Wankel Scott

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Wankel

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Scott

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0000-0002-7683-0225

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Nitrite oxidation exceeds reduction and fixed nitrogen loss in anoxic Pacific waters

(Elsevier, 2020-08-20) Babbin, Andrew ; Buchwald, Carolyn ; Morel, Francois M. M. ; Wankel, Scott D. ; Ward, Bess B.

The diversity of nitrogen-based dissimilatory metabolisms in anoxic waters continues to increase with additional studies to the marine oxygen deficient zones (ODZs). Although the microbial oxidation of nitrite (NO2–) has been known for over a century, studies of the pathways and microbes involved have generally proceeded under the assumption that nitrite oxidation to nitrate requires dioxygen (O2). Anaerobic NO2– oxidation until now has been conclusively shown only for anammox bacteria, albeit only as a limited sink for NO2– in their metabolism compared to the NO2– reduced to N2. Here, using direct experimental techniques optimized for replicating in situ anoxic conditions, we show that NO2– oxidation is substantial, widespread, and consistent across the ODZs of the eastern tropical Pacific Ocean. Regardless of the specific oxidant, NO2– oxidation rates are up to an order of magnitude larger than simultaneous N2 production rates for which these zones are known, and cannot be explained by anammox rates alone. Higher rates of NO2– oxidation over reduction in anoxic waters are paradoxical but help to explain how anammox rates can be enhanced over denitrification in shallow anoxic waters (σθ < 26.4) at the edge of the ODZs but not within the ODZ core. Furthermore, nitrite oxidation may be the key to reconciliation of the perceived imbalance of the global fixed nitrogen loss budget.
Nitrogen cycling in the deep sedimentary biosphere : nitrate isotopes in porewaters underlying the oligotrophic North Atlantic

(Copernicus Publications on behalf of the European Geosciences Union, 2015-12-21) Wankel, Scott D. ; Buchwald, Carolyn ; Ziebis, Wiebke ; Wenk, Christine B. ; Lehmann, Moritz F.

Nitrogen (N) is a key component of fundamental biomolecules. Hence, its cycling and availability are central factors governing the extent of ecosystems across the Earth. In the organic-lean sediment porewaters underlying the oligotrophic ocean, where low levels of microbial activity persist despite limited organic matter delivery from overlying water, the extent and modes of nitrogen transformations have not been widely investigated. Here we use the N and oxygen (O) isotopic composition of porewater nitrate (NO3−) from a site in the oligotrophic North Atlantic (Integrated Ocean Drilling Program – IODP) to determine the extent and magnitude of microbial nitrate production (via nitrification) and consumption (via denitrification). We find that NO3- accumulates far above bottom seawater concentrations (~ 21 μM) throughout the sediment column (up to ~ 50 μM) down to the oceanic basement as deep as 90 m b.s.f. (below sea floor), reflecting the predominance of aerobic nitrification/remineralization within the deep marine sediments. Large changes in the δ15N and δ18O of nitrate, however, reveal variable influence of nitrate respiration across the three sites. We use an inverse porewater diffusion–reaction model, constrained by the N and O isotope systematics of nitrification and denitrification and the porewater NO3- isotopic composition, to estimate rates of nitrification and denitrification throughout the sediment column. Results indicate variability of reaction rates across and within the three boreholes that are generally consistent with the differential distribution of dissolved oxygen at this site, though not necessarily with the canonical view of how redox thresholds separate nitrate regeneration from dissimilative consumption spatially. That is, we provide stable isotopic evidence for expanded zones of co-occurring nitrification and denitrification. The isotope biogeochemical modeling also yielded estimates for the δ15N and δ18O of newly produced nitrate (δ15NNTR (NTR, referring to nitrification) and δ18ONTR), as well as the isotope effect for denitrification (15ϵDNF) (DNF, referring to denitrification), parameters with high relevance to global ocean models of N cycling. Estimated values of δ15NNTR were generally lower than previously reported δ15N values for sinking particulate organic nitrogen in this region. We suggest that these values may be, in part, related to sedimentary N2 fixation and remineralization of the newly fixed organic N. Values of δ18ONTR generally ranged between −2.8 and 0.0 ‰, consistent with recent estimates based on lab cultures of nitrifying bacteria. Notably, some δ18ONTR values were elevated, suggesting incorporation of 18O-enriched dissolved oxygen during nitrification, and possibly indicating a tight coupling of NH4+ and NO2− oxidation in this metabolically sluggish environment. Our findings indicate that the production of organic matter by in situ autotrophy (e.g., nitrification, nitrogen fixation) supplies a large fraction of the biomass and organic substrate for heterotrophy in these sediments, supplementing the small organic-matter pool derived from the overlying euphotic zone. This work sheds new light on an active nitrogen cycle operating, despite exceedingly low carbon inputs, in the deep sedimentary biosphere.
Design optimization of a submersible chemiluminescent sensor (DISCO) for improved quantification of reactive oxygen species (ROS) in surface waters

