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Browsing by Author "Druschel, Gregory K."
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Item A Combined Molecular and Isotopic Study of Sulfur Bacteria in Meromictic Lakes of the Pacific Northwest(2023-12) Harris, James H., IV; Gilhooly, William P., III; Druschel, Gregory K.; Bird, Broxton W.The isotope effects that result from the activity of modern sulfur metabolizing bacteria serve as analogs to interpreting the sulfur isotope values preserved in the geologic record. This biogenic signal is vital to reconstructing the history of Earth’s ancient oceans and atmosphere. However, the isotope compositions imprinted by these bacteria were influenced by multiple factors that must be considered when using these values to make interpretations about environmental change. These factors include: (1) sulfate availability, (2) the rapid and quantitative reoxidation of sulfide (i.e., cryptic sulfur cycling), (3) the initial oxygen isotope compositions of sulfate and water, and (4) the taxonomic structure of sulfur-metabolizing bacterial communities. To address these questions, this project studied four permanently stratified, anoxic and sulfidic (euxinic), lakes in southern British Columbia, Canada, and northern Washington, USA, that have a wide range of sulfate concentrations, from 0.15 – 120 mM. This project resulted in six key findings – (1) the measurement of large Δ34SSO4-H2S values at micromolar sulfate concentrations, (2) the consistent occurrence of δ18OSO4 minima at the chemocline that may be imparted during cryptic sulfur cycling, (3) that subsequent δ18OSO4 enrichments consistently preceded sulfide accumulation and δ34SSO4 enrichment in the suboxic zone of the water column, (4) that initial epilimnion Δ18OSO4-H2O values placed constraints on the maximum extent of δ18OSO4 evolution that occurred beneath the chemocline, (5) that observable changes in the metabolic composition of sulfur bacterial communities accompanied key inflections in the sulfur and oxygen isotope profiles of sulfate and sulfide within the water column, and (6) that, despite large overall differences in community structure, Δ34SSO4-H2S and Δ18OSO4-H2O values ultimately reached similar magnitudes in each lake.Item Analysing Urban Air Pollution Using Low-Cost Methods and Community Science(2022-12) Heintzelman, Asrah; Filippelli, Gabriel; Moreno-Madriñan, Max J.; Wilson, Jeffrey S.; Wang, Lixin; Druschel, Gregory K.Rise in air pollution resulting in negative health externalities for humans has created an urgent need for cities and communities to monitor it regularly. At present we have insufficient ground passive and active monitoring networks in place which presents a huge challenge. Satellite imagery has been used extensively for such analysis, but its resolution and methodology present other challenges in estimating pollution burden. The objective of this study was to propose three low-cost methods to fill in the gaps that exist currently. First, EPA grade sensors were used in 11 cities across the U.S. to examine NO2. This is a simplistic way to assess the burden of air pollution in a region. However, this technique cannot be applied to fine scale analysis, which resulted in the next two components of this research study. Second, a citizen science network was established on the east side of Indianapolis, IN who hosted 32 Ogawa passive sensors to examine NO2 and O3 at a finer scale. These low-cost passive sensors, not requiring power, and very little maintenance, have historically tracked very closely with Federal Reference Monitors. Third, a low-cost PurpleAir PA-II-SD active sensors measuring PM2.5 were housed with the citizen scientists identified above. This data was uploaded via Wi-Fi and available via a crowd sourced site established by PurpleAir. These data sets were analyzed to examine the burden of air pollution. The second and third research studies enabled granular analyses utilizing citizen science, tree canopy data, and traffic data, thus accommodating some of the present limitations. Advancement in low-cost sensor technology, along with ease of use and maintenance, presents an opportunity for not just communities, but cities to take charge of some of these analyses to help them examine health equity impacts on their citizens because of air pollution.Item Author Correction: Unraveling iron oxides as abiotic catalysts of organic phosphorus recycling in soil and sediment matrices(Springer Nature, 2024-08-30) Basinski, Jade J.; Bone, Sharon E.; Klein, Annaleise R.; Thongsomboon, Wiriya; Mitchell, Valerie; Shukle, John T.; Druschel, Gregory K.; Thompson, Aaron; Aristilde, Ludmilla; Earth and Environmental Sciences, School of ScienceCorrection to: Nature Communications 10.1038/s41467-024-47931-z, published online 18 July 2024 The original version