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Title: Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots

Abstract

Coastal environments like mangrove forests are increasingly recognized as potential hotspots for organic carbon burial, giving them a crucial and yet poorly constrained role in the global carbon cycle. Mangrove sediments are frequently anoxic, which facilitates elevated organic matter (OM) burial via several mechanisms, including sulfurization – abiotic reactions between dissolved (poly)sulfide and OM that decrease its lability. Although sulfurization was estimated to account for roughly half of OM preservation in a Bermuda mangrove forest, both its mechanisms and its global significance remain poorly understood. In this study, we investigate S cycling in mangrove forest sediments from Little Ambergris Cay, Turks and Caicos Islands, an environment with predominantly microbial OM inputs and no major source of terrestrial iron. We characterize the S- and C-isotope composition and organic S speciation of sedimentary OM fractions with varying degrees of resistance to acid hydrolysis, along with other inorganic S phases. Near the surface of a 3-mm-diameter, O 2-releasing root, abundant organic and elemental S with a 34S-depleted composition indicates microbial sulfur cycling and OM sulfurization. A mixture of pyrite, elemental S, and organic S form a plaque within the outer 50 μm of the root, which also contains strongly 34S-depleted sulfate in itsmore » xylem. OM sulfurization products in the sediments include both the alkyl sulfides and disulfides associated with the root plaque and more oxidized forms, especially sulfonates. Hydrolysis-resistant organic S in the sediments is consistently 3–5‰ more 34S-enriched than coexisting elemental S, matching the reported kinetic isotope fractionation factor for OM sulfurization via reaction with polysulfides. These sediments also contain a substantial pool of solid-phase, hydrolyzable organic S with a seawater sulfate-like isotope composition, largely in the form of sulfate esters, which may represent excretions from abundant gastropods. The coexistance of sulfurized OM and aerobic macrofauna highlights how understanding spatial scales and/or temporal cycles in local redox state is critical for predicting net OM preservation, especially in dynamic, coastal environments. Future attempts to mechanistically predict changes in carbon storage in coastal systems will benefit from incorporating OM sulfurization as both a sink for microbially produced sulfide and a mechanism for enhanced carbon sequestration.« less

Authors:
 [1];  [2];  [3];  [4]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. Johns Hopkins Univ., Baltimore, MD (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; Dept. of Environment and Coastal Resources (DECR); Turks and Caicos Island Gov't.
OSTI Identifier:
1528860
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Frontiers in Earth Science
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2296-6463
Publisher:
Frontiers Research Foundation
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; X-ray absorption spectroscopy; sulfur isotope; coastal carbon cycle; organic sulfur; organic matter liability; mangrove sediment; sulfurization

Citation Formats

Raven, M. R., Fike, D. A., Gomes, M. L., and Webb, S. M. Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots. United States: N. p., 2019. Web. doi:10.3389/feart.2019.00098.
Raven, M. R., Fike, D. A., Gomes, M. L., & Webb, S. M. Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots. United States. doi:10.3389/feart.2019.00098.
Raven, M. R., Fike, D. A., Gomes, M. L., and Webb, S. M. Wed . "Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots". United States. doi:10.3389/feart.2019.00098. https://www.osti.gov/servlets/purl/1528860.
@article{osti_1528860,
title = {Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots},
author = {Raven, M. R. and Fike, D. A. and Gomes, M. L. and Webb, S. M.},
abstractNote = {Coastal environments like mangrove forests are increasingly recognized as potential hotspots for organic carbon burial, giving them a crucial and yet poorly constrained role in the global carbon cycle. Mangrove sediments are frequently anoxic, which facilitates elevated organic matter (OM) burial via several mechanisms, including sulfurization – abiotic reactions between dissolved (poly)sulfide and OM that decrease its lability. Although sulfurization was estimated to account for roughly half of OM preservation in a Bermuda mangrove forest, both its mechanisms and its global significance remain poorly understood. In this study, we investigate S cycling in mangrove forest sediments from Little Ambergris Cay, Turks and Caicos Islands, an environment with predominantly microbial OM inputs and no major source of terrestrial iron. We characterize the S- and C-isotope composition and organic S speciation of sedimentary OM fractions with varying degrees of resistance to acid hydrolysis, along with other inorganic S phases. Near the surface of a 3-mm-diameter, O2-releasing root, abundant organic and elemental S with a 34S-depleted composition indicates microbial sulfur cycling and OM sulfurization. A mixture of pyrite, elemental S, and organic S form a plaque within the outer 50 μm of the root, which also contains strongly 34S-depleted sulfate in its xylem. OM sulfurization products in the sediments include both the alkyl sulfides and disulfides associated with the root plaque and more oxidized forms, especially sulfonates. Hydrolysis-resistant organic S in the sediments is consistently 3–5‰ more 34S-enriched than coexisting elemental S, matching the reported kinetic isotope fractionation factor for OM sulfurization via reaction with polysulfides. These sediments also contain a substantial pool of solid-phase, hydrolyzable organic S with a seawater sulfate-like isotope composition, largely in the form of sulfate esters, which may represent excretions from abundant gastropods. The coexistance of sulfurized OM and aerobic macrofauna highlights how understanding spatial scales and/or temporal cycles in local redox state is critical for predicting net OM preservation, especially in dynamic, coastal environments. Future attempts to mechanistically predict changes in carbon storage in coastal systems will benefit from incorporating OM sulfurization as both a sink for microbially produced sulfide and a mechanism for enhanced carbon sequestration.},
doi = {10.3389/feart.2019.00098},
journal = {Frontiers in Earth Science},
number = ,
volume = 7,
place = {United States},
year = {2019},
month = {5}
}

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