19:I[42426,["/_next/static/immutable/chunks/1xctgzqre-wsy.js","/_next/static/immutable/chunks/06_-wz6pdtp2b.js","/_next/static/immutable/chunks/30e52g49hg40p.js","/_next/static/immutable/chunks/02yq6tul2z-oh.js","/_next/static/immutable/chunks/10bx_ec2vj7n_.js","/_next/static/immutable/chunks/33bfn03fo8xnt.js","/_next/static/immutable/chunks/0tfjf78scu61b.js","/_next/static/immutable/chunks/31xnvej4n1bi9.js"],"default"] 1a:T12a0,

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). 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.

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.

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).

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).

Dissolved Mn parameters:
The 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.

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.

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.

MnOₓ on unfiltered samples
The 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.

H₂S
O₂ and H₂S by the voltammetry method of Luther et al (2008) and Hudson et al (2019) using a flow cell. O₂ also from CTD sensor.

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). Typically, triplicate measurements performed.

Nitrite
Nitrite as determined by the method of Grasshoff (1983).

Dissolved Mn speciation references:
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⁺]. 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.
Thibault 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.

Dissolved Fe speciation references:
Stookey (1970)
Lewis et al. (2007)

H2S (in situ voltammetry)– water column:
Luther et al. (2008)

H2S (UV-Vis spectrophotometry) – sedimentary porewater samples:
Luther et al. (2011)

MnOₓ solids:
Jones et al. (2019)

pH and inorganic carbon parameters:
Gran (1952)
Huang et al. (2012)

Nitrite:
Determination of nitrite, nitrate, oxygen, thiosulphate in Grasshoff et al. (1983)

1b:Tb71,NSF Award Abstract: Manganese (Mn) is an important trace nutrient for biological growth in marine organisms. In the past, all Mn dissolved in seawater was thought to exist in only one chemical form: Mn(II). Recent work in waters and sediments with little or no oxygen has shown that Mn(III) can be the dominant form of dissolved Mn and can even be present in oxygenated water if attached to specific organic molecules called ligands. This research will further investigate these discoveries, aiming to quantify the chemical and microbiological processes responsible for Mn(III) cycling under varying oxygen concentrations. The research will compare field sites in the Broadkill River wetland, the Chesapeake Bay, and the Lower St. Lawrence Estuary; measuring the water column and sediments known to have strong oxygen gradients and different organic carbon sources that could change the availability and binding strength of ligands that would stabilize dissolved Mn(III). In some chemical forms, Mn tends to act like iron, so this research may have broader implications by helping marine chemists to understand more about iron cycling in similar oxygen gradients. With growing concerns over diminished oxygen concentrations (hypoxia) in the ocean, and particularly in coastal regions, understanding the reactions of Mn(III) with organic ligands across oxygen gradients could become important for understanding Mn availability to organisms. The project includes support for the participation and mentoring of one graduate student and two postdoctoral researchers, and there will be a U.S.-Canada collaboration. A variety of public outreach activities are planned with a K-12 teacher to be selected as a participant on a research cruise. Mn(III) has only recently been recognized as an important redox state for Mn in seawater. Previously, it was widely accepted that all Mn that passes through a 0.2 or 0.4 µm filter is dissolved Mn(II) while the retained portion is solid Mn(III, IV) oxide. Research in the Black Sea, the Baltic Sea, and the Chesapeake Bay has shown that soluble Mn(III) can be up to 100% of the dissolved Mn in the water column. Also, Mn(III) can exist as complexes with organic ligands in oxygenated seawater. This project will quantify and constrain the mechanisms surrounding weak and strong Mn(III) ligand transformations across vertical and horizontal oxygen gradients. Field sites to be studied include systems with a variety of organic carbon sources and oxygen dynamics: the Lower St. Lawrence Estuary, Chesapeake Bay, and Broadkill River wetland estuary. This research will continue to inform the fundamental shift that is taking place in our current understanding of Mn biogeochemistry in coastal systems. The results should also be applicable to redox processes involving Fe(III) ligand transformations, since Mn and Fe tend to exhibit similar redox chemistry under similar environmental conditions.6:["$","$L19",null,{"dataset":{"_id":"840678","description":"","problem":"","acquisition":"$1a","processing":"

Data Processing:
\nNM is used to indicate sensor not available or no measurement. BDL indicates measurements below the detection limit. Refer to parameter definitions for detection limits.

BCO-DMO Processing:
\n- converted date field to YYYY-MM-DD format;
\n- added date/time column in ISO8601 format (UTC/GMT);
\n- converted latitude and longitude to decimal degrees from degrees and decimal minutes.