of this Article contained an error in the Abstract, which was previously incorrectly given as ‘ten-fold’. The correct version states ‘twenty-fold’ in place of ‘ten-fold’. This has been corrected in both the PDF and HTML versions of the Article.Item Bioenergetic characterization of a shallow-sea hydrothermal vent system: Milos Island, Greece(Public Library of Science, 2020-06-05) Lu, Guang-Sin; LaRowe, Douglas E.; Fike, David A.; Druschel, Gregory K.; Gilhooly, William P., III; Price, Roy E.; Amend, Jan P.; Earth and Environmental Sciences, School of ScienceShallow-sea hydrothermal systems, like their deep-sea and terrestrial counterparts, can serve as relatively accessible portals into the microbial ecology of subsurface environments. In this study, we determined the chemical composition of 47 sediment porewater samples along a transect from a diffuse shallow-sea hydrothermal vent to a non-thermal background area in Paleochori Bay, Milos Island, Greece. These geochemical data were combined with thermodynamic calculations to quantify potential sources of energy that may support in situ chemolithotrophy. The Gibbs energies (ΔGr) of 730 redox reactions involving 23 inorganic H-, O-, C-, N-, S-, Fe-, Mn-, and As-bearing compounds were calculated. Of these reactions, 379 were exergonic at one or more sampling locations. The greatest energy yields were from anaerobic CO oxidation with NO2- (-136 to -162 kJ/mol e-), followed by reactions in which the electron acceptor/donor pairs were O2/CO, NO3-/CO, and NO2-/H2S. When expressed as energy densities (where the concentration of the limiting reactant is taken into account), a different set of redox reactions are the most exergonic: in sediments affected by hydrothermal input, sulfide oxidation with a range of electron acceptors or nitrite reduction with different electron donors provide 85~245 J per kg of sediment, whereas in sediments less affected or unaffected by hydrothermal input, various S0 oxidation reactions and aerobic respiration reactions with several different electron donors are most energy-yielding (80~95 J per kg of sediment). A model that considers seawater mixing with hydrothermal fluids revealed that there is up to ~50 times more energy available for microorganisms that can use S0 or H2S as electron donors and NO2- or O2 as electron acceptors compared to other reactions. In addition to revealing likely metabolic pathways in the near-surface and subsurface mixing zones, thermodynamic calculations like these can help guide novel microbial cultivation efforts to isolate new species.Item Detection and Quantification of Taste and Odor Producing Bacteria in Eagle Creek Reservoir(2019-08) Koltsidou, Ioanna; Picard, Christine J.; Druschel, Gregory K.; Anderson, Gregory G.The accelerated growth of algal blooms in water bodies has caused the increased occurrence of taste and odor (T&O) episodes worldwide. Even though T&O compounds have not been associated with adverse health effects, their presence can have extensive socio-economic impacts in contaminated waters. Eagle Creek Reservoir, a eutrophic water body, which supplies about 80% of Indianapolis drinking water, experiences frequent and sometimes severe odorous outbreaks. The terpenoid bacterial metabolites, 2-methylisoborneol (2-MIB) and geosmin, have been identified as the main compounds contributing to those T&O problems, which occur seasonally when the reservoir receives most of its water and nutrient loads from discharge events. In this study, ECR’s microbial community composition was assessed by a 16S next generation sequencing approach, confirming the presence of the major bacterial phyla of Cyanobacteria, Proteobacteria, Actinobacteria and Bacteroidetes, which are commonly found in freshwater environments. The relative abundance of Cyanobacteria, which are regarded as the main T&O producers in freshwater, followed the fluctuation of 2-MIB and geosmin concentrations closely. Mapping sequence analysis of a metagenomic dataset, successfully recovered the genes responsible for the synthesis of geosmin and 2-MIB, demonstrating the microbial ability for odorous compound production in ECR. Quantification of the geoA and MIBS genes in Cyanobacteria was achieved by the development and application of qPCR assays on water samples collected from the reservoir. A statistically significant positive correlation was found between MIBS gene quantity and MIB concentration for all sampling locations, implying that this assay could potentially be used as a tool for the early prediction of upcoming T&O episodes. The geoA gene detection assay, did not correlate well with geosmin concentrations, suggesting that even though the gene might be present, this does not necessarily mean that it is metabolically active.Item Efficacy of Low-Cost Sensor Networks at Detecting Fine-Scale Variations in