benzyl and related radical intermediates.
In the third chapter of the dissertation, a novel hydrothermal photochemical method is studied, which enabled in situ independent generation of the relevant radicals and effectively separated the radical and ionic reactions that occur simultaneously in pure thermal reactions. In the following chapter, I focus on the role of minerals on ketone hydrothermal reactions. Minerals such as quartz and corundum have no detectable effect on DBK, whereas magnetite, hematite, and troilite all increase ketone reactivity to various extents. The influence of these iron-bearing minerals can be attributed to the mineral surface catalysis or the solution chemistry change that is presumably caused by dissolved inorganic species from minerals. In addition, some new discoveries on strong oxidizing effect of copper (II) ion under hydrothermal conditions are described in the latter chapter of the dissertation, where examples of clean and rapid reactions that converted alcohols to aldehyde and aldehydes to carboxylic acids are included.
In the third chapter of the dissertation, a novel hydrothermal photochemical method is studied, which enabled in situ independent generation of the relevant radicals and effectively separated the radical and ionic reactions that occur simultaneously in pure thermal reactions. In the following chapter, I focus on the role of minerals on ketone hydrothermal reactions. Minerals such as quartz and corundum have no detectable effect on DBK, whereas magnetite, hematite, and troilite all increase ketone reactivity to various extents. The influence of these iron-bearing minerals can be attributed to the mineral surface catalysis or the solution chemistry change that is presumably caused by dissolved inorganic species from minerals. In addition, some new discoveries on strong oxidizing effect of copper (II) ion under hydrothermal conditions are described in the latter chapter of the dissertation, where examples of clean and rapid reactions that converted alcohols to aldehyde and aldehydes to carboxylic acids are included.
ContributorsYang, Ziming (Author) / Shock, Everett L (Thesis advisor) / Gould, Ian R (Committee member) / Wolf, George H. (Committee member) / Arizona State University (Publisher)
Created2014
Description
Sea ice algae dominated by diatoms inhabit the brine channels of the Arctic sea ice and serve as the base of the Arctic marine food web in the spring. I studied sea ice diatoms in the bottom 10 cm of first year land-fast sea ice off the coast of Barrow, AK, in spring of 2011, 2012, and 2013. I investigated the variability in the biomass and the community composition of these sea-ice diatoms between bloom phases, as a function of overlying snow depth and over time. The dominant genera were the pennate diatoms Nitzschia, Navicula, Thalassiothrix, and Fragilariopsis with only a minor contribution by centric diatoms. While diatom biomass as estimated by organic carbon changed significantly between early, peak, and declining bloom phases (average of 1.6 mg C L-1, 5.7 mg C L-1, and 1.0 mg C L-1, respectively), the relative ratio of the dominant diatom groups did not change. However, after export, when the diatoms melt out of the ice into the underlying water, diatom biomass dropped by ~73% and the diatom community shifted to one dominated by centric diatoms. I also found that diatom biomass was ~77% lower under high snow cover (>20 cm) compared to low snow cover (<8 cm); however, the ratio of the diatom categories relative to particulate organic carbon (POC) was again unchanged. The diatom biomass was significantly different between the three sampling years (average of 2.4 mg C L-1 in 2011, 1.1 mg C L-1 in 2012, and 5.4 mg C L-1 in 2013, respectively) as was the contribution of all of the dominant genera to POC. I hypothesize the latter to be due to differences in the history of ice sheet formation each year. The temporal variability of these algal communities will influence their availability for pelagic or benthic consumers. Furthermore, in an Arctic that is changing rapidly with earlier sea ice and snowmelt, this time series study will constitute an important baseline for further studies on how the changing Arctic influences the algal community immured in sea ice.
ContributorsKinzler, Kyle (Author) / Neuer, Susanne (Thesis advisor) / Juhl, Andrew (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2014
Description
The occurrence of exogenic, meteoritic materials on the surface of any world presents opportunities to explore a variety of significant problems in the planetary sciences. In the case of Mars, meteorites found on its surface may help to 1) constrain atmospheric conditions during their time of arrival; 2) provide insights into possible variabilities in meteoroid type sampling between Mars and Earth space environments; 3) aid in our understanding of soil, dust, and sedimentary rock chemistry; 4) assist with the calibration of crater-age dating techniques; and 5) provide witness samples for chemical and mechanical weathering processes. The presence of reduced metallic iron in approximately 88 percent of meteorite falls renders the majority of meteorites particularly sensitive to oxidation by H2O interaction. This makes them excellent markers for H2O occurrence. Several large meteorites have been discovered at Gusev Crater and Meridiani Planum by the Mars Exploration Rovers (MERs). Significant morphologic characteristics interpretable as weathering features in the Meridiani suite of iron meteorites include a 1) large pit lined with delicate iron protrusions suggestive of inclusion removal by corrosive interaction; 2) differentially eroded kamacite and taenite lamellae on three of the meteorites, providing relative timing through cross-cutting relationships with deposition of 3) an iron oxide-rich dark coating; and 4) regmaglypted surfaces testifying to regions of minimal surface modification; with other regions in the same meteorites exhibiting 5) large-scale, cavernous weathering. Iron meteorites found by Mini-TES at both Meridiani Planum and Gusev Crater have prompted laboratory experiments designed to explore elements of reflectivity, dust cover, and potential oxide coatings on their surfaces in the thermal infrared using analog samples. Results show that dust thickness on an iron substrate need be only one tenth as great as that on a silicate rock to obscure its infrared signal. In addition, a database of thermal emission spectra for 46 meteorites was prepared to aid in the on-going detection and interpretation of these valuable rocks on Mars using Mini-TES instruments on both MER spacecraft. Applications to the asteroidal sciences are also relevant and intended for this database.
