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  • 1
    Publication Date: 2022-10-26
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Brinkmann, I., Ni, S., Schweizer, M., Oldham, V. E., Quintana Krupinski, N. B., Medjoubi, K., Somogyi, A., Whitehouse, M. J., Hansel, C. M., Barras, C., Bernhard, J. M., & Filipsson, H. L. Foraminiferal Mn/Ca as bottom-water hypoxia proxy: an assessment of Nonionella stella in the Santa Barbara Basin, USA. Paleoceanography and Paleoclimatology, 36(11), (2021): e2020PA004167, https://doi.org/10.1029/2020PA004167.
    Description: Hypoxia is of increasing concern in marine areas, calling for a better understanding of mechanisms leading to decreasing dissolved oxygen concentrations ([O2]). Much can be learned about the processes and implications of deoxygenation for marine ecosystems using proxy records from low-oxygen sites, provided proxies, such as the manganese (Mn) to calcium (Ca) ratio in benthic foraminiferal calcite, are available and well calibrated. Here we report a modern geochemical data set from three hypoxic sites within the Santa Barbara Basin (SBB), USA, where we study the response of Mn/Caforam in the benthic foraminifer Nonionella stella to variations in sedimentary redox conditions (Mn, Fe) and bottom-water dissolved [O2]. We combine molecular species identification by small subunit rDNA sequencing with morphological characterization and assign the SBB N. stella used here to a new phylotype (T6). Synchrotron-based scanning X-ray fluorescence (XRF) imaging and Secondary Ion Mass Spectrometry (SIMS) show low Mn incorporation (partition coefficient DMn 〈 0.05) and limited proxy sensitivity of N. stella, at least within the range of dissolved [O2] (2.7–9.6 μmol/l) and Mnpore-water gradients (2.12–21.59 μmol/l). Notably, even though intra- and interspecimen Mn/Ca variability (33% and 58%, respectively) was only partially controlled by the environment, Mn/Caforam significantly correlated with both pore-water Mn and bottom-water [O2]. However, the prevalent suboxic bottom-water conditions and limited dissolved [O2] range complicate the interpretation of trace-elemental trends. Additional work involving other oxygenation proxies and samples from a wider oxygen gradient should be pursued to further develop foraminiferal Mn/Ca as an indicator for hypoxic conditions.
    Description: We acknowledge funding from the Swedish Research Council VR (grant numbers 2017-04190 and 2017-00671), the Crafoord Foundation, and the Royal Physiographic Society in Lund, Sweden. Shiptime provided by US NSF IOS 1557430. We acknowledge SOLEIL for provision of synchrotron radiation facilities and the beamline NANOSCOPIUM (proposal number 20181115). The synchrotron-based experiments were supported by CALIPSOplus under the EU Framework Programme for Research and Innovation HORIZON 2020 (grant agreement 730872). The SIMS analyses were jointly supported by the Swedish Museum of Natural History and Swedish Research Council. This is NordSIMS contribution No. 694. J. M. Bernhard and C. M. Hansel also acknowledge funding from the US National Science Foundation (IOS 1557430).
    Keywords: Benthic foraminifera ; Deoxygenation ; Micro-analytical techniques ; Mn/Ca ; Proxy calibration
    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: 2022-05-27
    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
    Type: Article
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