Table of Contents

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

Water column, sediment, and pore water samples were collected following the methods in Abbott et al. (2015) during R/V Kilo Moana cruise KM2012 in October and November 2020. Pore water aliquots for REE (Rare Earth Elemental) concentration and εNd were collected by centrifuge and filtration (<0.45 micrometers (μm)). The REE aliquots were extracted from one core, while the εNd aliquots were multiple, combined extractions from corresponding layers of 20 to 25 cores. See 'Related Datasets' for the data from the water column samples and sediment cores.

Pore water aliquots for nutrient analyses were extracted using Rhizon samplers and filtered (<0.2 µm). Pore water aliquots for DOC analysis were extracted via Rhizon, filtered (<0.45 μm with GFF filter), poisoned with mercuric chloride, and stored in a glass vial.

Pore water dissolved O2 concentration was measured using a fiber-optic oxygen microsensor inserted into pre-drilled holes through the core into the sediments. The sensor readings are converted to oxygen concentration by linearly calibrating against the published bottom water O2 concentration at the study sites.

Pore water pH was measured on unfiltered samples using a portable pH sensor post-extraction via centrifugation. Analyses of pH in pore waters is notoriously difficult due to the changes in pressure upon recovery, and thus the pH data have finite utility.

Elemental concentrations, including the REEs, were analyzed at Oregon State University (OSU) using an Elemental Scientific seaFAST-pico offline preconcentration technique, and the procedure has been extensively documented as part of the GEOTRACES intercalibration effort (Behrens et al., 2016). Elemental concentrations of the εNd aliquots (~10 milliliters (mL)) were analyzed at ETH Zurich using Nobias Chelate-PA1 resin in a manual column procedure (K. Deng et al., 2022).

Isotope analysis of the εNd aliquots (400~700 mL of pore water or ~1.5 liters (L) of seawater) were done at ETH Zurich. Samples were buffered to a pH of 5.5 ± 5 and pre-concentrated using an in-house extraction manifold containing Nobias Chelate-PA1 resin. After pre-concentration, separation of Nd from the matrix elements and other REE was done using Eichrom RE and LN spec resins. Procedural blanks are <3 picograms (pg). Isotope analysis was done on an Neptune Plus MC-ICP-MS (Thermo-Fisher) following the procedure of Vance and Thirlwall (2002). Internally normalized sample data was renormalized to the 143Nd/144Nd ratio of La Jolla (Thirlwall, 1991). Repeated analysis of 8 parts per billion (ppb) La Jolla solutions results in a long-term external reproducibility of 0.27 ε (2σ). Nd isotope analysis was also quality-controlled by repeated measurements of the USGS reference materials BCR-2 (εNd = -0.11 ± 0.25, 2σ) and BHVO-2 (εNd = 6.70 ± 0.24, 2σ) at the same concentration (5-10 ppb) as the pore water samples in agreement with literature results (Jochum et al., 2005).

Nutrients were analyzed at Oregon State University using Technicon AutoAnalyzer II (phosphate and ammonium) and Alpkem RFA 300 (silicic acid, nitrate+nitrite). The method and data processing follow Gordon et al. (1993). DOC was analyzed with a V-CSN/TNM-1 (Shimadzu Corp, Kyoto, Japan) at the Scripps Institution of Oceanography following White et al. (2023).

Sediment samples were analysed for total organic carbon contents using a GVI (now Elementar) Isoprime 1000 with Eurovector EA at Bigelow Laboratory for Ocean Sciences. Samples were measured for the total carbon (organic plus inorganic) and a separate sample split was acidified to remove carbonate and then measured for the organic fraction.

​X-ray diffraction (XRD) of freeze-dried raw samples were made at K/T GeoServices Inc. (Colorado, USA), using a Siemens D500 automated powder diffractometer equipped with a copper X-ray source (40kV, 30mA) and a scintillation X-ray detector. Semi-quantitative determinations of whole-sediment mineral amounts were done using Jade Software (Materials Data, Inc.) with the Whole Pattern Fitting option.

