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  • 1
    Publication Date: 2022-06-10
    Description: Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Isotopic constraints on nitrogen transformation rates in the deep sedimentary marine biosphere. Global Biogeochemical Cycles, 32, (2018):1688–1702., doi: 10.1029/2018GB005948.
    Description: 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.
    Description: Samples analyzed for this study were collected during the final expedition of the RV Knorr, KN223. The expedition would not have been possible without the captain and crew of the RV Knorr and the efforts of the shipboard science party. We would like to acknowledge Robert Pockalny for planning and facilitating the expedition. Inorganic geochemistry sample collection, processing, and analysis were performed shipboard by Arthur Spivack,Dennis Graham, Chloe Anderson, Emily Estes, Kira Homola, Claire McKinley, Theodore Present, and Justine Sauvage. Coring capabilities were provided by the Oregon State University and Woods Hole Oceanographic Institute Coring Facilities, directed and funded by the U. S. National Science Foundation (NSF) Ship Facilities Program. The cored materials and discrete samples from the expedition are curated and stored by the Marine Geological Samples Laboratory at the University of Rhode Island, codirected by Rebecca Robinson and Katherine Kelly and funded by the NSF Ocean Sciences Division. The nutrient and isotope data from pore waters in this study will be available at The Biological and Chemical Data Management Office (https://www.bcodmo.org/project/567401). This project was partially funded by an NSF CDEBI postdoctoral fellowship to C. Buchwald. Portions of this material are based upon work supported while R. W. M. was serving at the National Science Foundation.
    Description: 2019-04-18
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 46(12), (2019): 6786-6795, doi:10.1029/2019GL082075.
    Description: 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.
    Description: We thank CalCOFI and Shonna Dovel for sample collection and two anonymous reviewers for improving the manuscript. Thanks also to Daniel Sigman for useful discussions, and Zoe Sandwith and Jen Karolewski for help with sample analysis. Data sets presented here were supported in part by CCE‐LTER augmented funding (NSF grant OCE‐1026607). Additional funding came from the Edna Bailey Sussman Foundation and the San Diego Foundation Blasker Environment grant. All data can be accessed at http://calcofi.org and https://oceaninformatics.ucsd.edu/datazoo/catalogs/ccelter/datasets. SDW acknowledges the support of a fellowship through the Hanse‐Wissenschaftskolleg (Institute for Advanced Studies).
    Description: 2019-12-11
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 3
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 46(12), (2019): 6745-6754, doi:10.1029/2019GL082867.
    Description: Although photochemical oxidation is an environmental process that drives organic carbon (OC) cycling, its quantitative detection remains analytically challenging. Here, we use samples from the Deepwater Horizon oil spill to test the hypothesis that the stable oxygen isotope composition of oil (δ18OOil) is a sensitive marker for photochemical oxidation. In less than one‐week, δ18OOil increased from −0.6 to 7.2‰, a shift representing ~25% of the δ18OOC dynamic range observed in nature. By accounting for different oxygen sources (H2O or O2) and kinetic isotopic fractionation of photochemically incorporated O2, which was −9‰ for a wide range of OC sources, a mass balance was established for the surface oil's elemental oxygen content and δ18O. This δ18O‐based approach provides novel insights into the sources and pathways of hydrocarbon photo‐oxidation, thereby improving our understanding of the fate and transport of petroleum hydrocarbons in sunlit waters, and our capacity to respond effectively to future spills.
    Description: We thank Robert Ricker and Greg Baker (NOAA) for helping secure the oil residues, James Payne (Payne Environmental Consultants, Inc.) for collecting many of the surface oil residues, Joy Matthews (UC Davis) for exceptional assistance in preparing and analyzing the oil residues for oxygen content and isotopes, Hank Levi and Art Gatenby at CSC Scientific Company for assistance with the water content measurements, Robyn Comny (US EPA) for providing the Alaska North Slope oil, and Rose Cory (UMich) for discussions about our findings. Special thanks to John Hayes who provided constructive feedback on a preliminary version of this dataset prior to his passing in February of 2017. We thank Alex Sessions (CalTech) for his constructive feedback during the review process. This work was supported, in part, by National Science Foundation grants RAPID OCE‐1043976 (CMR), OCE‐1333148 (CMR), OCE‐1333026 (CMS), OCE‐1333162 (DLV), OCE‐1841092 (CPW), NASA NESSF NNX15AR62H (KMS), the Gulf of Mexico Research Initiative grants ‐ 015, SA 16‐30, and DEEP‐C consortium, a fellowship through the Hansewissenschaftskolleg (Institute for Advanced Studies) to SDW, and assistant scientist salary support from the Frank and Lisina Hoch Endowed Fund (CPW).
    Description: 2019-11-30
    Keywords: Petroleum hydrocarbons ; Photochemical oxidation ; Deepwater Horizon ; Stable oxygen isotopes ; Organic carbon
    Repository Name: Woods Hole Open Access Server
    Type: Article
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