Table of Contents

• Dataset Description
  • Methods & Sampling
  • Data Processing Description
  • Problem Description
• Related Publications
• Related Datasets
• Parameters
• Instruments
• Project Information
• Funding

Laboratory barite–fluid isotope-tracer experiments were conducted in the NIRVANA Labs at the Woods Hole Oceanographic Institution. A four-condition matrix combined two fluid types, artificial seawater and filtered seawater from Vineyard Sound, Massachusetts, with two barite types, synthetic barium sulfate and natural pelagic barite isolated from Equatorial Pacific sediments. Artificial seawater was prepared following Smith & Chanley (1975) and adjusted to approximately pH 8.1 with concentrated potassium hydroxide. Filtered seawater was collected using the flow-through seawater system at the Environmental Systems Laboratory at the Woods Hole Oceanographic Institution (Huguenin, 1975), collected into 1 liter acid-washed high-density polyethylene bottles, and filtered through a 0.4 micrometer acid-washed polyethersulfone membrane in a clean room. Synthetic barite was Alfa Aesar barium sulfate powder, Lot 24177, and natural pelagic barite was isolated from Equatorial Pacific sediments. Known quantities of barite powder were added to each fluid and kept under constant agitation for up to six months. In each experiment, the dissolved pool was amended with a 136Ba-enriched solution such that the initial fluid 138Ba:136Ba ratio was approximately 0.35 ± 0.03 (±2 standard error, n = 4). Barium-136 additions were adjusted to achieve an initial barite saturation state of 1.3, calculated using PHREEQC. Aliquots of 2 milliliters were sampled over 174 days and filtered through a 0.22 micrometer polyethersulfone membrane filter prior to analysis of the fluid 138Ba:136Ba ratio.

For tracer analyses, a 100 microliter aliquot was taken from each isotope-tracer subsample, diluted with 2 percent nitric acid, and spiked with indium as an internal standard to achieve a final indium concentration of 1 nanogram per milliliter. Samples were measured at a salinity of 1.75 to minimize non-spectral matrix effects. Filtered samples were analyzed for 138Ba:136Ba on a quadrupole inductively coupled plasma mass spectrometer.

NSF Award Abstract:
The biological cycling of carbon in the oceans entrains many other elements, some directly (like nutrients that are essential for life) and some indirectly, as they become chemically involved in the processes that are affecting carbon. One such element is barium (Ba). Particles of the mineral barite (barium sulfate) have been found to form in association with microbial consumption of organic material in the ocean’s “twilight zone.” These particles settle to the ocean floor, and their presence in sediments has been used to infer changes in the conditions in the ocean back in time. Both the amount of barite in sediments and the isotope composition of Ba in barite are potentially sensitive to processes occurring in the twilight zone. However, several long-standing questions remain about Ba cycling in the oceans, which complicates the interpretation of barium-based proxy records. Examples of remaining questions include how much barium enters the oceans at mid-ocean ridge hydrothermal sites, and what controls the precipitation and dissolution of barite in the water column. This project seeks to tackle these questions using new approaches, on three scheduled research expeditions in the Pacific and Southern Oceans. In doing so, this project will support the education, training, and career development of a graduate student, postdoctoral researcher, and junior investigator. Undergraduate students from underrepresented groups will be recruited to conduct complementary shore-based experiments.

This proposal seeks to answer four questions central to the utility of barium-based proxies in oceanography: What are the major inputs of new Ba to the ocean? What are their isotopic compositions? What controls the amount of pelagic barite precipitated during the remineralization of organic matter? What influences its isotopic composition? These questions will be addressed using a field-centric approach combining: in situ and shipboard tracer-incubation experiments, AUV-led adaptive sampling of Ba cycling ‘hotpots’, and section-based surveying of the surrounding oceanographic features. This multi-pronged approach will be used to investigate: the flux and isotopic composition of Ba released from the largest hydrothermal fields in the ocean, the Southern East Pacific Rise, with a focus on low-temperature venting; rates and signatures of pelagic barite precipitation associated with different phytoplankton assemblages in the Southern Ocean; and, the importance of environmental conditions, such as low ambient oxygen concentrations, in setting the efficiency of barite precipitation in the Eastern Tropical Pacific. The significance of each transformation will be assessed, which may lead to ruling out the importance of certain processes, or identifying new dependencies that could form the basis of new proxies.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.