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- Genre: Masters Thesis
Description
Microbially induced calcium carbonate precipitation (MICP) is attracting increasing attention as a sustainable means of soil improvement. While there are several possible MICP mechanisms, microbial denitrification has the potential to become one of the preferred methods for MICP because complete denitrification does not produce toxic byproducts, readily occurs under anoxic conditions, and potentially has a greater carbonate yield per mole of organic electron donor than other MICP processes. Denitrification may be preferable to ureolytic hydrolysis, the MICP process explored most extensively to date, as the byproduct of denitrification is benign nitrogen gas, while the chemical pathways involved in hydrolytic ureolysis processes produce undesirable and potentially toxic byproducts such as ammonium (NH4+). This thesis focuses on bacterial denitrification and presents preliminary results of bench-scale laboratory experiments on denitrification as a candidate calcium carbonate precipitation mechanism. The bench-scale bioreactor and column tests, conducted using the facultative anaerobic bacterium Pseudomonas denitrificans, show that calcite can be precipitated from calcium-rich pore water using denitrification. Experiments also explore the potential for reducing environmental impacts and lowering costs associated with denitrification by reducing the total dissolved solids in the reactors and columns, optimizing the chemical matrix, and addressing the loss of free calcium in the form of calcium phosphate precipitate from the pore fluid. The potential for using MICP to sequester radionuclides and metal contaminants that are migrating in groundwater is also investigated. In the sequestration process, divalent cations and radionuclides are incorporated into the calcite structure via substitution, forming low-strontium calcium carbonate minerals that resist dissolution at a level similar to that of calcite. Work by others using the bacterium Sporosarcina pasteurii has suggested that in-situ sequestration of radionuclides and metal contaminants can be achieved through MICP via hydrolytic ureolysis. MICP through bacterial denitrification seems particularly promising as a means for sequestering radionuclides and metal contaminants in anoxic environments due to the anaerobic nature of the process and the ubiquity of denitrifying bacteria in the subsurface.
ContributorsHamdan, Nasser (Author) / Kavazanjian, Edward (Thesis advisor) / Rittmann, Bruce E. (Thesis advisor) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2013
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
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
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
Dissolved organic matter (DOM) is an important part of aquatic foodwebs because it contains carbon, nitrogen, and other elements required by heterotrophic organisms. It has many sources that determine its molecular composition, nutrient content, and biological lability and in turn, influence whether it is retained and processed in the stream reach or exported downstream. I examined the composition of DOM from vascular wetland plants, filamentous algae, and riparian tree leaf litter in Sonoran Desert streams and its decomposition by stream microbes. I used a combination of field observations, in-situ experiments, and a manipulative laboratory incubation to test (1) how dominant primary producers influence DOM chemical composition and ecosystem metabolism at the reach scale and (2) how DOM composition and nitrogen (N) content control microbial decomposition and stream uptake of DOM. I found that differences in streamwater DOM composition between two distinct reaches of Sycamore Creek did not affect in-situ stream respiration and gross primary production rates. Stream sediment microbial respiration rates did not differ significantly when incubated in the laboratory with DOM from wetland plants, algae, and leaf litter, thus all sources were similarly labile. However, whole-stream uptake of DOM increased from leaf to algal to wetland plant leachate. Desert streams have the potential to process DOM from leaf, wetland, and algal sources, though algal and wetland DOM, due to their more labile composition, can be more readily retained and mineralized.
ContributorsKemmitt, Kathrine (Author) / Grimm, Nancy (Thesis advisor) / Hartnett, Hilairy (Committee member) / Throop, Heather (Committee member) / Arizona State University (Publisher)
Created2018
Description
The biological carbon pump in the ocean is initiated by the photosynthetic fixation of atmospheric carbon dioxide into particulate or dissolved organic carbon by phytoplankton. A fraction of this organic matter sinks to depth mainly in the form of microaggregates (5-60 μm) and visible macroaggregates. These aggregates are composed of cells, minerals, and other sources of organic carbon. Exopolymeric substances (EPS) are exudated by heterotrophic bacteria and phytoplankton and may form transparent exopolymeric particles (TEP) that act as a glue-like matrix for marine aggregates. Heterotrophic bacteria have been found to influence the aggregation of phytoplankton and in some cases result in an increase in TEP production, but it is unclear if marine heterotrophic bacteria can produce TEP and how they contribute to aggregation. Pseudoalteromonas carrageenovora, Vibrio thalassae, and Marinobacter adhaerens HP15 are heterotrophic marine bacteria that were found associated with sinking particles in an oligotrophic gyre station in the subtropical North Atlantic. These bacteria were grown in axenic cultures to determine growth, TEP production, and aggregation. They were also inoculated into roller tanks used to simulate open ocean conditions to determine their ability to form macroaggregates. Treatments with added kaolinite clay simulated aeolic dust input from the Sahara. M. adhaerens HP15 had the highest TEP concentration but the lowest cell-normalized TEP production at all growth stages compared to the other bacteria. Additionally, M. adhaerens HP15 also had the lowest microaggregate formation. The cell-normalized TEP production and microaggregate formation was not significantly different between P. carrageenovora and V. thalassae. All bacteria formed visible macroaggregates in roller tanks with clay addition and exhibited high sinking velocities (150-1200 m d-1) that are comparable to those of aggregates formed by large mineral ballasted phytoplankton. Microaggregates in the clay treatments declined during incubation, indicating that they aggregated to form the macroaggregates. The findings from this study show for the first time that heterotrophic bacteria can contribute to aggregation and the export of organic carbon to depth in the ocean.
