The spatial and temporal variability of Mn speciation in the coastal Northwest Atlantic Ocean

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.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.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).2020-06-2

Oxidative Formation and Removal of Complexed Mn(III) by Pseudomonas Species

© 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.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.This work was funded by grants from the Chemical Oceanography program of the National Science Foundation (OCE-1558738 and OCE-1558692)

Inhibited manganese oxide formation hinders cobalt scavenging in the Ross Sea

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.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.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-AC02-76SF00515.2021-10-3

Inhibited Manganese Oxide Formation Hinders Cobalt Scavenging in the Ross Sea

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.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.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-AC02-76SF00515.2021-10-3

DataSheet1.DOCX

<p>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.</p

Dark reduction drives evasion of mercury from the ocean

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Lamborg, C. H., Hansel, C. M., Bowman, K. L., Voelker, B. M., Marsico, R. M., Oldham, V. E., Swarr, G. J., Zhang, T., & Ganguli, P. M. Dark reduction drives evasion of mercury from the ocean. Frontiers in Environmental Chemistry, 2, (2021): 659085, https://doi.org/10.3389/fenvc.2021.659085.Much of the surface water of the ocean is supersaturated in elemental mercury (Hg0) with respect to the atmosphere, leading to sea-to-air transfer or evasion. This flux is large, and nearly balances inputs from the atmosphere, rivers and hydrothermal vents. While the photochemical production of Hg0 from ionic and methylated mercury is reasonably well-studied and can produce Hg0 at fairly high rates, there is also abundant Hg0 in aphotic waters, indicating that other important formation pathways exist. Here, we present results of gross reduction rate measurements, depth profiles and diel cycling studies to argue that dark reduction of Hg2+ is also capable of sustaining Hg0 concentrations in the open ocean mixed layer. In locations where vertical mixing is deep enough relative to the vertical penetration of UV-B and photosynthetically active radiation (the principal forms of light involved in abiotic and biotic Hg photoreduction), dark reduction will contribute the majority of Hg0 produced in the surface ocean mixed layer. Our measurements and modeling suggest that these conditions are met nearly everywhere except at high latitudes during local summer. Furthermore, the residence time of Hg0 in the mixed layer with respect to evasion is longer than that of redox, a situation that allows dark reduction-oxidation to effectively set the steady-state ratio of Hg0 to Hg2+ in surface waters. The nature of these dark redox reactions in the ocean was not resolved by this study, but our experiments suggest a likely mechanism or mechanisms involving enzymes and/or important redox agents such as reactive oxygen species and manganese (III).This work was supported by NSF Grant OCE-1355720 (to CH, CL, and BV)

Foraminiferal Mn/Ca as bottom-water hypoxia proxy: an assessment of Nonionella stella in the Santa Barbara Basin, USA

© 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.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.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)

Effect of Marine Antifouling Paint Particles Waste on Survival of Natural Bermuda Copepod Communities

Marine antifouling paints (MAPs) are widely used to prevent organisms from fouling vessel hulls. When scraped from vessels as part of regular maintenance, MAP particles discharged into the seawater become a source of toxic substances, like copper (Cu), to the environment, and biocides leaching from them are known to cause toxic effects on non-target organisms. We investigated the toxicity of MAP particles collected from a Bermuda boatyard on local copepod communities using two experiments. Copepod survival, Chlorophyll a and total dissolved Cu concentrations were measured before and after MAP particles addition. In an acute toxicity test, the addition of 0.3 g/L of MAP particles resulted in 0% copepods survival within 88 h and increased dissolved Cu by 1.8 μM. A significant inverse relationship was observed between copepod survival and MAP particles quantity, highlighting the toxic effects of MAP particles from boat maintenance on copepod communities in the surrounding seawater