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  • 1
    Publication Date: 2022-10-26
    Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Sutherland, K. M., Grabb, K. C., Karolewski, J. S., Plummer, S., Farfan, G. A., Wankel, S. D., Diaz, J. M., Lamborg, C. H., & Hansel, C. M. Spatial heterogeneity in particle-associated, light-independent superoxide production within productive coastal waters. Journal of Geophysical Research: Oceans, 125(10), (2020): e2020JC016747, https://doi.org/10.1029/2020JC016747.
    Description: In the marine environment, the reactive oxygen species (ROS) superoxide is produced through a diverse array of light‐dependent and light‐independent reactions, the latter of which is thought to be primarily controlled by microorganisms. Marine superoxide production influences organic matter remineralization, metal redox cycling, and dissolved oxygen concentrations, yet the relative contributions of different sources to total superoxide production remain poorly constrained. Here we investigate the production, steady‐state concentration, and particle‐associated nature of light‐independent superoxide in productive waters off the northeast coast of North America. We find exceptionally high levels of light‐independent superoxide in the marine water column, with concentrations ranging from 10 pM to in excess of 2,000 pM. The highest superoxide concentrations were particle associated in surface seawater and in aphotic seawater collected meters off the seafloor. Filtration of seawater overlying the continental shelf lowered the light‐independent, steady‐state superoxide concentration by an average of 84%. We identify eukaryotic phytoplankton as the dominant particle‐associated source of superoxide to these coastal waters. We contrast these measurements with those collected at an off‐shelf station, where superoxide concentrations did not exceed 100 pM, and particles account for an average of 40% of the steady‐state superoxide concentration. This study demonstrates the primary role of particles in the production of superoxide in seawater overlying the continental shelf and highlights the importance of light‐independent, dissolved‐phase reactions in marine ROS production.
    Description: This work was funded by grants from the Chemical Oceanography program of the National Science Foundation (OCE‐1355720 to C. M. H. and C. H. L.), NASA Earth and Space Science Fellowship (Grant NNX15AR62H to K. M. S.), Agouron Institute Postdoctoral Fellowship (K. M. S.), NSF GRFPs (2016230268 to K. C. G. and 2017250547 to S. P.), and a Sloan Research Fellowship (J. M. D.). The Guava flow cytometer was purchased through an NSF equipment improvement grant (1624593).
    Keywords: reactive oxygen species ; Extracellular superoxide ; Light‐independent ROS
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-10-26
    Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Farfan, G. A., Cordes, E. E., Waller, R. G., DeCarlo, T. M., & Hansel, C. M. (2018). Mineralogy of deep-sea coral aragonites as a function of aragonite saturation state. Frontiers in Marine Science, 5, (2018): 473. doi:10.3389/fmars.2018.00473.
    Description: In an ocean with rapidly changing chemistry, studies have assessed coral skeletal health under projected ocean acidification (OA) scenarios by characterizing morphological distortions in skeletal architecture and measuring bulk properties, such as net calcification and dissolution. Few studies offer more detailed information on skeletal mineralogy. Since aragonite crystallography will at least partially govern the material properties of coral skeletons, such as solubility and strength, it is important to understand how it is influenced by environmental stressors. Here, we take a mineralogical approach using micro X-ray diffraction (XRD) and whole pattern Rietveld refinement analysis to track crystallographic shifts in deep-sea coral Lophelia pertusa samples collected along a natural seawater aragonite saturation state gradient (Ωsw = 1.15–1.44) in the Gulf of Mexico. Our results reveal statistically significant linear relationships between rising Ωsw and increasing unit cell volume driven by an anisotropic lengthening along the b-axis. These structural changes are similarly observed in synthetic aragonites precipitated under various saturation states, indicating that these changes are inherent to the crystallography of aragonite. Increased crystallographic disorder via widening of the full width at half maximum of the main (111) XRD peaks trend with increased Ba substitutions for Ca, however, trace substitutions by Ba, Sr, and Mg do not trend with crystal lattice parameters in our samples. Instead, we observe a significant trend of increasing calcite content as a function of both decreasing unit cell parameters as well as decreasing Ωsw. This may make calcite incorporation an important factor to consider in coral crystallography, especially under varying aragonite saturation states (ΩAr). Finally, by defining crystallography-based linear relationships between ΩAr of synthetic aragonite analogs and lattice parameters, we predict internal calcifying fluid saturation state (Ωcf = 11.1–17.3 calculated from b-axis lengths; 15.2–25.2 calculated from unit cell volumes) for L. pertusa, which may allow this species to calcify despite the local seawater conditions. This study will ideally pave the way for future studies to utilize quantitative XRD in exploring the impact of physical and chemical stressors on biominerals.
    Description: Funding for this project was made possible by Mineralogical Society of America Edward H. Kraus Crystallographic Research Fund and the WHOI Ocean Ventures Fund. GF was supported by a National Science Foundation Graduate Research Fellowship grant no. 1122374 and a Ford Foundation Dissertation Fellowship. Sample collections from RW were funded under NSF grant nos. 1245766 and 1127582 and NOAA Ocean Exploration Deep Atlantic Stepping Stones. Collections from the Gulf of Mexico were supported by NSF BIO-OCE grant #1220478 to EC.