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Luther","role":"Chief Scientist"}]}],"funding":[{"_id":"715476","name":"OCE-1558738","fundingSource":{"_id":"355","name":"NSF Division of Ocean Sciences"},"url":"https://www.nsf.gov/awardsearch/show-award?AWD_ID=1558738"},{"_id":"715486","name":"OCE-1558692","fundingSource":{"_id":"355","name":"NSF Division of Ocean Sciences"},"url":"https://www.nsf.gov/awardsearch/show-award?AWD_ID=1558692"}],"instruments":[{"_id":"840734","name":"infrared CO2 analyzer (AS-C3, Apollo Scitech)","description":"","type_id":"491476","type_name":"CO2 Analyzer","type_desc":"Measures atmospheric carbon dioxide (CO2) concentration.","type_acronym":"CO2 Analyzer"},{"_id":"840732","name":"In situ pump profiler","description":"Profiling was conducted with a pump profiler for using solid state gold-amalgam electrodes for voltammetry (Luther et al, 2008; Analytical Instrument Systems DLK-60). See Hudson et al (2019), doi: 10.1016/j.talanta.2019.02.076.","type_id":"726","type_name":"Pump","type_desc":"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","type_acronym":""},{"_id":"840733","name":"AS-ALK2 Apollo Scitech","description":"","type_id":"682","type_name":"Titrator","type_desc":"Titrators are instruments that incrementally add quantified aliquots of a reagent to a sample until the end-point of a chemical reaction is reached.","type_acronym":"Titrator"}],"parameters":[{"_id":"840883","name":"Region","format":"","frictionlessType":"string","description":"

Sampling location

","units":{"_id":"","name":"unitless"},"type":{"_id":"1124","name":"site","description":"

Sampling site identification.

"}},{"_id":"840884","name":"cruise","format":"","frictionlessType":"string","description":"

Cruise identifier

","units":{"_id":"","name":"unitless"},"type":{"_id":"1102","name":"cruise_id","description":"

cruise designation; name

"}},{"_id":"840885","name":"cast","format":"","frictionlessType":"number","description":"

Cast number

","units":{"_id":"","name":"unitless"},"type":{"_id":"761","name":"cast","description":"

cast or profile number

"}},{"_id":"840886","name":"sample","format":"","frictionlessType":"string","description":"

Bottle number or pump-profiler number

","units":{"_id":"","name":"unitless"},"type":{"_id":"960","name":"sample","description":"

unique sample identification or number; any combination of alpha numeric characters; precise definition is file dependent

"}},{"_id":"840887","name":"date","format":"%Y-%m-%d","frictionlessType":"date","description":"

Date of sample collection; format: YYYY-MM-DD

","units":{"_id":"","name":"unitless"},"type":{"_id":"1070","name":"date","description":"

date; generally reported in GMT as YYYYMMDD (year; month; day); also as MMDD (month; day); EqPac dates are local Hawaii time. ISO_Date format is YYYY-MM-DD (http://www.iso.org/iso/home/standards/iso8601.htm)

"}},{"_id":"840888","name":"local_time_EST","format":"%H:%M","frictionlessType":"time","description":"

Time of sample collection in the local time zone (US Eastern Daylight); format: hh:mm

","units":{"_id":"","name":"unitless"},"type":{"_id":"1075","name":"time","description":"

Time GMT defined as HHMM; time of day; generally reported in GMT as HHMM (hours and minutes) but may also be HH.H (decimal hours) or HHMMSS (hours; minutes and seconds); in EqPac time is reported as Hawaii local time

"}},{"_id":"840889","name":"ISO_DateTime_UTC","format":"%Y-%m-%dT%H:%MZ","frictionlessType":"datetime","description":"

Date and time of sample collection (UTC/GMT) formatted to ISO8601 standard: YYYY-mm-ddTHH:MMZ

","units":{"_id":"","name":"unitless"},"type":{"_id":"1908","name":"ISO_DateTime_UTC","description":"

Date/Time (UTC) ISO formatted
\nThis standard is based on ISO 8601:2004(E) and takes on any of the following forms:
\n2009-08-30T09:05:00[.xx] (local time)
\n2009-08-30T14:05:00[.xx]Z (UTC time)
\n2009-08-30T14:05:00[.xx]-05:00
\nThe dashes and the colons can be dropped.
\nThe T can also be dropped \"by mutual agreement\", but one needs the trailing Z if the time is UTC.

