Gregory K. Druschel

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https://hdl.handle.net/1805/43173

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Unraveling iron oxides as abiotic catalysts of organic phosphorus recycling in soil and sediment matrices
(Springer Nature, 2024-07-18) 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 Science
In biogeochemical phosphorus cycling, iron oxide minerals are acknowledged as strong adsorbents of inorganic and organic phosphorus. Dephosphorylation of organic phosphorus is attributed only to biological processes, but iron oxides could also catalyze this reaction. Evidence of this abiotic catalysis has relied on monitoring products in solution, thereby ignoring iron oxides as both catalysts and adsorbents. Here we apply high-resolution mass spectrometry and X-ray absorption spectroscopy to characterize dissolved and particulate phosphorus species, respectively. In soil and sediment samples reacted with ribonucleotides, we uncover the abiotic production of particulate inorganic phosphate associated specifically with iron oxides. Reactions of various organic phosphorus compounds with the different minerals identified in the environmental samples reveal up to ten-fold greater catalytic reactivities with iron oxides than with silicate and aluminosilicate minerals. Importantly, accounting for inorganic phosphate both in solution and mineral-bound, the dephosphorylarion rates of iron oxides were within reported enzymatic rates in soils. Our findings thus imply a missing abiotic axiom for organic phosphorus mineralization in phosphorus cycling.
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 Science
Shallow-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.
The mobility of phosphorus, iron, and manganese through the sediment–water continuum of a shallow eutrophic freshwater lake under stratified and mixed water-column conditions
(Springer, 2016) Giles, Courtney D.; Isles, Peter D. F.; Manley, Tom; Xu, Yaoyang; Druschel, Gregory K.; Schroth, Andrew W.; Earth and Environmental Sciences, School of Science
The management of external nutrient inputs to eutrophic systems can be confounded due to a persistent pool of phosphorus (P) in lake sediments. The behaviors of P and trace metals depend largely on the reductive dissolution of amorphous iron (Fe) and manganese (Mn) (oxy)hydroxides in sediments; however, a holistic understanding of these dynamics in relation to the broader ecological and hydrodynamic conditions of the system remains elusive. We used a high-frequency monitoring approach to develop a comprehensive conceptual model of P, Mn, and Fe dynamics across the sediment water continuum of a shallow bay in Lake Champlain (Missisquoi Bay, USA). The greatest release of sediment P, Mn, and Fe occurred under stable hydrodynamic conditions, particularly during the onset of the cyanobacterial bloom and was associated with low available P and the accumulation of soluble Mn and Fe above the sediment–water interface (SWI). During the warmest part of the season, bloom severity and sediment P release was partially regulated by hydrodynamic drivers, which changed on hourly time scales to affect redox conditions at the SWI and bottom water concentrations of soluble P, Mn, and Fe. A geochemically distinct increase in soluble P and Fe concentrations, but not Mn, marked the influence of riverine inputs during a late season storm disturbance. Despite continued depletion of the reactive sediment P and metals pool into the bloom period, declining temperatures and a well-mixed water column resulted in bloom senescence and the return of P, Mn, and Fe to surface sediments. The closed cycling of P and metals in Missisquoi Bay poses a significant challenge for the long-term removal of P from this system. Multiple time-scale measures of physical and biogeochemical changes provide a basis for understanding P and trace metals behavior across sediments and the water column, which shape seasonally variable cyanobacterial blooms in shallow eutrophic systems.
Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs
(Springer Nature, 2014-05-28) Kamyshny, Alexey, Jr.; Druschel, Gregory; Mansaray, Zahra F.; Farquhar, James; Earth and Environmental Sciences, School of Science
Background: The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Results: Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 μmol L(-1)) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ(34)S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ(34)S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope ((32)S, (33)S, (34)S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆(33)S among species and between pools are observed. Conclusions: The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in ∆(33)S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.
