Data from in situ pump profiler system collected on R/V Hugh R. Sharp cruise HRS1415 in August 2014

Website: https://www.bco-dmo.org/dataset/718887
Data Type: Cruise Results
Version: 1
Version Date: 2017-11-08

Project
» The role of soluble Mn(III) in the biogeochemical coupling of the Mn, Fe and sulfur cycles (Soluble ManganeseIII)
ContributorsAffiliationRole
Luther, George W.University of DelawarePrincipal Investigator
Tebo, Bradley M.Oregon Health & Science University (IEH/OHSU)Co-Principal Investigator
Rauch, ShannonWoods Hole Oceanographic Institution (WHOI BCO-DMO)BCO-DMO Data Manager

Abstract
Data from in situ pump profiler system collected on R/V Hugh R. Sharp cruise HRS1415 in August 2014


Coverage

Spatial Extent: N:38.9768 E:-76.3663 S:38.9758 W:-76.368
Temporal Extent: 2014-08-19 - 2014-08-22

Dataset Description

Data from in situ pump profiler system collected on cruise HRS1415.

See Related Publicatons (below) for field papers published as a result of this project (methods included).


Methods & Sampling

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. 

In situ pump profiler cast refers to profiling with a pump profiler for O2 and H2S using solid state gold-amalgam electrodes for voltammetry (Luther et al, 2008; Analytical Instrument Systems DLK-60) along with a temperature and salinity sensor from YSI. Water was pumped aboard to make measurements on discrete samples for Mn and Fe speciation as well. 

Methods papers used in this project (full citations in Related Publications section)
Dissolved Mn speciation parameters:

Madison et al. (2011)

Madison et al. (2013) 

Oldham et al. (2015)

Oldham 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 [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 (1972)

Krumbein & Altmann (1973)

Dissolved Fe speciation parameters:
Stookey (1970)

Lewis et al. (2007)

O2 and H2S, polysulfides:
Luther et al. (2008)

Luther et al. (2013)

S8:
Yücel et al. (2010)

pH and inorganic carbon parameters:
Gran (1952)

Huang & Cai (2012)


Data Processing Description

BCO-DMO Processing:
- added column for cast (was contained in header rows);
- modified parameter names to conform with BCO-DMO naming conventions;
- formatted date to mm/dd/yyyy to match CTD dataset;
- replaced blanks/missing data with "nd" ("no data");
- replaced "ND" (in all caps) with "not_detected_or_BDL";
- replaced "NA" (in all caps) with "not_analyzed";
- coverted lat and lon from degrees and decimal minutes to decimal degrees;
- added date-time in ISO8601 format using original date and time_GMT fields.


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Data Files

File
Pump_HRS1415.csv
(Comma Separated Values (.csv), 25.68 KB)
MD5:1278c0ac323db3b323be1bf698c07560
Primary data file for dataset ID 718887