ContributorsLivar, Britni (Author) / Neuer, Susanne (Thesis advisor) / Hartnett, Hilairy (Committee member) / Cadillo-Quiroz, Hinsby (Committee member) / Arizona State University (Publisher)
Created2022
Description
Soil organic carbon (SOC) is a critical component of the global carbon (C) cycle, accounting for more C than the biotic and atmospheric pools combined. Microbes play an important role in soil C cycling, with abiotic conditions such as soil moisture and temperature governing microbial activity and subsequent soil C processes. Predictions for future climate include warmer temperatures and altered precipitation regimes, suggesting impacts on future soil C cycling. However, it is uncertain how soil microbial communities and subsequent soil organic carbon pools will respond to these changes, particularly in dryland ecosystems. A knowledge gap exists in soil microbial community responses to short- versus long-term precipitation alteration in dryland systems. Assessing soil C cycle processes and microbial community responses under current and altered precipitation patterns will aid in understanding how C pools and cycling might be altered by climate change. This study investigates how soil microbial communities are influenced by established climate regimes and extreme changes in short-term precipitation patterns across a 1000 m elevation gradient in northern Arizona, where precipitation increases with elevation. Precipitation was manipulated (50% addition and 50% exclusion of ambient rainfall) for two summer rainy seasons at five sites across the elevation gradient. In situ and ex situ soil CO2 flux, microbial biomass C, extracellular enzyme activity, and SOC were measured in precipitation treatments in all sites. Soil CO2 flux, microbial biomass C, extracellular enzyme activity, and SOC were highest at the three highest elevation sites compared to the two lowest elevation sites. Within sites, precipitation treatments did not change microbial biomass C, extracellular enzyme activity, and SOC. Soil CO2 flux was greater under precipitation addition treatments than exclusion treatments at both the highest elevation site and second lowest elevation site. Ex situ respiration differed among the precipitation treatments only at the lowest elevation site, where respiration was enhanced in the precipitation addition plots. These results suggest soil C cycling will respond to long-term changes in precipitation, but pools and fluxes of carbon will likely show site-specific sensitivities to short-term precipitation patterns that are also expected with climate change.
ContributorsMonus, Brittney (Author) / Throop, Heather L (Thesis advisor) / Ball, Becky A (Committee member) / Hultine, Kevin R (Committee member) / Munson, Seth M (Committee member) / Arizona State University (Publisher)
Created2019
Description
Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to petroleum generation and to chemoautotrophic microbial communities. There have been numerous studies on the reactivity of organic compounds in water at elevated temperatures, but these studies rarely explore the consequences of inorganic solutes in hydrothermal fluids. The experiments in this thesis explore new reaction pathways of organic compounds mediated by aqueous and solid phase metals, mainly Earth-abundant copper. These experiments show that copper species have the potential to oxidize benzene and toluene, which are typically viewed as unreactive. These pathways add to the growing list of known organic transformations that are possible in natural hydrothermal systems. In addition to the characterization of reactions in natural systems, there has been recent interest in using hydrothermal conditions to facilitate organic transformations that would be useful in an applied, industrial or synthetic setting. This thesis identifies two sets of conditions that may serve as alternatives to commonplace industrial processes. The first process is the oxidation of benzene with copper to form phenol and chlorobenzene. The second is the copper mediated dehalogenation of aryl halides. Both of these processes apply the concepts of geomimicry by carrying out organic reactions under Earth-like conditions. Only water and copper are needed to implement these processes and there is no need for exotic catalysts or toxic reagents.
ContributorsLoescher, Grant (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2020
Description
Dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) are crucial nutrients for autotrophic and heterotrophic microbial life, respectively, in hydrothermal systems. Biogeochemical processes that control amounts of DIC and DOC in Yellowstone hot springs can be investigated by measuring carbon abundances and respective isotopic values. A decade and a half of field work in 10 regions within Yellowstone National Park and subsequent geochemical lab analyses reveal that sulfate-dominant acidic regions have high DOC (Up to 57 ppm C) and lower DIC (up to 50 ppm C) compared to neutral-chloride regions with low DOC (< 2 ppm C) and higher DIC (up to 100 ppm C). Abundances and isotopic data suggest that sedimentary rock erosion by acidic hydrothermal fluids, fresh snow-derived meteoric water, and exogenous carbon input allowed by local topography may affect DOC levels. Evaluating the isotopic compositions of DIC and DOC in hydrothermal fluids gives insight on the geology and microbial life in the subsurface between different regions. DIC δ13C values range from -4‰ to +5‰ at pH 5-9 and from -10‰ to +3‰ at pH 2-5 with several springs lower than -10‰. DOC δ13C values parkwide range from -10‰ to -30‰. Within this range, neutral-chloride regions in the Lower Geyser Basin have lighter isotopes than sulfate-dominant acidic regions. In hot springs with elevated levels of DOC, the range only varies between -20‰ and -26‰ which may be caused by local exogenous organic matter runoff. Combining other geochemical measurements, such as differences in chloride and sulfate concentrations, demonstrates that some regions contain mixtures of multiple fluids moving through the complex hydrological system in the subsurface. The mixing of these fluids may account for increased levels of DOC in meteoric sulfate-dominant acidic regions. Ultimately, the foundational values of dissolved carbon and their isotopic composition is provided in a parkwide study, so results can be combined with future studies that apply different sequencing analyses to understand specific biogeochemical cycling and microbial communities that occur in individual hot springs.
ContributorsBarnes, Tanner (Author) / Shock, Everett (Thesis advisor) / Meyer-Dombard, D'Arcy (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2023