- Imported sheet "BCO-DMO pore water" from original file "BCO-DMOv2.xlsx" into the BCO-DMO system.
- Renamed fields to comply with BCO-DMO naming conventions.
- Corrected bottom depth of station 4 from 505 to 5050.
- Saved the final file as "928246_v1_pore_water_geochemical_composition.csv".

NSF Award Abstract:
Circulation of water is a fundamental trait of the oceans that impacts its physics, chemistry and biology; however, understanding modern and past patterns of circulation - especially in the vast bodies of deep water - is challenging because global circulation defies direct measurement. The problems with direct measurement largely stem from the vast scales of space and time that are of interest in understanding global circulation. One tool for estimating global circulation patterns that holds promise is seen in neodymium isotopes which appear to be powerful tracers of deep ocean circulation, over a variety of timescales. Unfortunately, the elemental behavior of neodymium contrasts the isotopic behavior of neodymium in the oceans, a puzzle branded the "neodymium paradox." This inconsistency of geochemical behavior opens to question the application of neodymium isotopes as a tracer of circulation. Therefore, scientists from Oregon State University, Tulane University, and Bigelow Laboratory of Ocean Sciences propose to test the hypothesis that there is a yet unconstrained (even poorly identified) source of neodymium to the oceans that can explain the discrepancies seen between the elemental and isotopic neodymium marine budgets. The scientists further seek to understand the mechanistic cause of this source and thus be able to start making global constraints on its influence. Understanding these processes will fundamentally change our interpretations of neodymium data and allow us to more accurately quantify ocean circulation with a greater degree of confidence. For outreach activities, the scientists plan to participate in open house days held at Oregon State University, da Vinci days, National Ocean Science Bowls, Salmon Bowl and Bigelow Laboratory for Ocean Sciences' Cafe Scientifique. Undergraduate students and one graduate student from Tulane University would be supported and trained as part of this project.

Scientists from Oregon State University, Tulane University, and Bigelow Laboratory for Ocean Sciences propose to test the hypothesis that there is a benthic source of neodymium (Nd) to the oceans that exerts a primary control over the distribution of this element and its isotopes (eNd) in the ocean. This benthic flux results from early diagenetic reactions that release rare earth elements (REEs) from the solid phase to pore fluid. The scientists contend this flux will explain eNd distributions throughout the modern and past global oceans. The planned research will be guided by three questions:

(1) What are the mechanisms that control the magnitude and isotope composition of the benthic flux?
(2) What are the relationships among bottom water, pore fluid, and the terminal solid phase compositions? Particularly, how and under what chemical conditions does an eNd signature become part of a preserved archival record of [Nd] and eNd?
(3) Can our understanding of the deep water benthic fluxes account for the integrated bottom water eNd as a function of apparent water mass age and circulation path (e.g., how do the pore fluid and solid phase values reconcile with the existing water column signature and water mass age data)?

To test these ideas, sediments and their pore fluids will be collected from a diverse set of deep sea sites in the Pacific Ocean that reflect slow-to-fast sedimentation rates, carbonate-, terrigenous-, volcaniclastic- and siliceous-sediment, and low-to-high organic carbon. The sediments and porewater samples, as well as samples from the overlying water column will be characterized for the following parameters: major, minor, and trace metals, Nd isotopes, carbonate chemistry, oxygen, nutrients, particulate organic carbon, particulate organic nitrogen, radiocarbon, porosity, and grain size. With these observations we will build a quantitative numeric geochemical model (e.g., PHREEQC, Geochemist's Workbench, Humic Ion Binding Model) that can capture the cardinal controls over the benthic source. Our goal is to provide a new interpretive framework for Nd and eNd, such that we can offer quantitative estimates of benthic fluxes for use in models of global circulation. This work has potentially transformative implications on our understanding and application of REEs and Nd isotope data in both the modern and ancient oceans.

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.