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Title: Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging

Abstract

Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8–51 μm) and large size fraction (LSF; >51 μm) particles from the near-field and far-field plumes were examined using micro X-ray fluorescence spectrometry (μ-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of ~30%. They are a mixture of δ-MnO2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed δ-MnO2, suggesting that both microbial andmore » autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of μm in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, 231Pa are associated with pMn, but not in the far-field plume. 231Pa is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn. Our findings suggest that the mineralogical age of Mn oxides may be an important parameter that controls the scavenging of many other trace elements and isotopes.« less

Authors:
 [1];  [1]; ORCiD logo [2];  [3];  [2];  [4];  [5]; ORCiD logo [5];  [6];  [1];  [7]
+ Show Author Affiliations
  1. Univ. of California, Santa Cruz, CA (United States)
  2. Columbia Univ., Palisades, NY (United States). Lamont-Doherty Earth Observatory; Columbia Univ., New York, NY (United States)
  3. Columbia Univ., Palisades, NY (United States). Lamont-Doherty Earth Observatory; Columbia Univ., New York, NY (United States); California Institute of Technology (CalTech), Pasadena, CA (United States)
  4. Univ. of Minnesota, Minneapolis, MN (United States); Nanyang Technological Univ. (Singapore). Earth Observatory of Singapore
  5. Univ. of Minnesota, Minneapolis, MN (United States); Xi'an Jiaotong Univ. (China). Inst. of Global Environmental Change
  6. Univ. of Minnesota, Minneapolis, MN (United States)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF); National Institutes of Health (NIH)
OSTI Identifier:
1788039
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231; P30GM133894; OCE-1518110; OCE-1233688; OCE-1233903
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 300; Journal ID: ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; manganese; particle chemistry; hydrothermal plume particles; scavenging; micro x-ray fluorescence spectrometry; x-ray absorption near edge structure spectroscopy; x-ray microprobe chemical speciation mapping; extended x-ray absorption fine-structure spectroscopy; East Pacific Rise; GEOTRACES GP16; Eastern Pacific Zonal Transect

Citation Formats

Lee, Jong-Mi, Lam, Phoebe J., Vivancos, Sebastian M., Pavia, Frank J., Anderson, Robert F., Lu, Yanbin, Cheng, Hai, Zhang, Pu, Edwards, R. Lawrence, Xiang, Yang, and Webb, Samuel M. Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging. United States: N. p., 2021. Web. doi:10.1016/j.gca.2021.02.020.
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Lee, Jong-Mi, Lam, Phoebe J., Vivancos, Sebastian M., Pavia, Frank J., Anderson, Robert F., Lu, Yanbin, Cheng, Hai, Zhang, Pu, Edwards, R. Lawrence, Xiang, Yang, & Webb, Samuel M. Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging. United States. https://doi.org/10.1016/j.gca.2021.02.020
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Lee, Jong-Mi, Lam, Phoebe J., Vivancos, Sebastian M., Pavia, Frank J., Anderson, Robert F., Lu, Yanbin, Cheng, Hai, Zhang, Pu, Edwards, R. Lawrence, Xiang, Yang, and Webb, Samuel M. Sun . "Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging". United States. https://doi.org/10.1016/j.gca.2021.02.020. https://www.osti.gov/servlets/purl/1788039.
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@article{osti_1788039,
title = {Changing chemistry of particulate manganese in the near- and far-field hydrothermal plumes from 15°S East Pacific Rise and its influence on metal scavenging},
author = {Lee, Jong-Mi and Lam, Phoebe J. and Vivancos, Sebastian M. and Pavia, Frank J. and Anderson, Robert F. and Lu, Yanbin and Cheng, Hai and Zhang, Pu and Edwards, R. Lawrence and Xiang, Yang and Webb, Samuel M.},
abstractNote = {Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8–51 μm) and large size fraction (LSF; >51 μm) particles from the near-field and far-field plumes were examined using micro X-ray fluorescence spectrometry (μ-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of ~30%. They are a mixture of δ-MnO2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed δ-MnO2, suggesting that both microbial and autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of μm in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, 231Pa are associated with pMn, but not in the far-field plume. 231Pa is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn. Our findings suggest that the mineralogical age of Mn oxides may be an important parameter that controls the scavenging of many other trace elements and isotopes.},
doi = {10.1016/j.gca.2021.02.020},
journal = {Geochimica et Cosmochimica Acta},
number = ,
volume = 300,
place = {United States},
year = {Sun Feb 21 00:00:00 EST 2021},
month = {Sun Feb 21 00:00:00 EST 2021}
}
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  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 28
  • DOI: 10.1073/pnas.1305530110

Surface-Generated Mesoscale Eddies Transport Deep-Sea Products from Hydrothermal Vents
journal, April 2011

Manganese scavenging and oxidation at hydrothermal vents and in vent plumes
journal, August 1993

Manganese geochemistry in the Guaymas Basin, Gulf of California
journal, February 1988

  • Campbell, Andrew C.; Gieskes, Joris M.; Lupton, John E.
  • Geochimica et Cosmochimica Acta, Vol. 52, Issue 2
  • DOI: 10.1016/0016-7037(88)90090-7

Size distribution of particulate trace elements in the U.S. GEOTRACES Eastern Pacific Zonal Transect (GP16)
journal, April 2018

Geomicrobial transformation of manganese in Gorda Ridge event plumes
journal, December 1998

  • Cowen, James P.; Bertram, Miriam A.; Baker, Edward T.
  • Deep Sea Research Part II: Topical Studies in Oceanography, Vol. 45, Issue 12
  • DOI: 10.1016/S0967-0645(98)00090-3

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides
journal, December 2008

  • Wasylenki, Laura E.; Rolfe, Bryan A.; Weeks, Colin L.
  • Geochimica et Cosmochimica Acta, Vol. 72, Issue 24
  • DOI: 10.1016/j.gca.2008.08.027

Variability in 210Pb and 210Po partition coefficients (Kd) along the US GEOTRACES Arctic transect
journal, February 2020

Mechanisms of Pb(II) Sorption on a Biogenic Manganese Oxide
journal, January 2005

  • Villalobos, Mario; Bargar, John; Sposito, Garrison
  • Environmental Science & Technology, Vol. 39, Issue 2
  • DOI: 10.1021/es049434a

Anoxic aggregates - an ephemeral phenomenon in the pelagic environment?
journal, January 1997

  • Ploug, H.; Kühl, M.; Buchholz-Cleven, B.
  • Aquatic Microbial Ecology, Vol. 13
  • DOI: 10.3354/ame013285

Intensity of Th and Pa scavenging partitioned by particle chemistry in the North Atlantic Ocean
journal, March 2015

Size-fractionated major particle composition and concentrations from the US GEOTRACES North Atlantic Zonal Transect
journal, June 2015

  • Lam, Phoebe J.; Ohnemus, Daniel C.; Auro, Maureen E.
  • Deep Sea Research Part II: Topical Studies in Oceanography, Vol. 116
  • DOI: 10.1016/j.dsr2.2014.11.020

Manganese(II) oxidation kinetics on metal oxide surfaces
journal, April 1989

Precipitates from hydrothermal exhalations on the East Pacific rise
journal, November 1966

BIOGENIC MANGANESE OXIDES: Properties and Mechanisms of Formation
journal, May 2004

Identification and characterization of a gene cluster involved in manganese oxidation by spores of the marine Bacillus sp. strain SG-1.
journal, June 1996

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