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  • 1
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2021. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 35(5), (2021): e2020GB006706, https://doi.org/10.1029/2020GB006706.
    Description: The Southern Ocean plays a critical role in regulating global uptake of atmospheric CO2. Trace elements like iron (Fe), cobalt (Co), and manganese (Mn) have been shown to modulate this primary productivity. Despite limited data, the vertical profiles for Mn, Fe, and Co in the Ross Sea show no evidence of scavenging, as typically observed in oceanic sites. This was previously attributed to low-particle abundance and/or by mixing rates exceeding scavenging rates. Scavenging of some trace metals such as cobalt (Co) is thought to be largely governed by Mn (oxyhydr)oxides, assumed to be the main component of particulate Mn (pMn). However, our data show that pMn has an average oxidation state below 3 and with nondetectable Mn oxides. In addition, soluble Co profiles show no evidence of scavenging and Co uptake measurements show little Co uptake in the euphotic zone and low/no scavenging at depth. Instead, high concentrations of dissolved Mn (dMn, up to 90 nM), which is primarily complexed as Mn(III)-L (up to 100%), are observed. Average dMn concentrations (10 ± 14 nM) are highest in bottom and surface waters. Manganese sources may include sediments and sea-ice melt, as elevated dMn was measured in sea ice (12 nM) compared to its surrounding waters (3 nM), and sea ice dMn was 97% Mn(III)-L. We contend that the lack of Co scavenging in the Ross Sea is due to a unique Mn redox cycle that favors the stabilization of Mn(III)-complexes at the expense of Mn oxide particle formation.
    Description: The authors acknowledge support from the NSF 1643684 (MS), NSF 1644073 (GRD), NSF OCE-1355720 (CMH), and the Woods Hole Oceanographic Institution Post-Doctoral Scholarship (VEO). The Stanford Synchrotron Radiation Lightsource was utilized in this study. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.
    Description: 2021-10-30
    Keywords: Cobalt ; Manganese ; Redox ; Ross sea ; Scavenging ; Southern Ocean
    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, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research-Oceans 125(1),(2020): e2019JC015167, doi:10.1029/2019JC015167.
    Description: Manganese (Mn) is distributed widely throughout the global ocean, where it cycles between three oxidation states that each play important biogeochemical roles. The speciation of Mn in seawater was previously operationally defined on filtration, with soluble Mn presumed to be Mn(II) and solid‐phase Mn as Mn(III/IV) oxides. Recent findings of abundant soluble Mn(III) complexes (Mn(III)‐L) highlights the need to reexamine the redox cycling of Mn, as these complexes can donate or accept electrons. To better understand the complex cycling of Mn in coastal waters, the distribution of Mn species at four Northwest Atlantic sites with different characteristics was examined. Diurnal influences on Mn speciation were investigated within a productive site. At all sites, Mn(III)‐L complexes dominated, particularly in surface waters, and Mn oxides were low in abundance in surface waters but high in bottom waters. Despite intrasite similarities, Mn speciation was highly variable between our stations, emphasizing the diverse processes that impact Mn redox. Diel Mn measurements revealed that the cycling of Mn is also highly variable over time, even on time scales as short as hours. We observed a change of over 100 nM total Mn over 17 hrs and find that speciation changed drastically. These changes could include contributions from biological, light‐mediated, and/or abiotic mechanisms but more likely point to the importance of lateral mixing at coastal sites. This exploration demonstrates the spatial and temporal variability of the Mn redox cycle and indicates that single timepoint vertical profiling is not sufficient when describing the geochemistry of dynamic coastal systems.
    Description: This work was funded by grants from the Chemical Oceanography program of the National Science Foundation (OCE‐1355720 to CMH and CHL). Véronique Oldham thanks Woods Hole Oceanographic Institution for the receipt of the WHOI Postdoctoral Scholarship. Thanks also to Kevin Sutherland, Jen Karolweski, Gabriella Farfan, Kalina Grabb, Kaitlin Bowman, Alison Agather, and Lindsey Starr for the shipboard sampling assistance, as well as the captain and crew of the R/V Endeavor who made the sampling for this research possible. All data presented in the manuscript are available through the Biological and Chemical Oceanography Data Management Office (BCO‐DMO) under Project 756930 at the following link (https://www.bco‐dmo.org/project/756930).
    Description: 2020-06-20
    Keywords: Manganese ; Redox ; Trace Metal ; Diel Cycle ; Coastal Ocean ; Organic Complexation
    Repository Name: Woods Hole Open Access Server
    Type: Article
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