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            <gco:CharacterString>Cite this dataset as: Capece, L. R., Raven, M. R. (2026) Speciation of sulfur in sediment, dissolved organic matter, and biogenic material determined by x-ray absorbance spectroscopy of samples collected at two mangrove locations in June 2022 through February 2024. Biological and Chemical Oceanography Data Management Office (BCO-DMO). (Version 1) Version Date 2026-02-17 [if applicable, indicate subset used]. doi:10.26008/1912/bco-dmo.988595.1 [access date]</gco:CharacterString>
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        <gco:CharacterString>Mangrove x-ray absorbance spectroscopy Dataset Description:  Methods and Sampling: &amp;lt;p&amp;gt;Sediment cores, biomass, and dissolved organic matter were collected from two mangrove locations in Rookery Bay National Estuarine Research Reserve (Florida, USA) and Little Ambergris Caye (Turks and Caicos) during the time period of June 2022 through February 2024 using a 5-centimeter PVC push corer. Sediment cores were extruded in the field and kept at -20 degrees Celsius (°C) until analysis could be carried out back in the lab at UC Santa Barbara along with biogenic material. Dissolved organic matter was kept refrigerated in SPE cartridges until eluted back in the lab at UC Santa Barbara.&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;To isolate major carbon and sulfur pools, a ~1 gram (g) aliquot of the freeze-dried sample from each sediment interval was subjected to two sequential microwave extractions (MARS-6, CEM, 70°C for 15 minutes) using a 9:1 dichloromethane. Solvent-extracted solids were rinsed with 0.7N NaCl solution, ultra-pure water, freeze dried, and then acid fumigated to remove carbonates for 12 hours with a 6N HCl solution. A 500-milligram (mg) subsample of the same microwave-extracted solid residue was then subjected to a strong acid hydrolysis (6N HCl, 60°C, 2 hours) to extract acid-volatile sulfur (AVS, operationally defined as iron monosulfides) following Canfield et al. 1986 and Raven et al. 2019. The remaining solid residue underwent a chromium (II) chloride extraction at 60°C for 2 hours to isolate chromium reducible sulfur (CRS, operationally defined as pyrite) following Canfield et al. 1986. The leftover solid residue following the CRS extraction contains highly hydrolysis-resistant OM that we refer to as protokerogen (Burdige 2007; Raven et al. 2019). Biogenic material went under the same set of extractions while the dissolved organic matter was eluted with methanol and dried down in a fume hood (Phillips et al. 2022).&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;The oxidation state and bonding environment of organic sulfur in the post-CRS extraction, post-CRS extraction biogenic material, and dissolved organic matter were characterized using x-ray absorption spectroscopy (XAS). Spectra were obtained on Stanford Synchrotron Radiation Lightsource (SSRL) on beam line 14–3 using a spot size of 0.5 square millimeters (mm2) and a Si(111) (Φ = 90) double crystal monochromator calibrated to the thiol pre-edge peak of thiosulfate at 2472.02 electron volts (eV). Samples were adhered onto Saint Gobain M60 S-free polyester tape and covered with 5-micrometer (µm) SPEX 3520 polypropylene XRF film. Spectra were averaged and normalized in the SIXPACK (Webb 2005) software package using a K-edge E0 of 2473 and pre-edge and post-edge linear normalization ranges of -20 to -7 and 35 to 70 eV, respectively. The relative abundance (percent (%)) of individual sulfur species were determined in sediments and biomass samples using least squares fitting and a set of OS standards (Raven et al. 2021). The relative abundances of different sulfur species were then used to determine the percentage of reduced (disulfide, monosulfide, aromatic) and oxidized (sulfoxide, sulfone/sulfonate, sulfate ester) sulfur in samples.&amp;lt;/p&amp;gt;</gco:CharacterString>
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Mangrove forest sediments are important hotspots of organic carbon preservation, and they have the potential to sequester substantial amounts of atmospheric CO2. Currently, however, is it not fully understood why these environments are able to bury so much organic carbon, or how they will respond to future changes in sea level, land use, and climate. This project will investigate a mechanism that may help explain this carbon burial: organic matter sulfurization, the transformation and effective ‘pickling’ of sedimentary organic matter by sulfide. Its central aim is to understand what controls the extent of sulfurization in mangrove sediments, and to estimate the contribution of organic matter sulfurization to sediment carbon storage in different parts of the environment. By providing some of the first constraints on how, when, and where organic matter sulfurization happens in mangroves, the results of this work will guide decisionmakers managing coastal watersheds and carbon stocks in the face of land use, climate and sea level change. As part of this work, four undergraduate students and one PhD student at UC Santa Barbara will gain field and research experience. And, in collaboration with local groups associated with the field site, the team will produce a season of ‘Ocean Solutions’ podcast episodes related to conservation and human impacts of Caribbean mangroves.&lt;/p&gt;
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		    <gco:CharacterString>For questions regarding this resource, please contact BCO-DMO via the email address provided.</gco:CharacterString>