(MDPI, 2022-09-03) Grabb, Kalina C. ; Pardis, William A. ; Kapit, Jason ; Wankel, Scott D. ; Hayden, Eric B. ; Hansel, Colleen M.

Reactive oxygen species (ROS) are key drivers of biogeochemical cycling while also exhibiting both positive and negative effects on marine ecosystem health. However, quantification of the ROS superoxide (O2−) within environmental systems is hindered by its short half-life. Recently, the development of the diver-operated submersible chemiluminescent sensor (DISCO), a submersible, handheld instrument, enabled in situ superoxide measurements in real time within shallow coral reef ecosystems. Here, we present a redesigned and improved instrument, DISCO II. Similar to the previous DISCO, DISCO II is a self-contained, submersible sensor, deployable to 30 m depth and capable of measuring reactive intermediate species in real time. DISCO II is smaller, lighter, lower cost, and more robust than its predecessor. Laboratory validation of DISCO II demonstrated an average limit of detection in natural seawater of 133.1 pM and a percent variance of 0.7%, with stable photo multiplier tube (PMT) counts, internal temperature, and flow rates. DISCO II can also be optimized for diverse environmental conditions by adjustment of the PMT supply voltage and integration time. Field tests showed no drift in the data with a percent variance of 3.0%. Wand tip adaptations allow for in situ calibrations and decay rates of superoxide using a chemical source of superoxide (SOTS-1). Overall, DISCO II is a versatile, user-friendly sensor that enables measurements in diverse environments, thereby improving our understanding of the cycling of reactive intermediates, such as ROS, across various marine ecosystems.
Biogeochemical exploration of the Pescardero Basin vents

(The Oceanography Society, 2018-03) Michel, Anna P. M. ; Wankel, Scott D. ; Beaulieu, Stace E. ; Soule, Samuel A. ; Mullineaux, Lauren S. ; Coleman, Dwight ; Escobar Briones, Elva ; Gaytan-Caballero, Adriana ; McDermott, Jill M. ; Mills, Susan W. ; Speth, Dan ; Zierenberg, Robert
Substantial oxygen consumption by aerobic nitrite oxidation in oceanic oxygen minimum zones

(Nature Research, 2021-12-02) Beman, J. Michael ; Vargas, Sonia M. ; Wilson, Jesse M. ; Perez-Coronel, Elisabet ; Karolewski, Jennifer S. ; Vazquez, Samantha ; Yu, Angela ; Cairo, Ariadna E. ; White, Margot E. ; Koester, Irina ; Aluwihare, Lihini I. ; Wankel, Scott D.

Oceanic oxygen minimum zones (OMZs) are globally significant sites of biogeochemical cycling where microorganisms deplete dissolved oxygen (DO) to concentrations <20 µM. Amid intense competition for DO in these metabolically challenging environments, aerobic nitrite oxidation may consume significant amounts of DO and help maintain low DO concentrations, but this remains unquantified. Using parallel measurements of oxygen consumption rates and 15N-nitrite oxidation rates applied to both water column profiles and oxygen manipulation experiments, we show that the contribution of nitrite oxidation to overall DO consumption systematically increases as DO declines below 2 µM. Nitrite oxidation can account for all DO consumption only under DO concentrations <393 nM found in and below the secondary chlorophyll maximum. These patterns are consistent across sampling stations and experiments, reflecting coupling between nitrate reduction and nitrite-oxidizing Nitrospina with high oxygen affinity (based on isotopic and omic data). Collectively our results demonstrate that nitrite oxidation plays a pivotal role in the maintenance and biogeochemical dynamics of OMZs.
Recent increases in water column denitrification in the seasonally suboxic bottom waters of the Santa Barbara Basin

(American Geophysical Union, 2019-06-11) White, Margot E. ; Rafter, Patrick ; Stephens, Brandon M. ; Wankel, Scott D. ; Aluwihare, Lihini I.