    Keywords: Deep-sea corals ; Lophelia pertusa ; Crystallography ; Mineralogy ; X-ray diffraction ; Ocean acidification ; Aragonite saturation state ; Aragonite
    Repository Name: Woods Hole Open Access Server
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  • 3
    Publication Date: 2022-05-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Hansel, C. M., Diaz, J. M., & Plummer, S.. Tight regulation of extracellular superoxide points to its vital role in the physiology of the globally relevant Roseobacter clade. Mbio, 10(2), (2019):e02668-18, doi:10.1128/mBio.02668-18.
    Description: There is a growing appreciation within animal and plant physiology that the reactive oxygen species (ROS) superoxide is not only detrimental but also essential for life. Yet, despite widespread production of extracellular superoxide by healthy bacteria and phytoplankton, this molecule remains associated with stress and death. Here, we quantify extracellular superoxide production by seven ecologically diverse bacteria within the Roseobacter clade and specifically target the link between extracellular superoxide and physiology for two species. We reveal for all species a strong inverse relationship between cell-normalized superoxide production rates and cell number. For exponentially growing cells of Ruegeria pomeroyi DSS-3 and Roseobacter sp. strain AzwK-3b, we show that superoxide levels are regulated in response to cell density through rapid modulation of gross production and not decay. Over a life cycle of batch cultures, extracellular superoxide levels are tightly regulated through a balance of both production and decay processes allowing for nearly constant levels of superoxide during active growth and minimal levels upon entering stationary phase. Further, removal of superoxide through the addition of exogenous superoxide dismutase during growth leads to significant growth inhibition. Overall, these results point to tight regulation of extracellular superoxide in representative members of the Roseobacter clade, consistent with a role for superoxide in growth regulation as widely acknowledged in fungal, animal, and plant physiology.
    Description: We thank Mary Ann Moran and Alison Buchan for providing Roseobacter cultures, Kevin Sutherland for providing helpful feedback on the manuscript, and Elizabeth Harvey for use of her flow cytometer. This research was supported by NSF OCE-1355720 and a WHOI Independent Study Award (27005303) to C.M.H., as well as a Junior Faculty Seed Grant from the University of Georgia Research Foundation to J.M.D. and a National Science Foundation Graduate Research Fellowship to S.P.
    Keywords: Roseobacter ; reactive oxygen species ; superoxide ; superoxide dismutase
    Repository Name: Woods Hole Open Access Server
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  • 4
    Publication Date: 2022-05-27
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Farfan, G. A., Apprill, A., Cohen, A., DeCarlo, T. M., Post, J. E., Waller, R. G., & Hansel, C. M. Crystallographic and chemical signatures in coral skeletal aragonite. Coral Reefs. (2121), https://doi.org/10.1007/s00338-021-02198-4.
    Description: Corals nucleate and grow aragonite crystals, organizing them into intricate skeletal structures that ultimately build the world’s coral reefs. Crystallography and chemistry have profound influence on the material properties of these skeletal building blocks, yet gaps remain in our knowledge about coral aragonite on the atomic scale. Across a broad diversity of shallow-water and deep-sea scleractinian corals from vastly different environments, coral aragonites are remarkably similar to one another, confirming that corals exert control on the carbonate chemistry of the calcifying space relative to the surrounding seawater. Nuances in coral aragonite structures relate most closely to trace element chemistry and aragonite saturation state, suggesting the primary controls on aragonite structure are ionic strength and trace element chemistry, with growth rate playing a secondary role. We also show how coral aragonites are crystallographically indistinguishable from synthetic abiogenic aragonite analogs precipitated from seawater under conditions mimicking coral calcifying fluid. In contrast, coral aragonites are distinct from geologically formed aragonites, a synthetic aragonite precipitated from a freshwater solution, and mollusk aragonites. Crystallographic signatures have future applications in understanding the material properties of coral aragonite and predicting the persistence of coral reefs in a rapidly changing ocean.
    Description: This project was funded by the Mineralogical Society of America Edward H. Kraus Crystallographic Research Fund and the WHOI Ocean Ventures Fund. G. Farfan was supported by a National Science Foundation Graduate Research Fellowship Grant No. 1122374 and a Ford Foundation Dissertation Fellowship. Sample collections from R. Waller were funded under NSF Grant Numbers 1245766, 1127582 and NOAA Ocean Exploration Deep Atlantic Stepping Stones. The authors thank Erik Cordes for the samples collected from the Gulf of Mexico, which were supported by NSF BIO-OCE Grant # 1220478. STZC collections from A. Apprill were funded by a Dalio Foundation (now ‘OceanX’) and a KAUST-WHOI Special Academic Partnership Funding Reserve with Christian Voolstra. Research and coral collections in Cuba were conducted under the LH112 AN (25) 2015 license granted by the Cuban Center for Inspection and Environmental Control with the assistance of Patricia Gonzalez and Michael Armenteros. Corals from Western Australia were collected under license number SF009558 obtained by M. McCulloch, and from the Maldives Ministry of Fisheries and Agriculture with collection permits (No. (OTHR)30-D/INDIV/2013/359). Matthew Neave assisted with the collections.
    Keywords: Aragonite ; Crystallography ; Geochemistry ; Biomineralization ; Environmental mineralogy ; Coral skeleton
    Repository Name: Woods Hole Open Access Server
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