Matching Items (9)
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- All Subjects: Biogeochemistry
- All Subjects: carbon cycling
- Creators: Hartnett, Hilairy
- Member of: Theses and Dissertations
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
Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients, such as iron, copper, and molybdenum. This work investigated the effects of BSC activity on soil solution concentrations of bioessential elements and examined the microbial production of organic chelators, called siderophores. I found that aluminum, vanadium, copper, zinc, and molybdenum were solubilized in the action of crusts, while nickel, zinc, arsenic, and zirconium were immobilized by crust activity. Potassium and manganese displayed behavior consistent with biological removal and mobilization, whereas phosphorus and iron solubility were dominated by abiotic processes. The addition of bioavailable nitrogen altered the effects of BSCs on soil element mobilization. In addition, I found that the biogeochemical activites of BSCs were limited by molybdenum, a fact that likely contributes to co-limitation by nitrogen. I confirmed the presence of siderophore producing microbes in BSCs. Siderophores are low-molecular weight organic compounds that are released by bacteria to increase element solubility and facilitate element uptake; siderophore production is likely the mechanism by which BSCs affect the patterns I observed in soil solution element concentrations. Siderophore producers were distributed across a range of bacterial groups and ecological niches within crusts, suggesting that siderophore production influences the availability of a variety of elements for use in many physiological processes. Four putative siderophore compounds were identified using electrospray ionization mass spectrometry; further attempts to characterize the compounds confirmed two true siderophores. Taken together, the results of my work provide information about micronutrient cycling within crusts that can be applied to BSC conservation and management. Fertilization with certain elements, particularly molybdenum, may prove to be a useful technique to promote BSC growth and development which would help prevent arid land degradation. Furthermore, understanding the effects of BSCs on soil element mobility could be used to develop useful biomarkers for the study of the existence and distribution of crust-like communities on ancient Earth, and perhaps other places, like Mars.
ContributorsNoonan, Kathryn Alexander (Author) / Hartnett, Hilairy (Thesis advisor) / Anbar, Ariel (Committee member) / Garcia-Pichel, Ferran (Committee member) / Shock, Everett (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2012
Description
Lipids perform functions essential to life and have a variety of structures that are influenced by the organisms and environments that produced them. Lipids tend to resist degradation after cell death, leading to their widespread use as biomarkers in geobiology, though their interpretation is often tricky. Many lipid structures are shared among organisms and function in many geochemical conditions and extremes. I argue it is useful to interpret lipid distributions as a balance of functional necessity and energy cost. This work utilizes a quantitative thermodynamic framework for interpreting energetically driven adaptation in lipids.
Yellowstone National Park is a prime location to study biological adaptations to a wide range of temperatures and geochemical conditions. Lipids were extracted and quantified from thermophilic microbial communities sampled along the temperature (29-91°C) and chemical gradients of four alkaline Yellowstone hot springs. I observed that decreased alkyl chain carbon content, increased degree of unsaturation, and a shift from ether to ester linkage caused a downstream increase in the average oxidation state of carbon (ZC) I hypothesized these adaptations were selected because they represent cost-effective solutions to providing thermostable membranes.
This hypothesis was explored by assessing the relative energetic favorability of autotrophic reactions to form alkyl chains from known concentrations of dissolved inorganic species at elevated temperatures. I found that the oxidation-reduction potential (Eh) predicted to favor formation of sample-representative alkyl chains had a strong positive correlation with Eh calculated from hot spring water chemistry (R2 = 0.72 for the O2/H2O redox couple). A separate thermodynamic analysis of bacteriohopanepolyol lipids found that predicted equilibrium abundances of observed polar headgroup distributions were also highly correlated with Eh of the surrounding water (R2= 0.84). These results represent the first quantitative thermodynamic assessment of microbial lipid adaptation in natural systems and suggest that observed lipid distributions represent energetically cost-effective assemblages along temperature and chemical gradients.
Yellowstone National Park is a prime location to study biological adaptations to a wide range of temperatures and geochemical conditions. Lipids were extracted and quantified from thermophilic microbial communities sampled along the temperature (29-91°C) and chemical gradients of four alkaline Yellowstone hot springs. I observed that decreased alkyl chain carbon content, increased degree of unsaturation, and a shift from ether to ester linkage caused a downstream increase in the average oxidation state of carbon (ZC) I hypothesized these adaptations were selected because they represent cost-effective solutions to providing thermostable membranes.
