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            <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/dataset/661659.rdf" xlink:actuate="onRequest">Sulfate reduction energetics at Main Endeavor grotto chimney from samples collected on RV Atlantis (AT18-08) during Jason II dives in the Juan de Fuca Ridge from July to August 2011</gmx:Anchor>
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            <gco:CharacterString>Cite this dataset as: Girguis, P., Rogers, K. (2016) Sulfate reduction energetics at Main Endeavor grotto chimney from samples collected on RV Atlantis (AT18-08) during Jason II dives in the Juan de Fuca Ridge from July to August 2011. Biological and Chemical Oceanography Data Management Office (BCO-DMO). (Version 1) Version Date 2016-10-14 [if applicable, indicate subset used]. doi:10.1575/1912/bco-dmo.661659.1 [access date]</gco:CharacterString>
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        <gco:CharacterString>Sulfate reduction energetics at Main Endeavor grotto chimney. Dataset Description: &amp;lt;p&amp;gt;The effects of key environmental variables (temperature, pH, H2S, SO42-, DOC) on sulfate reduction energetics in material recovered from a hydrothermal flange from the Grotto edifice in the Main Endeavor Field, Juan de Fuca Ridge. Sulfate reduction was measured in batch reactions across a range of&amp;amp;nbsp;physico-chemical&amp;amp;nbsp;conditions. Temperature and pH were the strongest stimuli, and maximum sulfate reduction rates were observed at 50 degrees celsius and pH 6.&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;Information for this dataset was derived from single massive piece of hydrothermal deposit (approximately ~100 kg in weight) that was recovered from a flange on the Grotto&amp;amp;nbsp;vent&amp;amp;nbsp;(47.949, -129.098) at a depth of 2188.3 m (Dive J2-575, AT-18-08,&amp;amp;nbsp;R/V Atlantis) and brought up to the surface in the basket of the&amp;amp;nbsp;ROV Jason II.&amp;amp;nbsp;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;&amp;lt;strong&amp;gt;Methodology for this dataset is from: Frank et al., 2015&amp;lt;/strong&amp;gt;&amp;lt;/p&amp;gt; Methods and Sampling: &amp;lt;p&amp;gt;&amp;lt;strong&amp;gt;Tables and Figures referenced in the acquisition description are found in the paper Frank et al., 2015&amp;lt;/strong&amp;gt;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;For each independent treatment, aliquots of 7.5 mL flange slurry (approx. 29 g wet weight and 20 g dry weight) were transferred into Balch tubes in an anaerobic chamber, and supplemented with 15 mL of sterile artificial seawater media designed to mimic the geochemical conditions within a hydrothermal flange (400 mM NaCl, 25 mM KCl, 30 mM CaCl2, 2.3 mM NaHCO3, 14 mM NaSO42-, 1 mM H2S, and 50 uM dissolved organic carbon - consisting of equimolar proportions 10 uM of pyruvate, citrate, formate, acetate, lactate) under a pure nitrogen headspace.&amp;amp;nbsp;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;Concentrations of sulfide, sulfate and dissolved organic carbon (DOC) were varied independently to investigate concentration dependent effects on the rates of SR. The range of experimental conditions tested was determined from previously published concentration profiles of aqueous species modeled as functions of temperature and position within the Grotto vent structure (Tivey, 2004). Concentrations were varied by orders of magnitude within the modeled ranges to simulate conditions representative of different mixing regimes between seawater and vent fluid (Table 1). The range of DOC (which we approximate as a mix of pyruvate, citrate, formate, acetate, lactate – most of which have been identified to varying degrees within vent fluid and are known carbon sources for heterotrophic SR in culture) concentrations tested were based on the average DOC concentrations measured within diffuse fluids at the Main Endeavor Field (Lang&amp;amp;nbsp;et al., 2006; Lang&amp;amp;nbsp;et al.,&amp;amp;nbsp;2010). Hydrogen sulfide was present as H2S (pKa&amp;amp;nbsp;in seawater of 6.60) across all the conditions tested (Amend &amp;amp;amp; Shock, 2001). Incubations were carried out at pH 4 (to simulate the pH of end-member Grotto vent fluid and the average calculated pH of&amp;amp;nbsp;mixed fluids in highly reduced zones within the flange; Tivey 2004) as well as pH 6 (representative of the calculated pH in fluid mixing zones; Tivey 2004). All the results are presented and discussed in the context of the initial measured media conditions.&amp;lt;/p&amp;gt;</gco:CharacterString>
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        <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/award/554913.rdf" xlink:title="OCE-1061934" xlink:actuate="onRequest">Funding provided by NSF Division of Ocean Sciences (NSF OCE) Award Number: OCE-1061934 Award URL: https://www.nsf.gov/awardsearch/show-award?AWD_ID=1061934</gmx:Anchor>
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        <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/award/626305.rdf" xlink:title="OCE-0838107" xlink:actuate="onRequest">Funding provided by NSF Division of Ocean Sciences (NSF OCE) Award Number: OCE-0838107 Award URL: https://www.nsf.gov/awardsearch/show-award?AWD_ID=0838107</gmx:Anchor>
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        <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/award/626308.rdf" xlink:title="NNX09AB78G" xlink:actuate="onRequest">Funding provided by NASA Astrobiology Science &amp; Technology for Exploring Planets (NASA-ASTEP) Award Number: NNX09AB78G</gmx:Anchor>
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        <gmx:Anchor xlink:href="http://lod.bco-dmo.org/id/award/626309.rdf" xlink:title="NNX07AV51G" xlink:actuate="onRequest">Funding provided by NASA Astrobiology Science &amp; Technology for Exploring Planets (NASA-ASTEP) Award Number: NNX07AV51G</gmx:Anchor>
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Note: Katrina Edwards was a former PI of C-DEBI; James Cowen is a former co-PI.
