Table of Contents

• Coverage
• Dataset Description
  • Methods & Sampling
  • Data Processing Description
• Data Files
• Related Publications
• Parameters
• Instruments
• Deployments
• Project Information
• Program Information
• Funding

Nitrate (NO3) aerosol isotopes from the U.S. GEOTRACES EPZT cruise

Samples were collected using Florida State University's high volume aerosol sampler (Tisch Environmental TSP TE5170V), during the US GEOTRACES EZPT cruise, R/V Thomas G. Thompson (TGT303), which took place from 25 October 2013 - 20 December 2013. Samples were collected at the rate of 1 cubic meter per minute on Whatman 41, 47 mm discs (glass fiber; GF) and were pre-combusted before deployment.

Methods for collection of filter and extraction of nitrate are described in Morton et al. (2013). 


Filters were stored frozen until processing. Filters were soaked in ultrapure (18 Megaohm) water, sonicated, and then filtered via syringe filters. Concentration analysis of samples was completed using an automated colorimetric system (WestCo SmartChem 200); the pooled standard deviation of control standards run within each sample set run was 0.1 micromoles per liter (6.2 ppb nitrate); detection limit was 0.09 micromoles per liter. Based upon nitrate concentration, 10 nmol of N were injected into vials containing denitrifying bacteria to convert nitrate to nitrous oxide for isotopic analysis on a ThermoFisher Delta V isotope ratio mass spectrometer. Analysis for d15N and d18O of nitrate are described in Sigman et al. (2001), Casciotti et al. (2002), McIlvin and Casciotti (2011). Kaiser et al. (2007) describes similar methodology for the determination of D17O of nitrate.

As described in Kaiser et al. (2007), isotopic data is corrected and standardized to international reference materials IAEA-N3, USGS34, and USGS35, which are run 3-9 times with each sample run. For d15N, samples are corrected for isobaric interferences and a blank associated with the bacteria. For d18O, samples are corrected for isobaric interferences, blank, and exchange between sample nitrate and background water that takes place during denitrification to nitrous oxide. The pooled standard deviation for the reference materials are (n=51): 0.3 per mil for d15N and 0.4 per mil for d18O of IAEA-N3; 0.2 per mil for d15N and 0.6 per mil for d18O of USGS34; and 0.8 per mil for d18O of USGS35 (sample d15N is not corrected for d15N of USGS35, this is used as an internal quality check and pooled standard deviation across all runs in 0.3 per mil). 30 samples were run in duplicate or triplicate and the paired pooled standard deviation (n=30) is 0.3 per mil for d15N and 0.7 per mil for d18O. Pooled standard deviation for USGS34 and USGS35 run for D17O is 0.3 per mil each (n=18), and replicate samples were the same (0.3 per mil, n=6).

BCO-DMO Processing:
- modified parameter names to conform with BCO-DMO and GEOTRACES naming conventions;
- created separate columns for date_start and date_end;
- added cruise_id column;
- joined to BCO-DMO GEOTRACES EPZT master data file.

Additional GEOTRACES Processing:
As was done for the GEOTRACES-NAT data, BCO-DMO added standard US GEOTRACES information, such as the US GEOTRACES event number, to each submitted dataset lacking this information. To accomplish this, BCO-DMO compiled a 'master' dataset composed of the following parameters:

cruise_id, EXPOCODE,SECT_ID, STNNBR, CASTNO, GEOTRC_EVENTNO, GEOTRC_SAMPNO, GEOTRC_INSTR, SAMPNO, GF_NO, BTLNBR, BTLNBR_FLAG_W, DATE_START_EVENT, TIME_START_EVENT, ISO_DATETIME_UTC_START_EVENT, EVENT_LAT, EVENT_LON, DEPTH_MIN, DEPTH_MAX,  BTL_DATE, BTL_TIME, BTL_ISO_DATETIME_UTC, BTL_LAT, BTL_LON, ODF_CTDPRS, SMDEPTH, FMDEPTH, BTMDEPTH, CTDPRS, CTDDEPTH.

This added information will facilitate subsequent analysis and inter comparison of the datasets.

Bottle parameters in the master file were taken from the GT-C_Bottle and ODF_Bottle datasets. Non-bottle parameters, including those from GeoFish tows, Aerosol sampling, and McLane Pumps, were taken from the TN303 Event Log (version 30 Oct 2014). Where applicable, pump information was taken from the PUMP_Nuts_Sals dataset.

A standardized BCO-DMO method (called "join") was then used to merge the missing parameters to each US GEOTRACES dataset, most often by matching on sample_GEOTRC or on some unique combination of other parameters.

If the master parameters were included in the original data file and the values did not differ from the master file, the original data columns were retained and the names of the parameters were changed from the PI-submitted names to the standardized master names. If there were differences between the PI-supplied parameter values and those in the master file, both columns were retained. If the original data submission included all of the master parameters, no additional columns were added, but parameter names were modified to match the naming conventions of the master file.

See the dataset parameters documentation for a description of which parameters were supplied by the PI and which were added via the join method.

From the NSF Award Abstract
The mission of the International GEOTRACES Program (https://www.geotraces.org/), of which the U.S. chemical oceanography research community is a founding member, is "to identify processes and quantify fluxes that control the distributions of key trace elements and isotopes in the ocean, and to establish the sensitivity of these distributions to changing environmental conditions" (GEOTRACES Science Plan, 2006). In the United States, ocean chemists are currently in the process of organizing a zonal transect in the eastern tropical South Pacific (ETSP) from Peru to Tahiti as the second cruise of the U.S.GEOTRACES Program. This Pacific section includes a large area characterized by high rates of primary production and particle export in the eastern boundary associated with the Peru Upwelling, a large oxygen minimum zone that is a major global sink for fixed nitrogen, and a large hydrothermal plume arising from the East Pacific Rise. This particular section was selected as a result of open planning workshops in 2007 and 2008, with a final recommendation made by the U.S.GEOTRACES Steering Committee in 2009. It is the first part of a two-stage plan that will include a meridional section of the Pacific from Tahiti to Alaska as a subsequent expedition.