Involvement of Intermediate Sulfur Species in Biological Reduction of Elemental Sulfur under Acidic, Hydrothermal Conditions
(American Society for Microbiology, 2013) Boyd, Eric S.; Druschel, Gregory K.; Earth and Environmental Sciences, School of Science
The thermoacidophile and obligate elemental sulfur (S(8)(0))-reducing anaerobe Acidilobus sulfurireducens 18D70 does not associate with bulk solid-phase sulfur during S(8)(0)-dependent batch culture growth. Cyclic voltammetry indicated the production of hydrogen sulfide (H(2)S) as well as polysulfides after 1 day of batch growth of the organism at pH 3.0 and 81°C. The production of polysulfide is likely due to the abiotic reaction between S(8)(0) and the biologically produced H(2)S, as evinced by a rapid cessation of polysulfide formation when the growth temperature was decreased, inhibiting the biological production of sulfide. After an additional 5 days of growth, nanoparticulate S(8)(0) was detected in the cultivation medium, a result of the hydrolysis of polysulfides in acidic medium. To examine whether soluble polysulfides and/or nanoparticulate S(8)(0) can serve as terminal electron acceptors (TEA) supporting the growth of A. sulfurireducens, total sulfide concentration and cell density were monitored in batch cultures with S(8)(0) provided as a solid phase in the medium or with S(8)(0) sequestered in dialysis tubing. The rates of sulfide production in 7-day-old cultures with S(8)(0) sequestered in dialysis tubing with pore sizes of 12 to 14 kDa and 6 to 8 kDa were 55% and 22%, respectively, of that of cultures with S(8)(0) provided as a solid phase in the medium. These results indicate that the TEA existed in a range of particle sizes that affected its ability to diffuse through dialysis tubing of different pore sizes. Dynamic light scattering revealed that S(8)(0) particles generated through polysulfide rapidly grew in size, a rate which was influenced by the pH of the medium and the presence of organic carbon. Thus, S(8)(0) particles formed through abiological hydrolysis of polysulfide under acidic conditions appeared to serve as a growth-promoting TEA for A. sulfurireducens.
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 Science
Correction 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.
Influence of Choline Chloride/Urea and Glycerol Plasticizers on the Mechanical Properties of Thermoplastic Starch Plastics
(MDPI, 2024-03-09) Staker, Jacob; Schott, Sydney; Singh, Riya; Collier, Kourtney; Druschel, Gregory; Siegel, Amanda P.; Tovar, Andres; Chemistry and Chemical Biology, School of Science
Bio-based plastics made of food-safe compostable materials, such as thermoplastic starch (TPS), can be designed into films that have potential to replace many non-biodegradable single-use plastic (SUP) items. TPS film characteristics, such as elongation at break and tensile strength, are largely affected by the choice of the plasticizers used in formulation. Our work identifies the mechanical properties and the chemical structural differences between TPS films made with two different plasticizer mixtures that have not yet been compared alongside one another: deep eutectic solvent choline chloride/urea (1:2) (CC:U) and glycerol with an acetic acid catalyst (AA:G). Potato-based TPS samples were formed by mixing each plasticizer with a consistent amount of potato starch and distilled water with heat. After gelation formation, the viscous TPS mixture was centrifuged to degas and extruded. Films were dried at controlled room temperature. Characterization included the tensile testing of coupons according to ASTM (American Society of Testing and Materials) standard D638, attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), melting point (MP), and scanning electron microscopy (SEM). The AA:G films displayed significantly higher tensile strength (M = 2.04 ± 1.24 MPa) than the CC:U films (M = 0.18 ± 0.08 MPa); however, the CC:U films had higher elongation at break (M = 47.2 ± 3.6%) than the AA:G films (M = 31.1 ± 12.6%). This can be explained by the difference in functional groups, composition, and the degree of crystallinity evidenced by the FTIR, XRD, MP, and SEM results. Our findings suggest that potato-based TPS films with an AA:G plasticizer mixture hold promise for SUP applications that require more strength, while CC:U films may be more suited for wraps and bags that require flexibility. These innovations can aid to mitigate the environmental impact of harmful plastic waste.
Sediment Disturbance Negatively Impacts Methanogen Abundance but Has Variable Effects on Total Methane Emissions
(Frontiers Media, 2022-02-21) Rowe, Annette; Urbanic, Megan; Trutschel, Leah; Shukle, John; Druschel, Gregory; Booth, Michael; Earth and Environmental Sciences, School of Science
Methane emissions from aquatic ecosystems are increasingly recognized as substantial, yet variable, contributions to global greenhouse gas emissions. This is in part due to the challenge of modeling biologic parameters that affect methane emissions from a wide range of sediments. For example, the impacts of fish bioturbation on methane emissions in the literature have been shown to result in a gradient of reduced to enhanced emissions from sediments. However, it is likely that variation in experimental fish density, and consequently the frequency of bioturbation by fish, impacts this outcome. To explore how the frequency of disturbance impacts the levels of methane emissions in our previous work we quantified greenhouse gas emissions in sediment microcosms treated with various frequencies of mechanical disturbance, analogous to different levels of activity in benthic feeding fish. Greenhouse gas emissions were largely driven by methane ebullition and were highest for the intermediate disturbance frequency (disturbance every 7 days). The lowest emissions were for the highest frequency treatment (3 days). This work investigated the corresponding impacts of disturbance treatments on the microbial communities associated with producing methane. In terms of total microbial community structure, no statistical difference was observed in the total community structure of any disturbance treatment (0, 3, 7, and 14 days) or sediment depth (1 and 3 cm) measured. Looking specifically at methanogenic Archaea however, a shift toward greater relative abundance of a putatively oxygen-tolerant methanogenic phylotype (ca. Methanothrix paradoxum) was observed for the highest frequency treatments and at depths impacted by disturbance (1 cm). Notably, quantitative analysis of ca. Methanothrix paradoxum demonstrated no change in abundance, suggesting disturbance negatively and preferentially impacted other methanogen populations, likely through oxygen exposure. This was further supported by a linear decrease in quantitative abundance of methanogens (assessed by qPCR of the mcrA gene), with increased disturbance frequency in bioturbated sediments (1 cm) as opposed to those below the zone of bioturbation (3 cm). However, total methane emissions were not simply a function of methanogen populations and were likely impacted by the residence time of methane in the lower frequency disturbance treatments. Low frequency mechanical disruption results in lower methane ebullition compared to higher frequency treatments, which in turn resulted in reduced overall methane release, likely through enhanced methanotrophic activities, though this could not be identified in this work. Overall, this work contributes to understanding how animal behavior may impact variation in greenhouse gas emissions and provides insight into how frequency of disturbance may impact emissions.