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Related Publications

Altmann, H. J. (1972). Bestimmung von in Wasser gel�stem Sauerstoff mit Leukoberbelinblau I. Fresenius’ Zeitschrift F�r Analytische Chemie, 262(2), 97–99. doi:10.1007/bf00425919 https://doi.org/10.1007/BF00425919
Methods
Cai, W.-J., Huang, W.-J., Luther, G. W., Pierrot, D., Li, M., Testa, J., … Kemp, W. M. (2017). Redox reactions and weak buffering capacity lead to acidification in the Chesapeake Bay. Nature Communications, 8(1). doi:10.1038/s41467-017-00417-7
Methods
Findlay, A. J., Bennett, A. J., Hanson, T. E., & Luther, G. W. (2015). Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria. Applied and Environmental Microbiology, 81(21), 7560–7569. doi:10.1128/aem.02062-15 https://doi.org/10.1128/AEM.02062-15
Methods
Findlay, A. J., Di Toro, D. M., & Luther, G. W. (2017). A model of phototrophic sulfide oxidation in a stratified estuary. Limnology and Oceanography, 62(5), 1853–1867. doi:10.1002/lno.10539
Methods
Findlay, A. J., Gartman, A., MacDonald, D. J., Hanson, T. E., Shaw, T. J., & Luther, G. W. (2014). Distribution and size fractionation of elemental sulfur in aqueous environments: The Chesapeake Bay and Mid-Atlantic Ridge. Geochimica et Cosmochimica Acta, 142, 334–348. doi:10.1016/j.gca.2014.07.032
Methods
Gran, G. (1952). Determination of the equivalence point in potentiometric titrations. Part II. The Analyst, 77(920), 661. doi:10.1039/an9527700661 https://doi.org/10.1039/AN9527700661
Methods
Huang, W.-J., Wang, Y., & Cai, W.-J. (2012). Assessment of sample storage techniques for total alkalinity and dissolved inorganic carbon in seawater. Limnology and Oceanography: Methods, 10(9), 711–717. doi:10.4319/lom.2012.10.711
Methods
Krumbein, W. E., & Altmann, H. J. (1973). A new method for the detection and enumeration of manganese oxidizing and reducing microorganisms. Helgoländer Wissenschaftliche Meeresuntersuchungen, 25(2-3), 347–356. doi:10.1007/bf01611203 https://doi.org/10.1007/BF01611203
Methods
Lewis, B. L., Glazer, B. T., Montbriand, P. J., Luther, G. W., Nuzzio, D. B., Deering, T., … Theberge, S. (2007). Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay. Marine Chemistry, 105(3-4), 296–308. doi:10.1016/j.marchem.2007.03.001
Methods
Luther, G. W., Madison, A. S., DeLaune, R. D., Reddy, K. R., Richardson, C. J., & Megonigal, J. P. (2013). Determination of Dissolved Oxygen, Hydrogen Sulfide, Iron(II), and Manganese(II) in Wetland Pore Waters. SSSA Book Series. doi:10.2136/sssabookser10.c6
Methods
Luther, G. W., Madison, A. S., Mucci, A., Sundby, B., & Oldham, V. E. (2015). A kinetic approach to assess the strengths of ligands bound to soluble Mn(III). Marine Chemistry, 173, 93–99. doi:10.1016/j.marchem.2014.09.006
Methods
MacDonald, D. J., Findlay, A. J., McAllister, S. M., Barnett, J. M., Hredzak-Showalter, P., Krepski, S. T., … Luther III, G. W. (2014). Using in situ voltammetry as a tool to identify and characterize habitats of iron-oxidizing bacteria: from fresh water wetlands to hydrothermal vent sites. Environ. Sci.: Processes Impacts, 16(9), 2117–2126. doi:10.1039/c4em00073k
Methods
Madison, A. S., Tebo, B. M., & Luther, G. W. (2011). Simultaneous determination of soluble manganese(III), manganese(II) and total manganese in natural (pore)waters. Talanta, 84(2), 374–381. doi:10.1016/j.talanta.2011.01.025
Methods
Madison, A. S., Tebo, B. M., Mucci, A., Sundby, B., & Luther, G. W. (2013). Abundant Porewater Mn(III) Is a Major Component of the Sedimentary Redox System. Science, 341(6148), 875–878. doi:10.1126/science.1241396
Methods
Oldham, V. E., Jones, M. R., Tebo, B. M., & Luther, G. W. (2017). Oxidative and reductive processes contributing to manganese cycling at oxic-anoxic interfaces. Marine Chemistry, 195, 122–128. doi:10.1016/j.marchem.2017.06.002
Methods
Oldham, V. E., Miller, M. T., Jensen, L. T., & Luther, G. W. (2017). Revisiting Mn and Fe removal in humic rich estuaries. Geochimica et Cosmochimica Acta, 209, 267–283. doi:10.1016/j.gca.2017.04.001
Methods
Oldham, V. E., Mucci, A., Tebo, B. M., & Luther, G. W. (2017). Soluble Mn(III)–L complexes are abundant in oxygenated waters and stabilized by humic ligands. Geochimica et Cosmochimica Acta, 199, 238–246. doi:10.1016/j.gca.2016.11.043
Methods
Oldham, V. E., Owings, S. M., Jones, M. R., Tebo, B. M., & Luther, G. W. (2015). Evidence for the presence of strong Mn(III)-binding ligands in the water column of the Chesapeake Bay. Marine Chemistry, 171, 58–66. doi:10.1016/j.marchem.2015.02.008
Methods
Olson, L., Quinn, K. A., Siebecker, M. G., Luther, G. W., Hastings, D., & Morford, J. L. (2017). Trace metal diagenesis in sulfidic sediments: Insights from Chesapeake Bay. Chemical Geology, 452, 47–59. doi:10.1016/j.chemgeo.2017.01.018
Methods
Stookey, L. L. (1970). Ferrozine---a new spectrophotometric reagent for iron. Analytical Chemistry, 42(7), 779–781. doi:10.1021/ac60289a016
Methods
Yücel, M., Konovalov, S. K., Moore, T. S., Janzen, C. P., & Luther, G. W. (2010). Sulfur speciation in the upper Black Sea sediments. Chemical Geology, 269(3-4), 364–375. doi:10.1016/j.chemgeo.2009.10.010
Methods

