Gregory K. Druschel

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

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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.
Elemental sulfur coarsening kinetics
(Springer (Biomed Central Ltd.), 2014) Garcia, Angel A.; Druschel, Gregory K.; Department of Earth Sciences, School of Science
BACKGROUND: 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.
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.
Microscale sulfur cycling in the phototrophic pink berry consortia of the Sippewissett Salt Marsh
(Wiley Blackwell (Blackwell Publishing), 2014-11) Wilbanks, Elizabeth G.; Jaekel, Ulrike; Salman, Verena; Humphrey, Parris T.; Eisen, Jonathan A.; Facciotti, Marc T.; Buckley, Daniel H.; Zinder, Stephen H.; Druschel, Gregory K.; Fike, David A.; Orphan, Victoria J.; Department of Earth Sciences, School of Science
Microbial metabolism is the engine that drives global biogeochemical cycles, yet many key transformations are carried out by microbial consortia over short spatiotemporal scales that elude detection by traditional analytical approaches. We investigate syntrophic sulfur cycling in the 'pink berry' consortia of the Sippewissett Salt Marsh through an integrative study at the microbial scale. The pink berries are macroscopic, photosynthetic microbial aggregates composed primarily of two closely associated species: sulfide-oxidizing purple sulfur bacteria (PB-PSB1) and sulfate-reducing bacteria (PB-SRB1). Using metagenomic sequencing and (34) S-enriched sulfate stable isotope probing coupled with nanoSIMS, we demonstrate interspecies transfer of reduced sulfur metabolites from PB-SRB1 to PB-PSB1. The pink berries catalyse net sulfide oxidation and maintain internal sulfide concentrations of 0-500 μm. Sulfide within the berries, captured on silver wires and analysed using secondary ion mass spectrometer, increased in abundance towards the berry interior, while δ(34) S-sulfide decreased from 6‰ to -31‰ from the exterior to interior of the berry. These values correspond to sulfate-sulfide isotopic fractionations (15-53‰) consistent with either sulfate reduction or a mixture of reductive and oxidative metabolisms. Together this combined metagenomic and high-resolution isotopic analysis demonstrates active sulfur cycling at the microscale within well-structured macroscopic consortia consisting of sulfide-oxidizing anoxygenic phototrophs and sulfate-reducing bacteria.
Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece
(Springer, 2015) Gilhooly, William P., III; Fike, David A.; Druschel, Gregory K.; Kafantaris, Fotios-Christos A.; Price, Roy E.; Amend, Jan P.; Department of Earth Sciences, School of Science
Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m2) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ34S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ34SSO4 and δ18OSO4 as expected of microbial sulfate reduction. Instead, pore water δ34SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ34SSO4 as a mixing process between oxic seawater and 34S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ34SSO4, the oxygen isotope composition of sulfate tended to be 18O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ18OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal fluids could not be determined with the present dataset; however, the end-member δ34S value of H2S discharged to the seafloor is consistent with equilibrium isotope exchange with subsurface anhydrite veins at a temperature of ~300°C. Any biological sulfur cycling within these hydrothermal systems is masked by abiotic chemical reactions driven by mixing between low-sulfate, H2S-rich hydrothermal fluids and oxic, sulfate-rich seawater.
Geomicrobiology and Microbial Geochemistry
(GeoScienceWorld, 2015-12) Druschel, Gregory K.; Kappler, Andreas; Department of Earth Sciences, School of Science
Geomicrobiology and microbial geochemistry (GMG) investigates the interaction between Earth, environmental systems, and microbial life. Microbes shape their geochemical surroundings through their metabolic and growth needs and thereby exert significant geochemical and mineralogical control on their local environments. In turn, local geochemical conditions dictate what metabolic processes are possible. These mutual influences mean that microbial evolution has occurred in concert with changing geosphere conditions and that microbes have driven major shifts in ocean, continent and atmospheric chemistry. If one wishes to understand element cycling in any system containing water, one must realize that microbes are critical to the story.
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.
The Effects of Surfactants on Colloidal, Nanoparticulate, and Dissolved Sulfur
(Office of the Vice Chancellor for Research, 2016-04-08) Kurek, Martin; Druschel, Greg; Gilhooly, William P., III