This hypothesis was explored by assessing the relative energetic favorability of autotrophic reactions to form alkyl chains from known concentrations of dissolved inorganic species at elevated temperatures. I found that the oxidation-reduction potential (Eh) predicted to favor formation of sample-representative alkyl chains had a strong positive correlation with Eh calculated from hot spring water chemistry (R2 = 0.72 for the O2/H2O redox couple). A separate thermodynamic analysis of bacteriohopanepolyol lipids found that predicted equilibrium abundances of observed polar headgroup distributions were also highly correlated with Eh of the surrounding water (R2= 0.84). These results represent the first quantitative thermodynamic assessment of microbial lipid adaptation in natural systems and suggest that observed lipid distributions represent energetically cost-effective assemblages along temperature and chemical gradients.
ContributorsBoyer, Grayson Maxwell (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Herckes, Pierre (Committee member) / Arizona State University (Publisher)
Created2018
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
Many acidic hot springs in Yellowstone National Park support microbial iron oxidation, reduction, or microbial iron redox cycling (MIRC), as determined by microcosm rate experiments. Microbial dissimilatory iron reduction (DIR) was detected in numerous systems with a pH < 4. Rates of DIR are influenced by the availability of ferric minerals and organic carbon. Microbial iron oxidation (MIO) was detected from pH 2 – 5.5. In systems with abundant Fe (II), dissolved oxygen controls the presence of MIO. Rates generally increase with increased Fe(II) concentrations, but rate constants are not significantly altered by additions of Fe(II). MIRC was detected in systems with abundant ferric mineral deposition.
The rates of microbial and abiological iron oxidation were determined in a variety of cold (T= 9-12°C), circumneutral (pH = 5.5-9) environments in the Swiss Alps. Rates of MIO were measured in systems up to a pH of 7.4; only abiotic processes were detected at higher pH values. Iron oxidizing bacteria (FeOB) were responsible for 39-89% of the net oxidation rate at locations where biological iron oxidation was detected. Members of putative iron oxidizing genera, especially Gallionella, are abundant in systems where MIO was measured. Speciation calculations reveal that ferrous iron typically exists as FeCO30, FeHCO3+, FeSO40 or Fe2+ in these systems. The presence of ferrous (bi)carbonate species appear to increase abiotic iron oxidation rates relative to locations without significant concentrations. This approach, integrating geochemistry, rates, and community composition, reveals biogeochemical conditions that permit MIO, and locations where the abiotic rate is too fast for the biotic process to compete.
For a reaction to provide habitability for microbes in a given environment, it must energy yield and this energy must dissipate slowly enough to remain bioavailable. Thermodynamic boundaries exist at conditions where reactions do not yield energy, and can be quantified by calculations of chemical energy. Likewise, kinetic boundaries exist at conditions where the abiotic reaction rate is so fast that reactants are not bioavailable; this boundary can be quantified by measurements biological and abiological rates. The first habitability maps were drawn, using iron oxidation as an example, by quantifying these boundaries in geochemical space.
The rates of microbial and abiological iron oxidation were determined in a variety of cold (T= 9-12°C), circumneutral (pH = 5.5-9) environments in the Swiss Alps. Rates of MIO were measured in systems up to a pH of 7.4; only abiotic processes were detected at higher pH values. Iron oxidizing bacteria (FeOB) were responsible for 39-89% of the net oxidation rate at locations where biological iron oxidation was detected. Members of putative iron oxidizing genera, especially Gallionella, are abundant in systems where MIO was measured. Speciation calculations reveal that ferrous iron typically exists as FeCO30, FeHCO3+, FeSO40 or Fe2+ in these systems. The presence of ferrous (bi)carbonate species appear to increase abiotic iron oxidation rates relative to locations without significant concentrations. This approach, integrating geochemistry, rates, and community composition, reveals biogeochemical conditions that permit MIO, and locations where the abiotic rate is too fast for the biotic process to compete.
For a reaction to provide habitability for microbes in a given environment, it must energy yield and this energy must dissipate slowly enough to remain bioavailable. Thermodynamic boundaries exist at conditions where reactions do not yield energy, and can be quantified by calculations of chemical energy. Likewise, kinetic boundaries exist at conditions where the abiotic reaction rate is so fast that reactants are not bioavailable; this boundary can be quantified by measurements biological and abiological rates. The first habitability maps were drawn, using iron oxidation as an example, by quantifying these boundaries in geochemical space.
