Table of Contents

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

Methodology:
Particulate acid volatile sulfide (pAVS) was determined at sea using the Radford-Knoery and Cutter (1993) method. This method entails placing the frozen Supor filter into a gas stripping vessel with DDI water and purging with helium, acidification to 1 M hydrochloric acid, and then gas stripping and cryogenically trapping the hydrogen sulfide and subsequent quantification using a gas chromatograph coupled with a flame photometric detector. The particulate chromium reducible sulfide (pCRS) was determined back at the ODU laboratory using the Radford-Knoery and Cutter (1993) method like pAVS but acidifying the QMA filter to 4 M hydrochloric acid with the addition of 1 M chromium (II) chloride.

Sampling and analytical procedures:
Particulate sulfide samples were collected using modified McLane in-situ pumps with two mini-MULVFS filter holders (Bishop et al., 2012). One of the holders contained a 51 μm polyester mesh prefilter and particles were collected on a 0.8 μm polyethersulfone Supor membrane filter (0.8 – 51 μm size fraction). The Supor filters had between 100 and 1,100 L filtered through them with an average of 400 L. The other filter holder contained the same prefilter but collected particles on a Whatman QMA quartz fiber filter (1 – 51 μm size fraction) and filtered between 300 and 1,540 L with an average of 1,100 L filtration volume. Excess seawater was removed using a vacuum pump within an hour of pump recovery. Both the Supor and QMA filters were then subsampled in the trace metal clean lab by P. Lam’s (UCSD) pump team and placed in cryovials that were subsequently stored frozen at -80°C until analysis. A subfraction of the Supor and QMA filters for particulate sulfide analysis were analyzed, yielding 12.5% and 2.3% of each filter with average filter volumes of 49.5 L and 23.4 L, respectively.

The pAVS samples were analyzed at sea when time allowed. Upon analysis, the frozen Supor filter was placed in a 50 mL gas stripping vessel with 10 mL of DDI water and purged with helium (100 mL/min) for 2 minutes. After 2 minutes has passed, the cryogenic trap was immersed in liquid nitrogen and 1 M hydrochloric acid was injected through the Teflon septum and stripped/trapped the gases for 15 minutes before quantifying pAVS using a gas chromatograph coupled with a flame photometric detector.

The pCRS samples were analyzed back at the ODU laboratory by the end of November 2019. Upon analysis, the frozen QMA filter was placed in the 50 mL gas stripping vessel with 10 mL of DDI water and purged with helium (100 mL/min) for 2 minutes. After 2 minutes has passed, the cryogenic trap was immersed in liquid nitrogen and 4 M hydrochloric acid and 1 M chromium (II) chloride were injected through the Teflon septum and stripped/trapped for 20 minutes before quantifying pCRS using a gas chromatography coupled with a flame photometric detector. Each day prior to analysis, chromium (II) chloride blanks were recorded and later applied as corrections to the pCRS concentration due to the addition of the chromium (II) chloride as a reducing agent.

This method has particle detection limits of 0.2 pmol S for acid volatile sulfide and 2 pmol S for chromium reducible sulfide (Radford-Knoery & Cutter, 1993) which corresponds to relative detection limits of 0.004 pmol L-1 pAVS and 0.085 pmol L-1 pCRS with average filtered volumes of 49.5 L and 23.4 L, respectively. Both pAVS and pCRS samples were analyzed mostly in single analyses, however, previous studies report pAVS and pCRS precision near 10% RSD (Cutter & Kluckhohn, 1999; Cutter & Radford-Knoery, 1991). To ensure accuracy, the H2S and OCS gases are calibrated using permeation tubes whose permeation rates have been gravimetrically measured for 2-4 years. By trapping and measuring known amounts of permeated H2S and OCS over a range of times, linear calibration curves for each gas were assembled daily and applied to the unknown samples.

Instruments:
These samples were processed following the analytical apparatus first stated by Radford-Knoery and Cutter (1993). All details can be found in that publication.

A Hewlett Packard (HP) 5890 Series II gas chromatograph coupled with a HP flame photometric detector (model 19256A) was used in the quantification of pAVS and pCRS. The output signal from the detector was processed using a PeakSimple Chromatography Data System (model 333). Hydrogen (130 mL/min) and air (130 mL/min) are used for the flame photometric detector’s flame while ultra-high purity helium is used as the carrier gas (30 mL/min) and the stripping gas (100 mL/min). While cylinders were used as the source of air and ultra-high purity helium, a VWR hydrogen generator (model H2PEM-165) was used for the hydrogen source. A VWR circulating water bath (model 1130S) was used to maintain 40°C for H2S and OCS permeation devices (Metronics) which were used to calibrate the instrument for H2S and OCS.

Known Problems/Issues:
Occasionally, there were technological errors where the connection between the detector and the PeakSimple data system became loose and resulted in peaks that were cut off and thus could no longer be quantified. These data have been flagged 9 according to the SeaDataNet scheme.

Quality Flags:
The SeaDataNet scheme was used to assign data quality flags to samples. More information can be found at https://www.seadatanet.org/Standards/Data-Quality-Control.

The reported codes for flagged data are:
0 = no quality control
1 = good value
2 = probably good value
3 = probably bad value
4 = bad value
5 = changed value
6 = value below detection
7 = value in excess
8 = interpolated value
9 = missing value

Data Processing:
The output signal from the flame photometric detector was processed using a PeakSimple Chromatography Data System (model 333). The sulfide peaks were manually integrated in the PeakSimple software and converted to a value in pmol S/L using the slope calculated from the system’s calibration immediately before or after processing the samples and the filtration volume of each subfraction of the main filter.