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            http://lod.bco-dmo.org/id/dataset-parameter/661704.rdf
	Name: experiment_num
	Units: unitless
	Description: &lt;p&gt;PI issued experiment ID number&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661705.rdf
	Name: sulfide
	Units: molar (M)
	Description: &lt;p&gt;Independently varied concentration of sulfide&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661706.rdf
	Name: sulfate
	Units: millimoles (mM)
	Description: &lt;p&gt;Independently varied concentration of sulfate&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661707.rdf
	Name: DOC
	Units: micromoles (uM)
	Description: &lt;p&gt;Independently varied dissolved oxygen concentration&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661708.rdf
	Name: citrate
	Units: molar (M)
	Description: &lt;p&gt;Citrate concentration which made up DOC&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661709.rdf
	Name: formate
	Units: molar (M)
	Description: &lt;p&gt;Formate concentration which made up DOC&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661710.rdf
	Name: pyruvate
	Units: molar (M)
	Description: &lt;p&gt;Pyruvate concentration which made up DOC&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661711.rdf
	Name: acetate
	Units: molar (M)
	Description: &lt;p&gt;Acetate concentration which made up DOC&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661712.rdf
	Name: lactate
	Units: molar (M)
	Description: &lt;p&gt;Lactate concentration which made up DOC&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661713.rdf
	Name: bicarbonate
	Units: millimoles (mM)
	Description: &lt;p&gt;Concentration of bicarbonate which made up artificial seawater mix&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661714.rdf
	Name: K
	Units: molar (M)
	Description: &lt;p&gt;Concentration of K which made up artificial seawater mix&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661715.rdf
	Name: Ca
	Units: molar (M)
	Description: &lt;p&gt;Concentration of Ca which made up artificial seawater mix&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661716.rdf
	Name: Na
	Units: molar (M)
	Description: &lt;p&gt;Concentration of Na which made up artificial seawater mix&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661717.rdf
	Name: Cl
	Units: molar (M)
	Description: &lt;p&gt;Concentration of Cl which made up artificial seawater mix&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661718.rdf
	Name: pH
	Units: pH
	Description: &lt;p&gt;pH of media added to incubations; Incubations were carried out at either pH 4 or 6; 4: simulates the pH of end-member Grotto vent fluid and the average calculated pH of mixed fluids in highly reduced zones within flange (Tivey 2004). 6: represents the calculated pH in fluid mixing zones (Tivey 2004).&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661719.rdf
	Name: temperature
	Units: celsius (C)
	Description: &lt;p&gt;Temperatures at which samples were incubated anaerobically for 1 3 or 7 days. 4 C: ambient seawater; 50 C: thermophilic; 90 C: hyperthermophilic.&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661720.rdf
	Name: sulfateRed_formate
	Units: DeltaGr KJ/mol e-
	Description: &lt;p&gt;(DeltaGr KJ/mol e-) of formate calculated at pH 6 and 50 deg C for heterotrophic sulfate reduction via organic acids&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661721.rdf
	Name: sulfateRed_acetate
	Units: DeltaGr KJ/mol e-
	Description: &lt;p&gt;(DeltaGr KJ/mol e-) of acetate calculated at pH 6 and 50 deg C for heterotrophic sulfate reduction via organic acids&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661722.rdf
	Name: sulfateRed_pyruvate
	Units: DeltaGr KJ/mol e-
	Description: &lt;p&gt;(DeltaGr KJ/mol e-) of pyruvate calculated at pH 6 and 50 deg C for heterotrophic sulfate reduction via organic acids&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661723.rdf
	Name: sulfateRed_lactate
	Units: DeltaGr KJ/mol e-
	Description: &lt;p&gt;(DeltaGr KJ/mol e-) of lactate calculated at pH 6 and 50 deg C for heterotrophic sulfate reduction via organic acids&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661724.rdf
	Name: sulfateRed_citrate
	Units: DeltaGr KJ/mol e-