Denitrification in the anoxic sediments of the Santa Barbara Basin has been well documented in the historic and modern record, but the regulation of and frequency with which denitrification occurs in the overlying water column are less understood. Since 2004, the magnitude and speciation of redox active nitrogen species in bottom waters have changed markedly. Most notable are periods of decreased nitrate and increased nitrite concentrations. Here we examine these changes in nitrogen cycling as recorded by the stable isotopes of dissolved nitrate from 2010–2016. When compared to previous studies, our data identify an increase in water column denitrification in the bottom waters of the basin. Observations from inside the basin as well as data from the wider California Current Ecosystem implicate a long‐term trend of decreasing oxygen concentrations as the driver for these observed changes, with ramifications for local benthic communities and regional nitrogen loss.
Discovery and quantification of anaerobic nitrogen metabolisms among oxygenated tropical Cuban stony corals

(Springer Nature, 2020-12-20) Babbin, Andrew ; Tamasi, Tyler ; Dumit, Diana ; Weber, Laura ; Rodríguez, María Victoria Iglesias ; Schwartz, Sarah L. ; Armenteros, Maickel ; Wankel, Scott D. ; Apprill, Amy

Coral reef health depends on an intricate relationship among the coral animal, photosynthetic algae, and a complex microbial community. The holobiont can impact the nutrient balance of their hosts amid an otherwise oligotrophic environment, including by cycling physiologically important nitrogen compounds. Here we use 15N-tracer experiments to produce the first simultaneous measurements of ammonium oxidation, nitrate reduction, and nitrous oxide (N2O) production among five iconic species of reef-building corals (Acropora palmata, Diploria labyrinthiformis, Orbicella faveolata, Porites astreoides, and Porites porites) in the highly protected Jardines de la Reina reefs of Cuba. Nitrate reduction is present in most species, but ammonium oxidation is low potentially due to photoinhibition and assimilatory competition. Coral-associated rates of N2O production indicate a widespread potential for denitrification, especially among D. labyrinthiformis, at rates of ~1 nmol cm−2 d−1. In contrast, A. palmata displays minimal active nitrogen metabolism. Enhanced rates of nitrate reduction and N2O production are observed coincident with dark net respiration periods. Genomes of bacterial cultures isolated from multiple coral species confirm that microorganisms with the ability to respire nitrate anaerobically to either dinitrogen gas or ammonium exist within the holobiont. This confirmation of anaerobic nitrogen metabolisms by coral-associated microorganisms sheds new light on coral and reef productivity.
Flow through sediment core incubations for nitrogen concentration and isotopic fluxes collected in 2013 on the Island of Sylt, Germany in the North Sea.

(Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu, 2022-04-08) Wankel, Scott ; Ziebis, Wiebke

Flow through sediment core incubations for nitrogen concentration and isotopic fluxes collected in 2013 on the Island of Sylt, Germany in the North Sea. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/827378
Discovering hydrothermalism from afar: in situ methane instrumentation and change-point detection for decision-making

(Woods Hole Oceanographic Institution, 2022-10-06) Michel, Anna P. M. ; Wankel, Scott D. ; Preston, Victoria Lynn ; Flaspohler, Genevieve Elaine ; Kapit, Jason ; Pardis, William A. ; Youngs, Sarah ; Martocello, Donald E. ; Girguis, Peter R. ; Roy, Nicholas