Particulate Matter in Urban Environments(MDPI, 2023-01) Heintzelman, Asrah; Filippelli, Gabriel M.; Moreno-Madriñan, Max J.; Wilson, Jeffrey S.; Wang, Lixin; Druschel, Gregory K.; Lulla, Vijay O.; Geography, School of Liberal ArtsThe negative health impacts of air pollution are well documented. Not as well-documented, however, is how particulate matter varies at the hyper-local scale, and the role that proximal sources play in influencing neighborhood-scale patterns. We examined PM2.5 variations in one airshed within Indianapolis (Indianapolis, IN, USA) by utilizing data from 25 active PurpleAir (PA) sensors involving citizen scientists who hosted all but one unit (the control), as well as one EPA monitor. PA sensors report live measurements of PM2.5 on a crowd sourced map. After calibrating the data utilizing relative humidity and testing it against a mobile air-quality unit and an EPA monitor, we analyzed PM2.5 with meteorological data, tree canopy coverage, land use, and various census variables. Greater proximal tree canopy coverage was related to lower PM2.5 concentrations, which translates to greater health benefits. A 1% increase in tree canopy at the census tract level, a boundary delineated by the US Census Bureau, results in a ~0.12 µg/m3 decrease in PM2.5, and a 1% increase in “heavy industry” results in a 0.07 µg/m3 increase in PM2.5 concentrations. Although the overall results from these 25 sites are within the annual ranges established by the EPA, they reveal substantial variations that reinforce the value of hyper-local sensing technologies as a powerful surveillance tool.Item Electrochemical triggering of the Chardonnay wine metabolome(Elsevier, 2019-07) Roullier-Gall, Chloé; Kanawati, Basem; Hemmler, Daniel; Druschel, Gregory K.; Gougeon, Régis D.; Schmitt-Kopplin, Philippe; Earth Sciences, School of ScienceOxidation of wine upon bottle ageing is a crucial matter of concern for the qualitative long-term storage of white wines. However, understanding the various molecular mechanisms potentially involved, which can impact the wine composition, requires that top-down analytical strategies are implemented. Here, we report the analysis of bottle aged Chardonnay wines made from the same must, but differing by the amount of SO2 initially added to the must at pressing (0 and 8 g·h L−1). Metabolomics fingerprints obtained from electrochemical simulation of oxidative reactions were obtained by coupling of either on-line or off-line electrochemical oxidation to FT-ICR-MS detection. We reveal that, whatever the electrochemical DC voltage is, wines with initial SO2 addition displayed molecular fingerprints, which remained more similar to the non-oxidized wine without initial SO2 addition. We further show that a diversity of sulfur-containing compounds appeared to be the most sensitive to oxidation, whereas nitrogen-containing compounds were mostly formed.Item Elemental sulfur coarsening kinetics(Springer (Biomed Central Ltd.), 2014) Garcia, Angel A.; Druschel, Gregory K.; Department of Earth Sciences, School of ScienceBACKGROUND: Elemental sulfur exists is a variety of forms in natural systems, from dissolved forms (noted as S8(diss) or in water as S8(aq)) to bulk elemental sulfur (most stable as α-S8). Elemental sulfur can form via several biotic and abiotic processes, many beginning with small sulfur oxide or polysulfidic sulfur molecules that coarsen into S8 rings that then coalesce into larger forms: [Formula: see text] Formation of elemental sulfur can be possible via two primary techniques to create an emulsion of liquid sulfur in water called sulfur sols that approximate some mechanisms of possible elemental sulfur formation in natural systems. These techniques produce hydrophobic (S8(Weimarn)) and hydrophilic (S8(polysulfide)) sols that exist as nanoparticle and colloidal suspensions. These sols begin as small sulfur oxide or polysulfidic sulfur molecules, or dissolved S8(aq) forms, but quickly become nanoparticulate and coarsen into micron sized particles via a combination of classical nucleation, aggregation processes, and/or Ostwald ripening. RESULTS: We conducted a series of experiments to study the rate of elemental sulfur particle coarsening using dynamic light scattering (DLS) analysis under different physical and chemical conditions. Rates of nucleation and initial coarsening occur over seconds to minutes at rates too fast to measure by DLS, with subsequent coarsening of S8(nano) and S8(sol) being strongly temperature dependent, with rates up to 20 times faster at 75°C compared to 20°C. The addition of surfactants (utilizing ionic and nonionic surfactants as model compounds) results in a significant reduction of coarsening rates, in addition to known effects of these molecules on elemental sulfur solubility. DLS and cryo-SEM results suggest coarsening is largely