ContributorsSt Clair, Brian (Author) / Shock, Everett L (Thesis advisor) / Anbar, Ariel (Committee member) / Garcia-Pichel, Ferran (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2017
Description
One goal of geobiochemistry is to follow geochemical energy supplies from the external environment to the inside of microbial cells. This can be accomplished by combining thermodynamic calculations of energy supplies from geochemical processes and energy demands for biochemical processes. Progress towards this goal is summarized here. A critique of all thermodynamic data for biochemical compounds involved in the citric acid cycle (CAC) and the formulation of metabolite properties allows predictions of the energy involved in each step of the cycle as well as the full forward and reverse cycles over wide ranges of temperature and pressure. These results allow evaluation of energy demands at the center of many microbial metabolic systems. Field work, sampling, and lab analyses from two low-temperature systems, a serpentinizing system, and a subglacial setting, provide the data used in these thermodynamic analyses of energy supplies. An extensive literature summary of microbial and molecular data from serpentinizing systems found is used to guide the evaluation and ranking of energy supplies used by chemolithoautotrophic microbes. These results constrain models of the distribution of microbial metabolisms throughout the low-temperature serpentinization systems in the Samail ophiolite in Oman (including locales of primary and subsequent alteration processes). Data collected from Robertson Glacier in Alberta, Canada, together with literature data from Lake Vida in Antarctica and bottom seawater, allowed thermodynamic analyses of low-temperature energy supplies in a glacial system. Results for 1460 inorganic redox reactions are used to fully inventory the geochemical energy sources that support the globally extensive cold biosphere.
ContributorsCanovas, Peter Anthony (Author) / Shock, Everett (Thesis advisor) / Hartnett, Hilairy (Committee member) / Sharp, Thomas (Committee member) / Tyburczy, James (Committee member) / Heimsath, Arjun (Committee member) / Arizona State University (Publisher)
Created2016
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
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
Iron Cycling May Lower Methane Fluxes at an Impounded Marsh: Evidence from the Herring River Estuary
Description
Wetlands produce approximately one third of total global methane emissions and sequester significant amounts of CO2. Salt marshes make up 5% of total wetland area, and therefore are key factors affecting global methane and CO2 emissions. Many marshes are anthropogenically managed either by diking, draining, impoundment, or otherwise restricting tidal exchange. This causes marsh freshening, increases methane emissions, and releases sequestered carbon, all of which can lead to a warming effect on the climate by the greenhouse effect. We studied the formerly impounded Old County salt marsh, found in the Herring River Estuary of Wellfleet, Massachusetts, USA. The USGS Woods Hole Coastal and Marine Science Center installed two eddy covariance flux towers in the Herring River Estuary. These showed that Old County had low methane fluxes (17 nmol/m2/s) compared to another site in the same estuary (112 nmol/m2/s). The question became; why did Old County experience lower methane emissions? We then did a focused study on the Old County location to investigate. We sampled various biogeochemical parameters including pH, salinity, ORP, dissolved Fe, sulfate, chloride, CH4, DOC, and DIC from pore water samples taken June 2022. We also measured extractable iron from a 2015 archived sediment core at Old County. Specifically, we explored the role of Fe in reducing methane through Fe coupled anaerobic oxidation of methane (Fe-AOM). The porewater depth profiles ranged from 10cm to 242 cm in depth and showed Old County as acidic (pH of 3-6.5), mostly fresh, anoxic, highly reducing, and high in dissolved organic carbon (DOC; 2,000-10,000 μM). I divided the depth profiles into two distinct zones, one above 50 cm and one below 50 cm. Overall, Fe-AOM was likely to occur below 50 cm because dissolved Fe increased as CH4 decreased, which is the expected pattern for Fe-AOM. Also, because the ratio of the calculated methane flux (-0.552 nmol m-2 s-1) to the dissolved Fe (0.072 nmol m-2 s-1) was 7.6, which closely matched the 1 to 8 stoichiometry of the Fe-AOM reactions.
ContributorsEinecker, Rachel (Author) / Hartnett, Hilairy (Thesis director) / Anbar, Ariel (Committee member) / Eagle, Meagan (Committee member) / Barrett, The Honors College (Contributor) / School of Molecular Sciences (Contributor)
Created2023-12