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In situ <\/em><\/strong>pump profiler cast<\/strong> refers to profiling with a pump profiler for O\u2082 and H\u2082S using solid state gold-amalgam electrodes for voltammetry (Luther et al, 2008; Analytical Instrument Systems DLK-60). Water was pumped aboard to make measurements on discrete samples for Mn and Fe speciation as well. See Hudson et al (2019) for more information.<\/p>\n Samples for Mn and Fe parameters were filtered through 0.20 um filters. Whatman track etched polycarbonate filters were soaked in 1M HCl for 1 week before rinsing and storage in DI.<\/p>\n C parameters<\/strong> performed by Dr. Wei-Jun Cai's group for: Uses Dickson CRM for calibration. DIC\/TA samples were filtered (0.45um) and fixed with 100 ul of saturated mercury bichloride. Uses the methods of Gran (1952) and Huang, et al. (2012).<\/p>\n Dissolved Mn parameters:<\/strong> Modification of Madison et al for Mn(III) bound to strong ligands by adding a reducing agent to a separate subsample with the porphyrin to obtain total Mn (Oldham 2015, 2017; Thibault de Chanvalon and Luther, 2019). Mn(III) bound to strong ligand complexes is determined by difference. Typically, triplicate measurements performed. Detection limit can be extended to 3.0 nanomolar with a 1m path length cell.<\/p>\n Modification of Madison et al. for water column samples by adding higher Cd(II) so that cadmium-chloride complex formation would not inhibit cadmium-porphyrin formation and thus incorporation of Mn into the porphyrin by Cd replacement (Thibault de Chanvalon and Luther, 2019, this work). This modification enhanced the kinetics of the reaction progress for both Mn(II) and weak Mn(III)-L complexes.<\/p>\n MnO<\/strong>\u2093 on unfiltered samples<\/strong> H\u2082<\/strong>S<\/strong> Fe parameters<\/strong> Nitrite<\/strong> Dissolved Mn speciation references:<\/strong> Dissolved Fe speciation references:<\/strong> H2S (in situ voltammetry)\u2013 water column:<\/strong> H2S (UV-Vis spectrophotometry) \u2013 sedimentary porewater samples:<\/strong> MnO\u2093\u200b <\/strong>solids:<\/strong> pH and inorganic carbon parameters:<\/strong> Nitrite:<\/strong> Data Processing:<\/strong> BCO-DMO Processing:<\/strong>
\nTA - Open cell Gran titration with semi-automatic AS-ALK2 Apollo Scitech titrator;
\npH - glass electrode, NBS buffers;
\nDIC - infrared CO\u2082 analyzer (AS-C3, Apollo Scitech).<\/p>\n
\nThe porphyrin spectrophotometric method of Madison et al (2011, 2013) measures dissolved Mn(II), Mn(III) bound to weaker ligands and total Mn. Method includes calibration and intercomparison of totals with other instrumentation (ICP, AA). Detection limit is 0.050 micromolar. Detection limit (DL) is 50 micromolar with a 1 cm path length cell.<\/p>\n
\nThe leucoberbelein blue method is that of Jones et al (2019, this work) in 1 cm cells, but can be modified for longer path length cells.<\/p>\n
\nO\u2082 and H\u2082S by the voltammetry method of Luther et al (2008) and Hudson et al (2019) using a flow cell. O\u2082 also from CTD sensor.<\/p>\n
\nThe method of Stookey (1972) is used to determine dissolved Fe(II) and on addition if hydroxylamine Fe total. Fe(III) is determined by difference. Modified and calibrated by many including Lewis et al (2007). Typically, triplicate measurements performed.<\/p>\n
\nNitrite as determined by the method of Grasshoff (1983).<\/p>\n
\nMadison et al. (2011)
\nMadison et al. (2013)
\nOldham et al. (2015)
\nOldham et al. (2017) - Here, we modified the method of Madison et al. (2011) for water column samples to achieve a detection limit of 3.0 nM (3 times the standard deviation of a blank) by using a 100-cm liquid waveguide capillary cell and the addition of a heating step as well as a strong reducing agent for Mn. Speciation [Mn\u00b3\u207a = MnT \u2013 Mn\u00b2\u207a]. As weak Mn(III)-L complexes could not be measured in our previous work (Oldham et al, 2015; paper above), this method was used throughout this cruise.
\nThibault de Chanvalon & Luther (2019) - Here, we modified the method of Madison et al. (2011) for water column samples by adding higher Cd(II) so that cadmium-chloride complex formation would not inhibit cadmium-porphyrin formation and thus incorporation of Mn into the porphyrin by Cd replacement. This modification enhanced the kinetics of the reaction progress for both Mn(II) and weak Mn(III)-L complexes.<\/p>\n
\nStookey (1970)
\nLewis et al. (2007)<\/p>\n
\nLuther et al. (2008)<\/p>\n
\nLuther et al. (2011)<\/p>\n
\nJones et al. (2019)<\/p>\n
\nGran (1952)
\nHuang et al. (2012)<\/p>\n
\nDetermination of nitrite, nitrate, oxygen, thiosulphate in Grasshoff et al. (1983)<\/p><\/div>","@type":"rdf:HTML"}],"http:\/\/ocean-data.org\/schema\/hasBriefDescription":[{"@value":"Water column Chesapeake Bay 2017","@language":"en-US"}],"http:\/\/www.w3.org\/2000\/01\/rdf-schema#label":[{"@value":"Water column Chesapeake Bay 2017","@type":"xsd:string"}],"http:\/\/ocean-data.org\/schema\/hasProcessingDescription":[{"@value":"
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\n- converted date field to YYYY-MM-DD format;
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