Seafloor hydrothermalism plays a critical role in fundamental interactions between geochemical and biological processes in the deep ocean. A significant number of hydrothermal vents are hypothesized to exist, but many of these remain undiscovered due in part to the difficulty of detecting hydrothermalism using standard sensors on rosettes towed in the water column or robotic platforms performing surveys. Here, we use in situ methane sensors to complement standard sensing technology for hydrothermalism discovery and compare sensing equipment on a towed rosette and autonomous underwater vehicle (AUV) during a 17 km long transect in the Northern Guaymas Basin. This transect spatially intersected with a known hydrothermally active venting site. These data show that methane signaled possible hydrothermal activity 1.5-3 km laterally (100-150m vertically) from a known vent. Methane as a signal for hydrothermalism performed similarly to standard turbidity sensors (plume detection 2.2-3.3 km from reference source), and more sensitively and clearly than temperature, salinity, and oxygen instruments which readily respond to physical mixing in background seawater. We additionally introduce change-point detection algorithms---streaming cross-correlation and regime identification---as a means of real-time hydrothermalism discovery and discuss related data monitoring technologies that could be used in planning, executing, and monitoring explorative surveys for hydrothermalism.
Revised microbial and photochemical triple-oxygen isotope effects improve marine gross oxygen production estimates

(Oxford University Press, 2022-10-12) Sutherland, Kevin M. ; Johnston, David T. ; Hemingway, Jordon D. ; Wankel, Scott D. ; Ward, Collin P.

AbstractThe biogeochemical fluxes that cycle oxygen (O2) play a critical role in regulating Earth’s climate and habitability. Triple-oxygen isotope (TOI) compositions of marine dissolved O2 are considered a robust tool for tracing oxygen cycling and quantifying gross photosynthetic O2 production. This method assumes that photosynthesis, microbial respiration, and gas exchange with the atmosphere are the primary influences on dissolved O2 content, and that they have predictable, fixed isotope effects. Despite its widespread use, there are major elements of this approach that remain uncharacterized, including the TOI dynamics of respiration by marine heterotrophic bacteria and abiotic O2 sinks such as the photochemical oxidation of dissolved organic carbon (DOC). Here, we report the TOI fractionation for O2 utilization by two model marine heterotrophs and by abiotic photo-oxidation of representative terrestrial and coastal marine DOC. We demonstrate that TOI slopes associated with these processes span a significant range of the mass-dependent domain (λ = 0.499 to 0.521). A sensitivity analysis reveals that even under moderate productivity and photo-oxidation scenarios, true gross oxygen production may deviate from previous estimates by more than 20% in either direction. By considering a broader suite of oxygen cycle reactions, our findings challenge current gross oxygen production estimates and highlight several paths forward to better understanding the marine oxygen and carbon cycles.
Discovering hydrothermalism from afar: In Situ methane instrumentation and change-point detection for decision-making

(Frontiers Media, 2022-10-25) Preston, Victoria Lynn ; Flaspohler, Genevieve Elaine ; Kapit, Jason ; Pardis, William A. ; Youngs, Sarah ; Martocello, Donald E., III ; Roy, Nicholas ; Girguis, Peter R. ; Wankel, Scott ; Michel, Anna P. M.

Seafloor hydrothermalism plays a critical role in fundamental interactions between geochemical and biological processes in the deep ocean. A significant number of hydrothermal vents are hypothesized to exist, but many of these remain undiscovered due in part to the difficulty of detecting hydrothermalism using standard sensors on rosettes towed in the water column or robotic platforms performing surveys. Here, we use in situ methane sensors to complement standard sensing technology for hydrothermalism discovery and compare sensors on a towed rosette and an autonomous underwater vehicle (AUV) during a 17 km long transect in the Northern Guaymas Basin in the Gulf of California. This transect spatially intersected with a known hydrothermally active venting site. These data show that methane signalled possible hydrothermal-activity 1.5–3 km laterally (100–150 m vertically) from a known vent. Methane as a signal for hydrothermalism performed similarly to standard turbidity sensors (plume detection 2.2–3.3 km from reference source), and more sensitively and clearly than temperature, salinity, and oxygen instruments which readily respond to physical mixing in background seawater. We additionally introduce change-point detection algorithms—streaming cross-correlation and regime identification—as a means of real-time hydrothermalism discovery and discuss related data supervision technologies that could be used in planning, executing, and monitoring explorative surveys for hydrothermalism.
Porewater measurements of nitrate and nitrite concentration and N and O isotopic ratios (d15N and d18O) collected from sites 3 and 10 on the North Atlantic Long Core Cruise R/V Knorr KN223 from October to December 2014

(Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu, 2019-03-15) Buchwald, Carolyn ; Spivack, Arthur J. ; Wankel, Scott

Porewater measurements of nitrate and nitrite concentration and N and O isotopic ratios (d15N and d18O) collected from sites 3 and 10 on the North Atlantic Long Core Cruise R/V Knorr KN223 from October to December 2014. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/748792
Microbial activity in the marine deep biosphere : progress and prospects

(Frontiers Media, 2013-07-11) Orcutt, Beth N. ; LaRowe, Douglas E. ; Biddle, Jennifer F. ; Colwell, Frederick S. ; Glazer, Brian T. ; Kiel Reese, Brandi ; Kirkpatrick, John B. ; Lapham, Laura L. ; Mills, Heath J. ; Sylvan, Jason B. ; Wankel, Scott D. ; Wheat, C. Geoffrey

The vast marine deep biosphere consists of microbial habitats within sediment, pore waters, upper basaltic crust and the fluids that circulate throughout it. A wide range of temperature, pressure, pH, and electron donor and acceptor conditions exists—all of which can combine to affect carbon and nutrient cycling and result in gradients on spatial scales ranging from millimeters to kilometers. Diverse and mostly uncharacterized microorganisms live in these habitats, and potentially play a role in mediating global scale biogeochemical processes. Quantifying the rates at which microbial activity in the subsurface occurs is a challenging endeavor, yet developing an understanding of these rates is essential to determine the impact of subsurface life on Earth's global biogeochemical cycles, and for understanding how microorganisms in these “extreme” environments survive (or even thrive). Here, we synthesize recent advances and discoveries pertaining to microbial activity in the marine deep subsurface, and we highlight topics about which there is still little understanding and suggest potential paths forward to address them. This publication is the result of a workshop held in August 2012 by the NSF-funded Center for Dark Energy Biosphere Investigations (C-DEBI) “theme team” on microbial activity (www.darkenergybiosphere.org).
Spectroscopic insights into ferromanganese crust formation and diagenesis

(American Geophysical Union, 2020-10-26) Sutherland, Kevin M. ; Wankel, Scott D. ; Hein, James R. ; Hansel, Colleen M.

Marine ferromanganese deposits, often called the scavengers of the sea, adsorb and coprecipitate with a wide range of metals of great interest for paleo‐environmental reconstructions and economic geology. The long (up to ∼75 Ma), near‐continuous record of seawater chemistry afforded by ferromanganese deposits offers much historical information about the global ocean and surface earth including crustal processes, mantle processes, ocean circulation, and biogeochemical cycles. The extent to which the ferromanganese deposits hosting these geochemical proxies undergo diagenesis on the seafloor, however, remains an important and challenging factor in assessing the fidelity of such records. In this study, we employ multiple X‐ray techniques including micro–X‐ray fluorescence, bulk and micro–X‐ray absorption spectroscopy, and X‐ray powder diffraction to probe the structural, compositional, redox, and mineral changes within a single ferromanganese crust. These techniques illuminate a complex two‐dimensional structure characterized by crust growth controlled by the availability of manganese (Mn), a dynamic range in Mn oxidation state from +3.4 to +4.0, changes in Mn mineralogy over time, and recrystallization in the lower phosphatized portions of the crust. Iron (Fe) similarly demonstrates spatial complexity with respect to concentration and mineralogy, but lacks the dynamic range of oxidation state seen for Mn. Micrometer‐scale measurements of metal abundances reveal complex element associations between trace elements and the two major oxide phases, which are not typically resolvable via bulk analytical methods. These findings provide evidence of post‐depositional processes altering chemistry and mineralogy, and provide important geochemical context for the interpretation of element and isotopic records in ferromanganese crusts.
Isotopic constraints on nitrogen transformation rates in the deep sedimentary marine biosphere

(American Geophysical Union, 2018-10-18) Buchwald, Carolyn ; Homola, Kira ; Spivack, Arthur J. ; Estes, Emily R. ; Wankel, Scott D.

