Description/methods for parameters measured:
C parameters performed by Dr. Wei-Jun Cai’s group for:
TA - Open cell Gran titration with semi-automatic AS-ALK2 Apollo Scitech titrator;
pH - glass electrode, NBS buffers;
DIC - infrared CO2 analyzer (AS-C3, Apollo Scitech).
Use Dickson CRM for calibration. DIC/TA samples were filtered (0.45um) and fixed with 100 ul of saturated mercury bichloride.
Use the methods of Gran (1952) and Huang, et al. (2012).

Fe parameters:
The 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) and MacDonald et al (2014). Typically, triplicate measurements performed.

Dissolved Mn parameters:
The porphyrin spectrophotometric method of Madison et al (2011) 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.

Modification of Madison for Mn(III) bound to strong ligands by adding a reducing agent to a separate subsample with the porphyrin to obtain total Mn. Mn(III) bound to strong ligand complexes is determined by difference. Typically, triplicate measurements performed. Detection limit is 3.0 nanomolar.

MnOx on unfiltered samples:
The leucoberbelein blue method is that of Altmann (1972) and Krumblein and Altmann (1973) in 1 cm cells, but can be modified for longer path length cells.

S parameters:
O2, H2S and polysulfides by the voltammetry method of Luther et al (2008).
A flow cell was also used to collect in situ O2 and H2S data as well as some additional samples. Analysis by voltammetry (Luther et al, 2008).
Solid and nanoparticulate S8 (Yücel et al 2010 and Findlay et al 2014).
Typically, triplicate measurements performed.

Methods papers used in this project:
Dissolved Mn speciation parameters:
Madison, A., B. M. Tebo, G. W. Luther, III. 2011. Simultaneous determination of soluble manganese(III), manganese(II) and total manganese in natural (pore)waters. Talanta 84, 374-381. http://dx.doi.org/10.1016/j.talanta.2011.01.025

Madison, A. S, B. M. Tebo, A. Mucci, B. Sundby and G. W. Luther, III. 2013. Abundant Mn(III) in porewaters is a major component of the sedimentary redox system. Science 341, 875-878. http://dx.doi.org/10.1126/science.1241396

Oldham, V. O., S. M. Owings, M. Jones, B. M. Tebo and G. W. Luther, III. 2015. Evidence for the presence of strong Mn(III)-binding ligands in the water column of the Chesapeake Bay. Marine Chemistry 171, 58-66. http://dx.doi.org/10.1016/j.marchem.2015.02.008

Oldham, V. O., A. Mucci, B. M. Tebo and G.W. Luther III. 2017. Soluble Mn(III)-L complexes are ubiquitous in oxygenated waters and stabilized by humic ligands. Geochimica Cosmochimica Acta 199, 238-246. http://dx.doi.org/10.1016/j.gca.2016.11.043
[[ 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 [Mn3+ = MnT – Mn2+]. See Table 1 in this paper for recovery tests. 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. ]]

MnOX solids:
Altmann, H.H., 1972. Bestimmung von inWasser gelöstem Sauerstoffmit Leukoberbelinblau I. Fresenius' Z. Anal. Chem. 6, 97–99.

Krumbein, W. E., and H. J. Altmann. 1973. ‘A New Method for the Detection and Enumeration of Manganese Oxidizing and Reducing Microorganisms’. Helgoländer Wissenschaftliche Meeresuntersuchungen 25 (2-3): 347–56. doi:10.1007/BF01611203.

Dissolved Fe speciation parameters:
Stookey L.L. 1970. Ferrozine- A New Spectrophotometric Reagent for Iron. Anal. Chem. 42, 779-781.

Lewis, B. L., B. T. Glazer, P. J. Montbriand, G. W. Luther, III, D. B. Nuzzio, T. Deering, S. Ma, and S. Theberge. 2007. Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay. Marine Chemistry 105, 296-308.

O2 and H2S, polysulfides:
Luther, III, G. W., B. T. Glazer, S. Ma, R. E. Trouwborst, T. S. Moore, E. Metzger, C. Kraiya, T. J. Waite, G. Druschel, B. Sundby, M. Taillefert, D. B. Nuzzio, T. M. Shank, B. L. Lewis and P. J. Brendel. 2008. Use of voltammetric solid-state (micro)electrodes for studying biogeochemical processes: laboratory measurements to real time measurements with an in situ electrochemical analyzer (ISEA). Marine Chemistry 108, 221-235. http://dx.doi.org/10.1016/j.marchem.2007.03.002

Luther, G. W., III, and A. S. Madison. 2013. Determination of Dissolved Oxygen, Hydrogen Sulfide, Iron(II), and Manganese(II) in Wetland Pore Waters. In: Methods in Biogeochemistry of Wetlands, R.D. DeLaune, K.R. Reddy, C.J. Richardson, and J.P. Megonigal, editors. SSSA Book Series, no. 10. SSSA, Madison, WI. p. 87-106. http://dx.doi.org/10.2136/sssabookser10.c6

S8:
Yücel, M., S. K. Konovalov, T. S. Moore, C. P. Janzen and G. W. Luther, III. 2010. Sulfur speciation in the upper Black Sea sediments. Chemical Geology 269, 364-375. http://dx.doi.org/10.1016/j.chemgeo.2009.10.010

pH and inorganic carbon parameters:
Gran G. 1952. Determination of the equivalence point in potentiometric titrations, Part II. Analyst, 77: 661-671.

Huang W.-J., Wang Y., and Cai W.-J. 2012. Assessment of sample storage techniques for total alkalinity and dissolved inorganic carbon in seawater. Limnology and Oceanography: Methods, 10: 711-717.

RosetteSamples_HRS1415.csv