	Description: &lt;p&gt;(DeltaGr KJ/mol e-) of citrate calculated at pH 6 and 50 deg C for heterotrophic sulfate reduction via organic acids&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661725.rdf
	Name: c_limiting_totalEnergy
	Units: joules (J)
	Description: &lt;p&gt;Carbon limiting total energy available in bottle for sulfate reduction&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661726.rdf
	Name: S_limiting_totalEnergy
	Units: joules (J)
	Description: &lt;p&gt;Sulfate limiting total energy available in bottle for sulfate reduction&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661727.rdf
	Name: total_energy
	Units: joules (J)
	Description: &lt;p&gt;Total energy available for sulfate reduction&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661821.rdf
	Name: lat
	Units: decimal degrees
	Description: &lt;p&gt;Latitude&lt;/p&gt; 
http://lod.bco-dmo.org/id/dataset-parameter/661822.rdf
	Name: lon
	Units: decimal degrees
	Description: &lt;p&gt;Longitude&lt;/p&gt; 
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&amp;lt;p&amp;gt;For each independent treatment, aliquots of 7.5 mL flange slurry (approx. 29 g wet weight and 20 g dry weight) were transferred into Balch tubes in an anaerobic chamber, and supplemented with 15 mL of sterile artificial seawater media designed to mimic the geochemical conditions within a hydrothermal flange (400 mM NaCl, 25 mM KCl, 30 mM CaCl2, 2.3 mM NaHCO3, 14 mM NaSO42-, 1 mM H2S, and 50 uM dissolved organic carbon - consisting of equimolar proportions 10 uM of pyruvate, citrate, formate, acetate, lactate) under a pure nitrogen headspace.&amp;amp;nbsp;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;Concentrations of sulfide, sulfate and dissolved organic carbon (DOC) were varied independently to investigate concentration dependent effects on the rates of SR. The range of experimental conditions tested was determined from previously published concentration profiles of aqueous species modeled as functions of temperature and position within the Grotto vent structure (Tivey, 2004). Concentrations were varied by orders of magnitude within the modeled ranges to simulate conditions representative of different mixing regimes between seawater and vent fluid (Table 1). The range of DOC (which we approximate as a mix of pyruvate, citrate, formate, acetate, lactate – most of which have been identified to varying degrees within vent fluid and are known carbon sources for heterotrophic SR in culture) concentrations tested were based on the average DOC concentrations measured within diffuse fluids at the Main Endeavor Field (Lang&amp;amp;nbsp;et al., 2006; Lang&amp;amp;nbsp;et al.,&amp;amp;nbsp;2010). Hydrogen sulfide was present as H2S (pKa&amp;amp;nbsp;in seawater of 6.60) across all the conditions tested (Amend &amp;amp;amp; Shock, 2001). Incubations were carried out at pH 4 (to simulate the pH of end-member Grotto vent fluid and the average calculated pH of&amp;amp;nbsp;mixed fluids in highly reduced zones within the flange; Tivey 2004) as well as pH 6 (representative of the calculated pH in fluid mixing zones; Tivey 2004). All the results are presented and discussed in the context of the initial measured media conditions.&amp;lt;/p&amp;gt;</gco:CharacterString>
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&amp;lt;p&amp;gt;Potential energy yields of the different metabolisms available in the incubations depend on temperature and fluid compositions. To quantify the energy yield from heterotrophic sulfate reduction (Table 2) in each incubation values of overall Gibbs energy () were calculated according to:&amp;lt;/p&amp;gt;

&amp;lt;p class=&amp;quot;rtecenter&amp;quot;&amp;gt;&amp;lt;img alt=&amp;quot;&amp;quot; src=&amp;quot;https://datadocs.bco-dmo.org/d3/data_docs/GrottoSRR/SRenergetics1.png&amp;quot; style=&amp;quot;height:70px; width:300px&amp;quot; /&amp;gt;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;where&amp;amp;nbsp; is the standard Gibbs energy of reaction at &amp;lt;em&amp;gt;in situ&amp;lt;/em&amp;gt; temperature and pressure conditions, R is the gas constant, T is the temperature (Kelvin), and Q is the activity product, defined as&amp;lt;/p&amp;gt;