Growth of microaerophilic Fe(II)-oxidizing bacteria using Fe(II) produced by Fe(III) photoreduction
(Wiley, 2022) Lueder, Ulf; Maisch, Markus; Jørgensen, Bo Barker; Druschel, Gregory; Schmidt, Caroline; Kappler, Andreas; Earth and Environmental Sciences, School of Science
Iron(II) (Fe(II)) can be formed by abiotic Fe(III) photoreduction, particularly when Fe(III) is organically complexed. Light-influenced environments often overlap or even coincide with oxic or microoxic geochemical conditions, for example, in sediments. So far, it is unknown whether microaerophilic Fe(II)-oxidizing bacteria are able to use the Fe(II) produced by Fe(III) photoreduction as electron donor. Here, we present an adaption of the established agar-stabilized gradient tube approach in comparison with liquid cultures for the cultivation of microaerophilic Fe(II)-oxidizing microorganisms by using a ferrihydrite-citrate mixture undergoing Fe(III) photoreduction as Fe(II) source. We quantified oxygen and Fe(II) gradients with amperometric and voltammetric microelectrodes and evaluated microbial growth by qPCR of 16S rRNA genes. We showed that gradients of dissolved Fe(II) (maximum Fe(II) concentration of 1.25 mM) formed in the gradient tubes when incubated in blue or UV light (400-530 nm or 350-400 nm). Various microaerophilic Fe(II)-oxidizing bacteria (Curvibacter sp. and Gallionella sp.) grew by oxidizing Fe(II) that was produced in situ by Fe(III) photoreduction. Best growth for these species, based on highest gene copy numbers, was observed in incubations using UV light in both liquid culture and gradient tubes containing 8 mM ferrihydrite-citrate mixtures (1:1), due to continuous light-induced Fe(II) formation. Microaerophilic Fe(II)-oxidizing bacteria contributed up to 40% to the overall Fe(II) oxidation within 24 h of incubation in UV light. Our results highlight the potential importance of Fe(III) photoreduction as a source of Fe(II) for Fe(II)-oxidizing bacteria by providing Fe(II) in illuminated environments, even under microoxic conditions.
Monitoring Phycocyanin with Landsat 8/Operational Land Imager Orange Contra-Band
(MDPI, 2022-03-19) Ogashawara, Igor; Li, Lin; Howard, Chase; Druschel, Gregory K.; Earth and Environmental Sciences, School of Science
The Operational Land Imager (OLI) onboard the Landsat 8 satellite has a panchromatic band (503–676 nm) that has been used to compute a virtual spectral band known as “orange contra-band” (590–635 nm). The major application of the orange contra-band is the monitoring of cyanobacteria which is usually quantified by the measurement of the concentration of phycocyanin (PC) which has an absorption peak around 620 nm. In this study, we evaluated the use of the orange contra-band approach for estimating PC concentration from in situ proximal hyperspectral data from Eagle Creek Reservoir (ECR), in Indiana, USA. We first validated the empirical relationship for the computation of the orange contra-band by using the panchromatic, red, and green spectral bands from ECR. PC concentration retrieval using the orange contra-band were not successful when using the entire dataset (R2 < 0.1) or when using only PC concentrations higher than 50 mg/m3 (R2 < 0.24). Better results were achieved when using samples in which PC was 1.5 times higher than the chlorophyll-a concentration (R2 = 0.84). These results highlighted the need for the development of remote sensing algorithms for the accurate estimation of PC concentration from non-PC dominant waters which could be use to track and/or predict cyanobacteria blooms.

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