This award provides funding for management of the U.S.GEOTRACES Pacific campaign to a team of scientists from the University of Southern California, Old Dominion University, and the Woods Hole Oceanographic Institution. The three co-leaders will provide mission leadership, essential support services, and management structure for acquiring the trace elements and isotopes samples listed as core parameters in the International GEOTRACES Science Plan, plus hydrographic and nutrient data needed by participating investigators. With this support from NSF, the management team will (1) plan and coordinate the 52-day Pacific research cruise described above; (2) obtain representative samples for a wide variety of trace metals of interest using conventional CTD/rosette and GEOTRACES Sampling Systems; (3) acquire conventional JGOFS/WOCE-quality hydrographic data (CTD, transmissometer, fluorometer, oxygen sensor, etc) along with discrete samples for salinity, dissolved oxygen (to 1 uM detection limits), plant pigments, redox tracers such as ammonium and nitrite, and dissolved nutrients at micro- and nanomolar levels; (4) ensure that proper QA/QC protocols are followed and reported, as well as fulfilling all GEOTRACES Intercalibration protocols; (5) prepare and deliver all hydrographic-type data to the GEOTRACES Data Center (and US data centers); and (6) coordinate cruise communications between all participating investigators, including preparation of a hydrographic report/publication.

Broader Impacts: The project is part of an international collaborative program that has forged strong partnerships in the intercalibration and implementation phases that are unprecedented in chemical oceanography. The science product of these collective missions will enhance our ability to understand how to interpret the chemical composition of the ocean, and interpret how climate change will affect ocean chemistry. Partnerships include contributions to the infrastructure of developing nations with overlapping interests in the study area, in this case Peru. There is a strong educational component to the program, with many Ph.D. students carrying out thesis research within the program.

Figure 1. The 2013 GEOTRACES EPZT Cruise Track. [click on the image to view a larger version]

Description from NSF award abstract:
Nitrogen (N) is an essential macronutrient whose availability can limit primary production and the capacity of the biological pump to export carbon from the surface ocean on seasonal, annual, decadal, and millennial timescales. The inventory of fixed (bioavailable) N in the ocean is driven by biological processes such as nitrogen fixation, denitrification, and anaerobic ammonia oxidation (anammox). Water column oxygen deficient zones (ODZs) are important sites for fixed N loss, as well as N2O production, and they are projected to expand and intensify in the coming years as global warming increases ocean stratification and decreases ventilation. It is important to understand the distribution of nitrate, nitrite, and N2O isotopes in relation to current ocean conditions of oxygen and trace element availability order to interpret past and future changes in nitrate signals.

In this project, a team of researchers from Stanford University, University of Massachusetts at Dartmouth, and Brown University will measure the nitrogen- and oxygen-isotopic composition (del15N and del18O) of nitrate, nitrite, and nitrous oxide in seawater samples collected along the GEOTRACES Pacific Peru-Tahiti Section. Values of del15N and del18O will also be measured in nitrate from aerosol and rain samples to inform our interpretation of the N isotope budget and isotopic gradients within the tropical South Pacific. Finally, N2/Ar and N2 del15N will be determined to close the N mass and isotope budgets. Nitrate del15N is a GEOTRACES "core parameter" that will complement other measurements, such as bioactive trace element concentrations and speciation, Si isotope variations, as well as redox and productivity proxies.

The GEOTRACES Peru-Tahiti section provides a rare opportunity to track the fate of the isotopic signals of N loss from one of the largest water column ODZs. Furthermore, little is known about the effect of N recycling through hydrothermal vents on nitrate isotopes in the deep ocean, and this section will allow quantitative tracking of this input. Together, these measurements will yield insight into the relative rates of modern N cycle processes and will provide background information for paleoceanographic applications.

GEOTRACES is a SCOR sponsored program; and funding for program infrastructure development is provided by the U.S. National Science Foundation.

GEOTRACES gained momentum following a special symposium, S02: Biogeochemical cycling of trace elements and isotopes in the ocean and applications to constrain contemporary marine processes (GEOSECS II), at a 2003 Goldschmidt meeting convened in Japan. The GEOSECS II acronym referred to the Geochemical Ocean Section Studies To determine full water column distributions of selected trace elements and isotopes, including their concentration, chemical speciation, and physical form, along a sufficient number of sections in each ocean basin to establish the principal relationships between these distributions and with more traditional hydrographic parameters;

* To evaluate the sources, sinks, and internal cycling of these species and thereby characterize more completely the physical, chemical and biological processes regulating their distributions, and the sensitivity of these processes to global change; and

* To understand the processes that control the concentrations of geochemical species used for proxies of the past environment, both in the water column and in the substrates that reflect the water column.

GEOTRACES will be global in scope, consisting of ocean sections complemented by regional process studies. Sections and process studies will combine fieldwork, laboratory experiments and modelling. Beyond realizing the scientific objectives identified above, a natural outcome of this work will be to build a community of marine scientists who understand the processes regulating trace element cycles sufficiently well to exploit this knowledge reliably in future interdisciplinary studies.

Expand "Projects" below for information about and data resulting from individual US GEOTRACES research projects.