Sample ISO_datetime_utc:
\n2009-08-30T14:05:00[.xx]Z (UTC time)

Format: YYYY-mm-ddTHH:MM:SS[.xx]Z (UTC time)

"}},{"_id":"840890","name":"Latitude","format":"","frictionlessType":"number","description":"

Latitude in decimal degrees; positive values = North

","units":{"_id":"","name":"degrees North"},"type":{"_id":"730","name":"latitude","description":"

latitude, in decimal degrees, North is positive, negative denotes South; Reported in some datasets as degrees, minutes

"}},{"_id":"840891","name":"Longitude","format":"","frictionlessType":"number","description":"

Longitude in decimal degrees; negative value = West

","units":{"_id":"","name":"degrees East"},"type":{"_id":"731","name":"longitude","description":"

longitude, in decimal degrees, East is positive, negative denotes West; Reported in some datsets as degrees, minutes

"}},{"_id":"840892","name":"depth","format":"","frictionlessType":"number","description":"

Sample depth

","units":{"_id":"","name":"meters (m)"},"type":{"_id":"808","name":"depth","description":"

Observation/sample depth below the sea surface. Units often reported as: meters, feet.

\nWhen used in a JGOFS/GLOBEC dataset the depth is a best estimate; usually but not always calculated from pressure; calculated either from CTD pressure using Fofonoff and Millard (1982; UNESCO Tech Paper #44) algorithm adjusted for 1980 equation of state for seawater (EOS80) or simply equivalent to nominal depth as recorded during sampling if CTD pressure was unavailable.

"}},{"_id":"840893","name":"temperature","format":"","frictionlessType":"number","description":"

Water temperature from CTD

","units":{"_id":"","name":"degrees Celsius"},"type":{"_id":"733","name":"temperature","description":"

water temperature at measurement depth

"}},{"_id":"840894","name":"salinity","format":"","frictionlessType":"number","description":"

Salinity from CTD

","units":{"_id":"","name":"PSU"},"type":{"_id":"955","name":"sal","description":"

Salinity: The amount (mass or quantity of matter) of salt per amount (volume or mass) of a body of water.

"}},{"_id":"840895","name":"CTD_O2","format":"","frictionlessType":"number","description":"

O2 from CTD

","units":{"_id":"","name":"micromolar (uM)"},"type":{"_id":"910","name":"dissolved Oxygen","description":"

dissolved oxygen concentration

"}},{"_id":"840896","name":"O2_100_pcnt_sat_at_T","format":"","frictionlessType":"number","description":"

100% O2 sat at T

","units":{"_id":"","name":"micromolar (uM)"},"type":{"_id":"911","name":"O2sat","description":"

oxygen saturation, in milliliters/liters or sometimes milligrams per liter.

"}},{"_id":"840897","name":"pcnt_O2_sat","format":"","frictionlessType":"number","description":"

Percent O2 saturation

","units":{"_id":"","name":"unitless (percent)"},"type":{"_id":"911","name":"O2sat","description":"

oxygen saturation, in milliliters/liters or sometimes milligrams per liter.

"}},{"_id":"840898","name":"fluor_voltage","format":"","frictionlessType":"number","description":"

Fluorescence (chl) voltage

","units":{"_id":"","name":"volts"},"type":{"_id":"836","name":"fluor voltage","description":"

fluorometer voltage measurements, in volts

"}},{"_id":"840899","name":"transmiss_voltage","format":"","frictionlessType":"number","description":"

Transmissometry voltage

","units":{"_id":"","name":"volts"},"type":{"_id":"1015","name":"trans_v","description":"

light transmission, as volts

"}},{"_id":"840900","name":"H2S","format":"","frictionlessType":"number","description":"

H2S

","units":{"_id":"","name":"micromolar (uM)"},"type":{"_id":"840800","name":"hydrogen sulfide","description":"

Hydrogen sulfide (H2S): A sulfur hydride consisting of a single sulfur atom bonded to two hydrogen atoms. A highly poisonous, flammable gas with a characteristic odor of rotten eggs, it is often produced by bacterial decomposition of organic matter in the absence of oxygen.

"}},{"_id":"840901","name":"TA","format":"","frictionlessType":"number","description":"

","units":{"_id":"","name":"micromoles per kilogram (umol/kg)"},"type":{"_id":"1224","name":"TALK","description":"

Total alkalinity

"}},{"_id":"840902","name":"DIC","format":"","frictionlessType":"number","description":"

DIC

","units":{"_id":"","name":"micromoles per kilogram (umol/kg)"},"type":{"_id":"1187","name":"DIC","description":"

Dissolved Inorganic Carbon

"}},{"_id":"840903","name":"pH_NBS","format":"","frictionlessType":"number","description":"

pH, NBS scale at 25 degrees C

","units":{"_id":"","name":"unitless"},"type":{"_id":"1892","name":"pH","description":"

pH: The measure of the acidity or basicity of an aqueous solution

"}},{"_id":"840904","name":"pMnOx","format":"","frictionlessType":"number","description":"

Particulate MnOx; particulate on the 0.20 micrometer filter; single measurement; detection limit = 0.01 uM