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Parameters

ParameterDescriptionUnits
CastCast identifier unitless
latLatitude; positive values = North decimal degrees
lonLongitude; positive values = East decimal degrees
dateDate of sampling formatted as m/dd/yyyy unitless
time_localTime of sampling (local time zone) formatted as HH:MM unitless
time_GMTTime of sampling (GMT) formatted as HH:MM unitless
ISO_DateTime_UTCDate and time of sampling formatted to ISO8601 standard (yyyy-mm-ddTHH:MM); constructed using original date and time_GMT fields. unitless
depthSample depth meters (m)
tempWater temperature degrees Celsius
salinitySalinity unitless
O2Oxygen micromolar (uM)
O2_stdevStandard deviation of oxygen micromolar (uM)
H2Splus_HSminusH2S+ HS- micromolar (uM)
H2Splus_HSminus_stdevStandard deviation of H2S+ HS- micromolar (uM)
Particulate_MnOx_eqvlnParticulate Manganese oxide (MnOx) nanomolar (nM)
Particulate_MnOx_eqvln_stdevStandard deviation of Particulate Manganese oxide nanomolar (nM)
Dissolved_MnTDissolved MnT nanomolar (nM)
Dissolved_MnT_stdevStandard deviation of dissolved MnT nanomolar (nM)
Dissolved_Mn2plusDissolved Mn2+ nanomolar (nM)
Dissolved_Mn2plus_stdevStandard deviation of dissolved Mn2+ nanomolar (nM)
Dissolved_Mn3plusDissolved Mn3+ where Mn3+ = [MnT - Mn2+] nanomolar (nM)
pcnt_Mn3%Mn(III) uM or %?
Filtered_Fe2plusFiltered Fe2+ micromolar (uM)
Filtered_Fe2plus_stdevStandard deviation of filtered Fe2+ micromolar (uM)
Unfiltered_Fe2plusUnfiltered Fe2+ micromolar (uM)
Unfiltered_Fe2plus_stdevStandard deviation of unfiltered Fe2+ micromolar (uM)
Filtered_Fe3plusFiltered Fe3+ micromolar (uM)
Filtered_Fe3plus_stdevStandard deviation of filtered Fe3+ micromolar (uM)
Unfiltered_Fe3plusUnfiltered Fe3+ micromolar (uM)
Unfiltered_Fe3plus_stdevStandard deviation of unfiltered Fe3+ micromolar (uM)
nanoparticulate_S0Nanoparticulate S(0) nanomolar (nM)
particulate_S0Particulate S(0) nanomolar (nM)


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Instruments

Dataset-specific Instrument Name
YSI model 350
Generic Instrument Name
Water Temperature Sensor
Dataset-specific Description
The YSI model 350 probe measures salinity and temperature.
Generic Instrument Description
General term for an instrument that measures the temperature of the water with which it is in contact (thermometer).