Little is known about the nature of microbial community activity contributing to the cycling of nitrogen in organic-poor sediments underlying the expansive oligotrophic ocean gyres. Here we use pore water concentrations and stable N and O isotope measurements of nitrate and nitrite to constrain rates of nitrogen cycling processes over a 34-m profile from the deep North Atlantic spanning fully oxic to anoxic conditions. Using a 1-D reaction-diffusion model to predict the distribution of nitrogen cycling rates, results converge on two distinct scenarios: (1) an exceptionally high degree of coupling between nitrite oxidation and nitrate reduction near the top of the anoxic zone or (2) an unusually large N isotope effect (~60‰) for nitrate reduction that is decoupled from the corresponding O isotope effect, which is possibly explained by enzyme-level interconversion between nitrite and nitrate.
Hunting Bubbles Falkor Cruise 2019

(Woods Hole Oceanographic Institution, 2019-12-23) Michel, Anna P. M. ; Wankel, Scott D. ; Nicholson, David P. ; Fauria, Kristen ; Preston, Victoria Lynn

The Hunting Bubbles Cruise took place in August-September 2018 on the R/V Falkor (cruise ID 180824). Ship time was provided by the Schmidt Ocean Institute. This cruise investigated transport of methane from seeps located on the Cascadia Margin. Data archived at the WHOAS repository supplements additional data from this cruise available at the R2R rolling deck to repository and at MGDS: Marine Geoscience Data System.
Quantifying population-specific growth in benthic bacterial communities under low oxygen using H218O

(Springer Nature, 2019-02-19) Coskun, Ömer K. ; Özen, Volkan ; Wankel, Scott D. ; Orsi, William D.

The benthos in estuarine environments often experiences periods of regularly occurring hypoxic and anoxic conditions, dramatically impacting biogeochemical cycles. How oxygen depletion affects the growth of specific uncultivated microbial populations within these diverse benthic communities, however, remains poorly understood. Here, we applied H218O quantitative stable isotope probing (qSIP) in order to quantify the growth of diverse, uncultured bacterial populations in response to low oxygen concentrations in estuarine sediments. Over the course of 7- and 28-day incubations with redox conditions spanning from hypoxia to euxinia (sulfidic), 18O labeling of bacterial populations exhibited different patterns consistent with micro-aerophilic, anaerobic, facultative anaerobic, and aerotolerant anaerobic growth. 18O-labeled populations displaying anaerobic growth had a significantly non-random phylogenetic distribution, exhibited by numerous clades currently lacking cultured representatives within the Planctomycetes, Actinobacteria, Latescibacteria, Verrucomicrobia, and Acidobacteria. Genes encoding the beta-subunit of the dissimilatory sulfate reductase (dsrB) became 18O labeled only during euxinic conditions. Sequencing of these 18O-labeled dsrB genes showed that Acidobacteria were the dominant group of growing sulfate-reducing bacteria, highlighting their importance for sulfur cycling in estuarine sediments. Our findings provide the first experimental constraints on the redox conditions underlying increased growth in several groups of “microbial dark matter”, validating hypotheses put forth by earlier metagenomic studies.
Evidence for fungal and chemodenitrification based N2O flux from nitrogen impacted coastal sediments

(Nature Publishing Group, 2017-06-05) Wankel, Scott D. ; Ziebis, Wiebke ; Buchwald, Carolyn ; Charoenpong, Chawalit N. ; de Beer, Dirk ; Dentinger, Jane ; Xu, Zhenjiang ; Zengler, Karsten