ContributorsAshley, James Warren (Author) / Christensen, Philip R. (Thesis advisor) / Sharp, Thomas G (Committee member) / Shock, Everett L (Committee member) / Hervig, Richard L (Committee member) / Zolotov, Mikhail Y (Committee member) / Arizona State University (Publisher)
Created2011
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
Molybdenum (Mo) is a key trace nutrient for biological assimilation of nitrogen, either as nitrogen gas (N2) or nitrate (NO3-). Although Mo is the most abundant metal in seawater (105 nM), its concentration is low (<5 nM) in most freshwaters today, and it was scarce in the ocean before 600 million years ago. The use of Mo for nitrogen assimilation can be understood in terms of the changing Mo availability through time; for instance, the higher Mo content of eukaryotic vs. prokaryotic nitrate reductase may have stalled proliferation of eukaryotes in low-Mo Proterozoic oceans. Field and laboratory experiments were performed to study Mo requirements for NO3- assimilation and N2 fixation, respectively. Molybdenum-nitrate addition experiments at Castle Lake, California revealed interannual and depth variability in plankton community response, perhaps resulting from differences in species composition and/or ammonium availability. Furthermore, lake sediments were elevated in Mo compared to soils and bedrock in the watershed. Box modeling suggested that the largest source of Mo to the lake was particulate matter from the watershed. Month-long laboratory experiments with heterocystous cyanobacteria (HC) showed that <1 nM Mo led to low N2 fixation rates, while 10 nM Mo was sufficient for optimal rates. At 1500 nM Mo, freshwater HC hyperaccumulated Mo intercellularly, whereas coastal HC did not. These differences in storage capacity were likely due to the presence in freshwater HC of the small molybdate-binding protein, Mop, and its absence in coastal and marine cyanobacterial species. Expression of the mop gene was regulated by Mo availability in the freshwater HC species Nostoc sp. PCC 7120. Under low Mo (<1 nM) conditions, mop gene expression was up-regulated compared to higher Mo (150 and 3000 nM) treatments, but the subunit composition of the Mop protein changed, suggesting that Mop does not bind Mo in the same manner at <1 nM Mo that it can at higher Mo concentrations. These findings support a role for Mop as a Mo storage protein in HC and suggest that freshwater HC control Mo cellular homeostasis at the post-translational level. Mop's widespread distribution in prokaryotes lends support to the theory that it may be an ancient protein inherited from low-Mo Precambrian oceans.
ContributorsGlass, Jennifer (Author) / Anbar, Ariel D (Thesis advisor) / Shock, Everett L (Committee member) / Jones, Anne K (Committee member) / Hartnett, Hilairy E (Committee member) / Elser, James J (Committee member) / Fromme, Petra (Committee member) / Arizona State University (Publisher)
Created2011
Description
The San Andreas Fault (SAF) is the primary structure within a system of faults accommodating motion between the North American and Pacific plates. Physical models of faulting and characterizations of seismic hazard are informed by investigations of paleoseismology, slip distribution, and slip rate. The impact of earthquakes on people is due in large part to social vulnerability. This dissertation contributes an analysis about the relationships between earthquake hazard and social vulnerability in Los Angeles, CA and investigations of paleoseismology and fault scarp array complexity on the central SAF. Analysis of fault scarp array geometry and morphology using 0.5 m digital elevation models along 122 km of the central SAF reveals significant variation in the complexity of SAF structure. Scarp trace complexity is measured by scarp separation, changes in strike, fault trace gaps, and scarp length per SAF kilometer. Geometrical complexity in fault scarp arrays indicates that the central SAF can be grouped into seven segments. Segment boundaries are controlled by interactions with subsidiary faults. Investigation of an offset channel at Parkfield, CA yields a late Holocene slip rate of 26.2 +6.4/- 4.3 mm/yr. This rate is lower than geologic measurements on the Carrizo section of the SAF and rates implied by far-field geodesy. However, it is consistent with historical observations of slip at Parkfield. Paleoseismology at Parkfield indicates that large earthquakes are absent from the stratigraphic record for at least a millennia. Together these observations imply that the amount of plate boundary slip accommodated by the main SAF varies along strike. Contrary to most environmental justice analyses showing that vulnerable populations are spatially-tied to environmental hazards, geospatial analyses relating social vulnerability and earthquake hazard in southern California show that these groups are not disproportionately exposed to the areas of greatest hazard. Instead, park and green space is linked to earthquake hazard through fault zone regulation. In Los Angeles, a parks poor city, the distribution of social vulnerability is strongly tied to a lack of park space. Thus, people with access to financial and political resources strive to live in neighborhoods with parks, even in the face of forewarned risk.
ContributorsToké, Nathan A (Author) / Arrowsmith, J R (Thesis advisor) / Boone, Christopher G (Committee member) / Heimsath, Arjun M (Committee member) / Shock, Everett L (Committee member) / Whipple, Kelin X (Committee member) / Arizona State University (Publisher)
Created2011