Elemental sulfur is generally insoluble in water unless in the presence of a surfactant. This phenomenon was investigated by Steudel and Holdt in 1988 by filtering mixtures of sulfur, water, and surfactants through a 0.45 micron filter; however, since then sulfur nanoparticles smaller than 0.45 microns have been detected. The smaller than expected particle size suggests that the distribution of elemental sulfur in water with surfactants may be partitioned into colloidal, nanoparticulate, and truly dissolved components. Experiments have been conducted measuring the sulfur solubility in water with several chemical surfactants and varying filter sizes smaller than 0.45 microns. These experiments were conducted under equilibrium conditions with the solubility being measured using HPLC and square wave voltammetry. Kinetic studies detailing the solubility of sulfur with the surfactants over time have also been investigated. Data regarding the size and occurrence of sulfur nanoparticles present in water and the surfactants has been collected as well to give a complete description of the system under examination. Sulfur isotope fractionation of the dissolved sulfur species is also an interesting component of the system that is currently being investigated using stable isotope ratio mass spectrometry of 34S.
Spatially resolved capture of hydrogen sulfide from the water column and sedimentary pore waters for abundance and stable isotopic analysis
(Elsevier, 2017) Fike, D. A.; Houghton, J. L.; Moore, S. E.; Gilhooly, William P., III; Dawson, K. S.; Druschel, Gregory K.; Amend, J. P.; Orphan, V. J.; Department of Earth Sciences, School of Science
Sulfur cycling is ubiquitous in sedimentary environments, where it plays a major role in mediating carbon remineralization and impacts both local and global redox budgets. Microbial sulfur cycling is dominated by metabolic activity that either produces (e.g., sulfate reduction, disproportionation) or consumes (sulfide oxidation) hydrogen sulfide (H2S). As such, improved constraints on the production, distribution, and consumption of H2S in the natural environment will increase our understanding of microbial sulfur cycling. These different microbial sulfur metabolisms are additionally associated with particular stable isotopic fractionations. Coupling measurements of the isotopic composition of the sulfide with its distribution can provide additional information about environmental conditions and microbial ecology. Here we investigate the kinetics of sulfide capture on photographic films as a way to document the spatial distribution of sulfide in complex natural environments as well as for in situ capture of H2S for subsequent stable isotopic analysis. Laboratory experiments and timed field deployments demonstrate the ability to infer ambient sulfide abundances from the yield of sulfide on the films. This captured sulfide preserves the isotopic composition of the ambient sulfide, offset to slightly lower δ34S values by ~ 1.2 ± 0.5‰ associated with the diffusion of sulfide into the film and subsequent reaction with silver to form Ag2S precipitates. The resulting data enable the exploration of cm-scale lateral heterogeneity that complement most geochemical profiles using traditional techniques in natural environments. Because these films can easily be deployed over a large spatial area, they are also ideal for real-time assessment of the spatial and temporal dynamics of a site during initial reconnaissance and for integration over long timescales to capture ephemeral processes.
Winter weather and lake-watershed physical configuration drive phosphorus, iron, and manganese dynamics in water and sediment of ice-covered lakes
(Wiley, 2017-06) Joung, DongJoo; Leduc, Meagan; Ramcharitar, Benjamin; Xu, Yaoyang; Isles, Peter D. F.; Stockwell, Jason D.; Druschel, Gregory K.; Manley, Tom; Schroth, Andrew W.; Earth Science, School of Science
While decreasing occurrence and duration of lake ice cover is well-documented, biogeochemical dynamics in frozen lakes remain poorly understood. Here, we interpret winter physical and biogeochemical time series from eutrophic Missisquoi Bay (MB) and hyper-eutrophic Shelburne Pond (SP) to describe variable drivers of under ice biogeochemistry in systems of fundamentally different lake-watershed physical configurations (lake area, lake : watershed area). The continuous cold of the 2015 winter drove the MB sediment-water interface to the most severe and persistent suboxic state ever documented at this site, promoting the depletion of redox-sensitive phases in sediments, and an expanding zone of bottom water enriched in reactive species of Mn, Fe, and P. In this context, lake sediment and water column inventories of reactive chemical species were sensitive to the severity and persistence of subfreezing temperatures. During thaws, event provenance and severity impact lake thermal structure and mixing, water column enrichment in P and Fe, and thaw capability to suppress redox front position and internal chemical loading. Nearly identical winter weather manifest differently in nearby SP, where the small surface and watershed areas promoted a warmer, less stratified water column and active phytoplankton populations, impacting biogeochemical dynamics. In SP, Fe and P behavior under ice were decoupled due to active biological cycling, and thaw impacts were different in distribution and composition due to SP's physical structure and related antecedent conditions. We find that under ice biogeochemistry is highly dynamic in both time and space and sensitive to a variety of drivers impacted by climate change.

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