Although increasing atmospheric nitrous oxide (N2O) has been linked to nitrogen loading, predicting emissions remains difficult, in part due to challenges in disentangling diverse N2O production pathways. As coastal ecosystems are especially impacted by elevated nitrogen, we investigated controls on N2O production mechanisms in intertidal sediments using novel isotopic approaches and microsensors in flow-through incubations. Here we show that during incubations with elevated nitrate, increased N2O fluxes are not mediated by direct bacterial activity, but instead are largely catalysed by fungal denitrification and/or abiotic reactions (e.g., chemodenitrification). Results of these incubations shed new light on nitrogen cycling complexity and possible factors underlying variability of N2O fluxes, driven in part by fungal respiration and/or iron redox cycling. As both processes exhibit N2O yields typically far greater than direct bacterial production, these results emphasize their possibly substantial, yet widely overlooked, role in N2O fluxes, especially in redox-dynamic sediments of coastal ecosystems.
Isotopic signals in an agricultural watershed suggest denitrification is locally intensive in riparian areas but extensive in upland soils

(Springer, 2022-02-11) Sigler, W. Adam ; Ewing, Stephanie A. ; Wankel, Scott D. ; Jones, Clain A. ; Leuthold, Sam J. ; Brookshire, E. N. Jack ; Payn, Robert A.

Nitrogen loss from cultivated soils threatens the economic and environmental sustainability of agriculture. Nitrate (NO3−) derived from nitrification of nitrogen fertilizer and ammonified soil organic nitrogen may be lost from soils via denitrification, producing dinitrogen gas (N2) or the greenhouse gas nitrous oxide (N2O). Nitrate that accumulates in soils is also subject to leaching loss, which can degrade water quality and make NO3− available for downstream denitrification. Here we use patterns in the isotopic composition of NO3− observed from 2012 to 2017 to characterize N loss to denitrification within soils, groundwater, and stream riparian corridors of a non-irrigated agroecosystem in the northern Great Plains (Judith River Watershed, Montana, USA). We find evidence for denitrification across these domains, expressed as a positive linear relationship between δ15N and δ18O values of NO3−, as well as increasing δ15N values with decreasing NO3− concentration. In soils, isotopic evidence of denitrification was present during fallow periods (no crop growing), despite net accumulation of NO3− from the nitrification of ammonified soil organic nitrogen. We combine previous results for soil NO3− mass balance with δ15N mass balance to estimate denitrification rates in soil relative to groundwater and streams. Substantial denitrification from soils during fallow periods may be masked by nitrification of ammonified soil organic nitrogen, representing a hidden loss of soil organic nitrogen and an under-quantified flux of N to the atmosphere. Globally, cultivated land spends ca. 50% of time in a fallow condition; denitrification in fallow soils may be an overlooked but globally significant source of agricultural N2O emissions, which must be reduced along-side other emissions to meet Paris Agreement goals for slowing global temperature increase.
Ebullition of oxygen from seagrasses under supersaturated conditions

(Wiley, 2019-08-08) Long, Matthew H. ; Sutherland, Kevin M. ; Wankel, Scott D. ; Burdige, David J. ; Zimmerman, Richard C.

Gas ebullition from aquatic systems to the atmosphere represents a potentially important fraction of primary production that goes unquantified by measurements of dissolved gas concentrations. Although gas ebullition from photosynthetic surfaces has often been observed, it is rarely quantified. The resulting underestimation of photosynthetic activity may significantly bias the determination of ecosystem trophic status and estimated rates of biogeochemical cycling from in situ measures of dissolved oxygen. Here, we quantified gas ebullition rates in Zostera marina meadows in Virginia, U.S.A. using simple funnel traps and analyzed the oxygen concentration and isotopic composition of the captured gas. Maximum hourly rates of oxygen ebullition (3.0 mmol oxygen m−2 h−1) were observed during the coincidence of high irradiance and low tides, particularly in the afternoon when oxygen and temperature maxima occurred. The daily ebullition fluxes (up to 11 mmol oxygen m−2 d−1) were roughly equivalent to net primary production rates determined from dissolved oxygen measurements indicating that bubble ebullition can represent a major component of primary production that is not commonly included in ecosystem‐scale estimates. Oxygen content comprised 20–40% of the captured bubble gas volume and correlated negatively with its δ18O values, consistent with a predominance of mixing between the higher δ18O of atmospheric oxygen in equilibrium with seawater and the lower δ18O of oxygen derived from photosynthesis. Thus, future studies interested in the metabolism of highly productive, shallow water ecosystems, and particularly those measuring in situ oxygen flux, should not ignore the bubble formation and ebullition processes described here.

Wankel Scott

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