Dataset-specific Instrument Name
AS-ALK2 Apollo Scitech titrator
Generic Instrument Name
Automatic titrator
Generic Instrument Description
Instruments that incrementally add quantified aliquots of a reagent to a sample until the end-point of a chemical reaction is reached.

Dataset-specific Instrument Name
Generic Instrument Name
Voltammetry Analyzers
Generic Instrument Description
Instruments that obtain information about an analyte by applying a potential and measuring the current produced in the analyte.

Dataset-specific Instrument Name
YSI 350
Generic Instrument Name
Salinity Sensor
Dataset-specific Description
The YSI model 350 probe measures salinity and temperature.
Generic Instrument Description
Category of instrument that simultaneously measures electrical conductivity and temperature in the water column to provide temperature and salinity data.

Dataset-specific Instrument Name
Generic Instrument Name
Pump
Dataset-specific Description
The pump is home made and consists of a West marine pump (12 V DC; flow rate of 160 L/hr) attached to 30 m of 1 inch ID and 1-3/8 inch OD high pressure clear PVC tubing. Valves and outlets are attached to the tubing outlet for sample collection and to go to the sensors onboard. 
Generic Instrument Description
A pump is a device that moves fluids (liquids or gases), or sometimes slurries, by mechanical action. Pumps can be classified into three major groups according to the method they use to move the fluid: direct lift, displacement, and gravity pumps

Dataset-specific Instrument Name
AS-C3, Apollo Scitech infrared CO2 analyzer
Generic Instrument Name
CO2 Analyzer
Generic Instrument Description
Measures atmospheric carbon dioxide (CO2) concentration.


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Deployments

HRS1415

Website
Platform
R/V Hugh R. Sharp
Start Date
2014-08-18
End Date
2014-08-25


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Project Information

The role of soluble Mn(III) in the biogeochemical coupling of the Mn, Fe and sulfur cycles (Soluble ManganeseIII)

Coverage: Chesapeake Bay and coastal Atlantic Ocean


Description from NSF award abstract:
The research conducted by investigators in the School of Marine Science and Policy at the University of Delaware and within the Department of Environmental and Biomolecular Systems of Oregon Health and Science University will examine the importance of soluble Mn(III) in the biogeochemical cycling of Mn. To date, most studies of Mn in marine environments have not considered Mn(III), the intermediate oxidation state between the soluble reduced state (Mn(II)) and the more insoluble oxidized state (Mn(IV)). The presence and stability of Mn(III) in marine systems, especially those where oxygen levels are reduced, changes the dynamics and stability, solubility and fate and transport of Mn in these locations, and at interfaces between oxic and low oxygen environments. This is not understood at present and the proposed research is poised to provide new information concerning the Mn cycle and is potentially transformative research. The PIs have developed new methods to examine Mn(III) levels in the environment and this capability will bolster the successful accomplishment of the project's goals. The studies will not only focus on understanding the cycling of Mn between its various oxidation states but will determine the concentration and distribution of Mn(III) in stratified coastal ocean waters and in sediment porewaters. The study will also examine the potentially important role of Mn(III) in mediating and influencing the biogeochemical cycling of Mn with that of Fe and S, which are both important components of the major ocean chemical cycles. A better understanding of the biogeochemistry of Mn will inform not only scientists interested in metal cycling in the ocean but also those focused on studies across redox transition zones. The proposed research has an international component and the investigators have developed plans to broadly disseminate their results to students at all levels and to the community. The Principal Investigators have a strong history in education and graduate student and post-doctoral support and mentoring and this will continue under the current grant.



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Funding

Funding SourceAward
NSF Division of Ocean Sciences (NSF OCE)

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