BCO-DMO Processing:
- corrected dates and times for those that were incrementing in Excel;
- re-named fields to comply with BCO-DMO naming conventions;
- added date/time columns in ISO8601 format.

A 60-day research cruise took place in 2018 along a transect form Alaska to Tahiti at 152° W. A description of the project titled "Collaborative Research: Management and implementation of the US GEOTRACES Pacific Meridional Transect", funded by NSF, is below. Further project information is available on the US GEOTRACES website and on the cruise blog. A detailed cruise report is also available as a PDF.

Description from NSF award abstract:
GEOTRACES is a global effort in the field of Chemical Oceanography in which the United States plays a major role. The goal of the GEOTRACES program is to understand the distributions of many elements and their isotopes in the ocean. Until quite recently, these elements could not be measured at a global scale. Understanding the distributions of these elements and isotopes will increase the understanding of processes that shape their distributions and also the processes that depend on these elements. For example, many "trace elements" (elements that are present in very low amounts) are also important for life, and their presence or absence can play a vital role in the population of marine ecosystems. This project will launch the next major U.S. GEOTRACES expedition in the Pacific Ocean between Alaska and Tahiti. The award made here would support all of the major infrastructure for this expedition, including the research vessel, the sampling equipment, and some of the core oceanographic measurements. This project will also support the personnel needed to lead the expedition and collect the samples.

This project would support the essential sampling operations and infrastructure for the U.S. GEOTRACES Pacific Meridional Transect along 152° W to support a large variety of individual science projects on trace element and isotope (TEI) biogeochemistry that will follow. Thus, the major objectives of this management proposal are: (1) plan and coordinate a 60 day research cruise in 2018; (2) obtain representative samples for a wide variety of TEIs using a conventional CTD/rosette, GEOTRACES Trace Element Sampling Systems, and in situ pumps; (3) acquire conventional CTD hydrographic data along with discrete samples for salinity, dissolved oxygen, algal pigments, 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 data to the GEOTRACES Data Assembly Centre (via the US BCO-DMO data center); and (6) coordinate all cruise communications between investigators, including preparation of a hydrographic report/publication. This project would also provide baseline measurements of TEIs in the Clarion-Clipperton fracture zone (~7.5°N-17°N, ~155°W-115°W) where large-scale deep sea mining is planned. Environmental impact assessments are underway in partnership with the mining industry, but the effect of mining activities on TEIs in the water column is one that could be uniquely assessed by the GEOTRACES community. In support of efforts to communicate the science to a wide audience the investigators will recruit an early career freelance science journalist with interests in marine science and oceanography to participate on the cruise and do public outreach, photography and/or videography, and social media from the ship, as well as to submit articles about the research to national media. The project would also support several graduate students.

NSF Award Abstract:
Trace metals like iron and zinc are essential for the growth of the microscopic plants (phytoplankton) that dominate photosynthesis in the sunlit surface ocean. Other trace metals like copper or mercury are highly toxic to these same organisms. Even at concentrations of as low as one gram in a trillion grams of seawater, trace elements can alter the community consumption of carbon dioxide and the production of oxygen by ocean ecosystems. The resulting beneficial and/or toxic response depends on the chemical form of each trace metal. Dissolved in seawater, these metals can exist either as individual, free ions or attached to other dissolved chemical compounds, generically called ligands. Complexation is the process by which trace metals become chemically attached to ligands. This project will study the complexation of six biologically important trace metals with a ligand known as hydrogen sulfide. Data from work done during an expedition in the Pacific Ocean from Alaska to Tahiti will provide new scientific insight on hydrogen sulfide's importance in controlling essential and toxic metal bioavailability in various marine waters and thus have scientific impact on ocean carbon and ecosystem models. A graduate student will play a leading role in the project. Educational opportunities will be greatly enhanced by working alongside other world-class scientists as a participant in a large collaborative program. Additional graduate learning and outreach will include communicating experiences and research findings with the public with a blog and by interactions with undergraduate students as a teaching assistant.

In the oxygenated ocean, hydrogen sulfide is biologically produced in sunlit surface waters and emitted from hydrothermal vents on ocean ridges. It can then complex dissolved trace metals or react with them to form insoluble metal sulfides. In both cases, the abundance and cycling of essential trace elements would be affected and the importance of these reactions are currently not known. These sulfide - trace metal studies will be conducted as part of the 2018 US GEOTRACES Pacific Meridional Transect (PMT), a cruise track that allows sampling of productive coastal waters, low nutrient surface waters, and plumes of metal- and sulfide-rich hydrothermal waters near the bottom. The dissolved ions of hydrogen sulfide will be measured at sea soon after collection. Metal sulfides contained in and on particles will also be filtered and analyzed. This project will address several specific scientific questions. To what degrees does sulfide complexation vary as a function of the various biological and chemical regimes encountered? Are essential metals removed by precipitating with hydrogen sulfide in the upper water column? Does the reaction of metals with hydrogen sulfide in hydrothermal waters stabilize these dissolved complexes and allow long range transport? Related study will develop from close collaborations with other GEOTRACES scientists studying trace metals and their complexation with ligands other that sulfide, providing overall context and novel capacity to fully understand trace element cycles in the ocean.

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.