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  • Mn(III)-citrate  (1)
  • Mn/Ca  (1)
  • 1
    Publication Date: 2022-05-25
    Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Frontiers in Microbiology 9 (2018): 560, doi:10.3389/fmicb.2018.00560.
    Description: The observation of significant concentrations of soluble Mn(III) complexes in oxic, suboxic, and some anoxic waters has triggered a re-evaluation of the previous Mn paradigm which focused on the cycling between soluble Mn(II) and insoluble Mn(III,IV) species as operationally defined by filtration. Though Mn(II) oxidation in aquatic environments is primarily bacterially-mediated, little is known about the effect of Mn(III)-binding ligands on Mn(II) oxidation nor on the formation and removal of Mn(III). Pseudomonas putida GB-1 is one of the most extensively investigated of all Mn(II) oxidizing bacteria, encoding genes for three Mn oxidases (McoA, MnxG, and MopA). P. putida GB-1 and associated Mn oxidase mutants were tested alongside environmental isolates Pseudomonas hunanensis GSL-007 and Pseudomonas sp. GSL-010 for their ability to both directly oxidize weakly and strongly bound Mn(III), and to form these complexes through the oxidation of Mn(II). Using Mn(III)-citrate (weak complex) and Mn(III)-DFOB (strong complex), it was observed that P. putida GB-1, P. hunanensis GSL-007 and Pseudomonas sp. GSL-010 and mutants expressing only MnxG and McoA were able to directly oxidize both species at varying levels; however, no oxidation was detected in cultures of a P. putida mutant expressing only MopA. During cultivation in the presence of Mn(II) and citrate or DFOB, P. putida GB-1, P. hunanensis GSL-007 and Pseudomonas sp. GSL-010 formed Mn(III) complexes transiently as an intermediate before forming Mn(III/IV) oxides with the overall rates and extents of Mn(III,IV) oxide formation being greater for Mn(III)-citrate than for Mn(III)-DFOB. These data highlight the role of bacteria in the oxidative portion of the Mn cycle and suggest that the oxidation of strong Mn(III) complexes can occur through enzymatic mechanisms involving multicopper oxidases. The results support the observations from field studies and further emphasize the complexity of the geochemical cycling of manganese.
    Description: This work was funded by grants from the Chemical Oceanography program of the National Science Foundation (OCE-1558738 and OCE-1558692).
    Keywords: Manganese(III) ; Mn(III)-DFOB ; Mn(III)-citrate ; Mn(III)-L ; Pseudomonas ; Bacterial manganese oxidation
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    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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