a product of ripening processes rather than particle aggregation, especially at higher temperatures. Fitting of the coarsening rate data to established models for Ostwald ripening additionally support this as a primary mechanism of coarsening. CONCLUSIONS: Elemental sulfur sols coarsen rapidly at elevated temperatures and experience significant effects on both solubility and particle coarsening kinetics due to interaction with surfactants. Growth of elemental sulfur nanoparticles and sols is largely governed by Ostwald ripening processes.Item Evaporating Planetesimals: A Modelling Approach(2021-10) Hogan, Arielle Ann; Macris, Catherine A.; Barth, Andrew P.; Druschel, Gregory K.This thesis is a comprehensive investigation into the mechanics of evaporation experienced by planetesimals during accretion, a planet-building process. The evaporation events that these rocky bodies experience govern their chemical evolution, impacting the chemistry of the final body – a planet. Studying these planet-building processes is notoriously difficult (e.g., Sossi et al., 2019). There are still many unknowns surrounding what controls the degree of evaporation these bodies experience, and the resulting chemical signatures. The current study was designed to attempt to define some important parameters that govern silicate melt evaporation. Here, we isolate and evaluate the effects of (1) pressure, (2) oxygen fugacity and (3) the activity coefficient of MgO on evaporating planetesimals through a series of computational models. The model introduced in this study, the ƒO2 Modified KNFCMAS Model, uses a robust stepwise routine for calculating evaporative fluxes from a shrinking sphere. The modelling results are then compared to data from partial evaporation experiments of synthetic chondrite spheres to demonstrate the validity of this model, and to expose unknowns about the physicochemical conditions of high temperature silicate melts experiencing evaporation (in this case, the effective pressure, and the activity coefficient of MgO). Major element-oxide and isotope data from the models yielded two main conclusions concerning planetesimals: (1) the rate of evaporation is controlled by pressure and oxygen fugacity and (2) the chemical composition of the residual melt is controlled by oxygen fugacity and the activity coefficient of MgO. Results from computational modelling and evaporation experiments were used to determine an approximation for the activity coefficient of MgO in a simplified chondritic composition, as well as the effective pressure experienced by the evaporating spheres during the partial evaporation experiments. This study outlines the controls on planetesimal chemistry during evaporation and provides a more accessible means of studying these complex processes.Item Geochemistry and speciation of Fe(II) and Fe(III) in natural geothermal water, Iceland(Elsevier, 2017-12) Kaasalainen, Hanna; Stefánsson, Andri; Druschel, Gregory K.; Earth Science, School of ScienceThe geochemistry of Fe(II) and Fe(III) was studied in natural geothermal waters in Iceland. Samples of surface and spring water and sub-boiling geothermal well water were collected and analyzed for Fe(II), Fe(III) and Fetotal concentrations. The samples had discharge temperatures in the range 27–99 °C, pH between 2.46 and 9.77 and total dissolved solids 155–1090 mg/L. The concentrations of Fe(II) and Fe(III) were determined in the <0.2 μm filtered and acidified fraction using a field-deployed ion chromatography spectrophotometry (IC-Vis) method within minutes to a few hours of sampling in order to prevent post-sampling changes. The concentrations of Fe(II) and Fe(III) were <0.1–130 μmoL/L and <0.2–42 μmoL/L, respectively. In-situ dialysis coupled with Fe(II) and Fe(III) determinations suggest that in some cases a significant fraction of Fe passing the standard <0.2 μm filtration method may be present in colloidal/particulate form. Therefore, such filter size may not truly represent the dissolved fraction of Fe but also nano-sized particles. The Fe(II) and Fe(III) speciation and Fetotal concentrations are largely influenced by the water pH, which in turn reflects the water type formed through various processes. In water having pH of ∼7–9, the total Fe concentrations were <2 μmoL/L with Fe(III) predominating. With decreasing pH, the total Fe concentrations increased with Fe(II) becoming increasingly important and predominating at pH < 3. In particular in waters having pH ∼6 and above, iron redox equilibrium may be approached with Fe(II) and Fe(III) possibly being controlled by equilibrium with respect to Fe minerals. In many acid waters, the Fe(II) and Fe(III) distribution may not have reached equilibrium and be controlled by the source(s), reaction kinetics or microbial reactions.
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