&amp;lt;p class=&amp;quot;rtecenter&amp;quot;&amp;gt;&amp;lt;img alt=&amp;quot;&amp;quot; src=&amp;quot;https://datadocs.bco-dmo.org/d3/data_docs/GrottoSRR/SRenergetics2.png&amp;quot; style=&amp;quot;height:70px; width:200px&amp;quot; /&amp;gt;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;where &amp;lt;em&amp;gt;a&amp;lt;sub&amp;gt;i&amp;lt;/sub&amp;gt;&amp;lt;/em&amp;gt; represents the activity of the &amp;lt;em&amp;gt;i&amp;lt;/em&amp;gt;th species and &amp;lt;em&amp;gt;v&amp;lt;sub&amp;gt;i &amp;lt;/sub&amp;gt;&amp;lt;/em&amp;gt;is the stoichiometric reaction coefficient, which is positive for products and negative for reactants. Values of&amp;amp;nbsp; were calculated at 1 bar and incubation temperatures using the geochemical software package SUPCRT92 (Johnson &amp;lt;em&amp;gt;et al.&amp;lt;/em&amp;gt;, 1992) and additional thermodynamic data from (Shock, 1995). Activities of aqueous species were calculated using the geochemical speciation program EQ3 (Wolery, 1992) based on the media composition described in section 2.2 and Table 1, with additional data from previously published work (Shock, 1995; Shock &amp;amp;amp; Koretsky, 1993). For concentrations equal to zero, a value of 10&amp;lt;sup&amp;gt;-13&amp;lt;/sup&amp;gt; mol/kg was used as input. Resulting aqueous activities were used to calculate values of&amp;amp;nbsp; normalized for the number of electrons transferred in the redox for the reactions in Table 2. These reflect the metabolic energy available at the start of each incubation experiment for the complete oxidation of each organic acid, metabolisms that are documented among known sulfate reducers (Amend and Shock, 2001). Furthermore, to calculate the energy density in each incubation (as in Amend &amp;lt;em&amp;gt;et al.&amp;lt;/em&amp;gt;, 2011), it was assumed that the amended organic acids were the limiting reactant for all experiments when sulfate concentrations were in excess of 1 mM; otherwise sulfate was assumed to be limiting. While some sulfate reducers are known to produce carboxylic acid and alcohol intermediates, incomplete oxidation reactions were not considered here, as the goal of these calculations was to generate a broad understanding of sulfate reduction energetics, and not the metabolic potential for a particular species. Such an approach is common when comparing microbial metabolisms independent of species-specific pathways (e.g. Amend &amp;lt;em&amp;gt;et al.&amp;lt;/em&amp;gt;, 2004; Rogers &amp;amp;amp; Amend, 2006; Skoog &amp;lt;em&amp;gt;et al.,&amp;lt;/em&amp;gt; 2007), although it should be noted that incomplete oxidation (fermentation) generally yields much less energy than complete oxidation (Rogers &amp;amp;amp; Amend, 2006; Skoog &amp;lt;em&amp;gt;et al.&amp;lt;/em&amp;gt;, 2007).&amp;amp;nbsp;&amp;lt;/p&amp;gt;

&amp;lt;p&amp;gt;To account for potential interactions between chimney-derived trace metals and amended sulfide, the saturation states of sulfide minerals were calculated as part of the initial fluid speciation. Using reported concentrations of relevant trace metals (Fe, Zn, Cu, etc.) in end-member Grotto hydrothermal fluid (Butterfield &amp;lt;em&amp;gt;et al.&amp;lt;/em&amp;gt;, 1994), maximum aqueous activities of trace metals were calculated with the EQ3 geochemical speciation program (EQ3/6 1998; EQ3NR 1998). Several sulfide minerals commonly found in hydrothermal chimneys (e.g. pyrite, chalcocite, sphalerite) were supersaturated under incubation conditions, particularly for incubations with high concentrations of amended sulfide. The irreversible abiotic precipitation of mineral sulfides has the potential to draw down aqueous sulfide concentrations and impact sulfate reductions rates. Therefore, the geochemical reaction path program EQ6 (EQ3/6 1998; EQ6 1998) was used to constrain fluid compositions to equilibrium with these minerals phases. Using the single point model in EQ6, the Gibbs energy of the system was allowed to reach local minima by mineral precipitation, however redox reactions among carbon and sulfur species was suppressed with a custom thermodynamic database. The resulting fluid compositions were used to calculate metabolic reaction energetics as well as to evaluate the potential effects of metal speciation on sulfate reduction rates.&amp;lt;/p&amp;gt;

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