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                <gco:CharacterString>&amp;lt;p&amp;gt;Sediment cores, biomass, and dissolved organic matter were collected from two mangrove locations in Rookery Bay National Estuarine Research Reserve (Florida, USA) and Little Ambergris Caye (Turks and Caicos) during the time period of June 2022 through February 2024 using a 5-centimeter PVC push corer. Sediment cores were extruded in the field and kept at -20 degrees Celsius (°C) until analysis could be carried out back in the lab at UC Santa Barbara along with biogenic material. Dissolved organic matter was kept refrigerated in SPE cartridges until eluted back in the lab at UC Santa Barbara.&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;To isolate major carbon and sulfur pools, a ~1 gram (g) aliquot of the freeze-dried sample from each sediment interval was subjected to two sequential microwave extractions (MARS-6, CEM, 70°C for 15 minutes) using a 9:1 dichloromethane. Solvent-extracted solids were rinsed with 0.7N NaCl solution, ultra-pure water, freeze dried, and then acid fumigated to remove carbonates for 12 hours with a 6N HCl solution. A 500-milligram (mg) subsample of the same microwave-extracted solid residue was then subjected to a strong acid hydrolysis (6N HCl, 60°C, 2 hours) to extract acid-volatile sulfur (AVS, operationally defined as iron monosulfides) following Canfield et al. 1986 and Raven et al. 2019. The remaining solid residue underwent a chromium (II) chloride extraction at 60°C for 2 hours to isolate chromium reducible sulfur (CRS, operationally defined as pyrite) following Canfield et al. 1986. The leftover solid residue following the CRS extraction contains highly hydrolysis-resistant OM that we refer to as protokerogen (Burdige 2007; Raven et al. 2019). Biogenic material went under the same set of extractions while the dissolved organic matter was eluted with methanol and dried down in a fume hood (Phillips et al. 2022).&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;The oxidation state and bonding environment of organic sulfur in the post-CRS extraction, post-CRS extraction biogenic material, and dissolved organic matter were characterized using x-ray absorption spectroscopy (XAS). Spectra were obtained on Stanford Synchrotron Radiation Lightsource (SSRL) on beam line 14–3 using a spot size of 0.5 square millimeters (mm2) and a Si(111) (Φ = 90) double crystal monochromator calibrated to the thiol pre-edge peak of thiosulfate at 2472.02 electron volts (eV). Samples were adhered onto Saint Gobain M60 S-free polyester tape and covered with 5-micrometer (µm) SPEX 3520 polypropylene XRF film. Spectra were averaged and normalized in the SIXPACK (Webb 2005) software package using a K-edge E0 of 2473 and pre-edge and post-edge linear normalization ranges of -20 to -7 and 35 to 70 eV, respectively. The relative abundance (percent (%)) of individual sulfur species were determined in sediments and biomass samples using least squares fitting and a set of OS standards (Raven et al. 2021). The relative abundances of different sulfur species were then used to determine the percentage of reduced (disulfide, monosulfide, aromatic) and oxidized (sulfoxide, sulfone/sulfonate, sulfate ester) sulfur in samples.&amp;lt;/p&amp;gt;</gco:CharacterString>
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                <gmd:description>
                  <gco:CharacterString>- Imported original file &amp;quot;988595_v2_mangrove_xas.xlsx&amp;quot; (internal version number) into the BCO-DMO system.
- Created &amp;quot;Year_month&amp;quot; column, containing date in YYYY-MM format.
- Saved the final file as &amp;quot;988595_v1_mangrove_xas.csv&amp;quot;.</gco:CharacterString>
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                <gmd:source>
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                          <gco:CharacterString>Specified by BCO-DMO Data Managers</gco:CharacterString>
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				    <gco:CharacterString>info@bco-dmo.org</gco:CharacterString>
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            <gmd:linkage>
              <gmd:URL>http://www.bco-dmo.org</gmd:URL>
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            <gmd:MD_Identifier>
              <gmd:code>
                <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/instrument/949105.rdf" xlink:title="Microwave Digestion Platform" xlink:actuate="onRequest">MARS-6 microwave CEM</gmx:Anchor>
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            <gco:CharacterString>MARS-6 microwave CEM</gco:CharacterString>
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            <gco:CharacterString>PI Supplied Instrument Name: MARS-6 microwave CEM PI Supplied Instrument Description:Used to extract lipids from sediments Instrument Name: Microwave Digestion Platform Instrument Short Name:   Instrument Description: Microwave digestion is a chemical technique used to decompose sample material into a solution suitable for quantitative elemental analysis</gco:CharacterString>
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      <gmi:instrument>
        <gmi:MI_Instrument>
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            <gmd:MD_Identifier>
              <gmd:code>
                <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/instrument/628287.rdf" xlink:title="Push Corer" xlink:actuate="onRequest">5-centimeter PVC push corer</gmx:Anchor>
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            <gco:CharacterString>PI Supplied Instrument Name: 5-centimeter PVC push corer Instrument Name: Push Corer Instrument Short Name:   Instrument Description: Capable of being performed in numerous environments, push coring is just as it sounds. Push coring is simply pushing the core barrel (often an aluminum or polycarbonate tube) into the sediment by hand. A push core is useful in that it causes very little disturbance to the more delicate upper layers of a sub-aqueous sediment.

Description obtained from: http://web.whoi.edu/coastal-group/about/how-we-work/field-methods/coring/</gco:CharacterString>
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              <gmd:code>
                <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/instrument/993547.rdf" xlink:title="Synchrotron light source" xlink:actuate="onRequest">Stanford Synchrotron Radiation Lightsource (SSRL) on beam line 14–3</gmx:Anchor>
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