Title: Investigating the Applications of Neodymium Isotopic Compositions and Rare Earth Elements as Water Mass Tracers in the South Atlantic and North Pacific
Description: Neodymium (Nd) isotopes have been increasingly used to trace the modern and past ocean circulation. This assumes that seawater Nd isotope ratios (εNd) effectively fingerprint different water masses and approximate expected values from water mass mixing. However, the decoupling of Nd isotopes and Nd concentration (the “Nd paradox”) in the water column, and the lack of understanding of sources and sinks of Nd, restrain our understanding of the “quasi-conservative” behavior of εNd in seawater. Nd is one of the lanthanide rare earth elements (REEs) with similar chemical characteristics that undergo some degree of fractionation. The shale-normalized REE patterns and REE ratios can be used to investigate potential sources/sinks of REEs. Combining REEs with εNd will provide additional information to study REE cycling in the ocean. To better understand the reliability of εNd as a water mass tracer, 17 high-resolution seawater profiles were sampled meridionally in the Southwest Atlantic (GEOTRACES GA02 Leg 3; RRS James Cook 057) and measured for εNd.

This region involves the major water masses in the Atlantic Meridional Overturning Circulation: southward flowing North Atlantic Deep Water (NADW), northward flowing Antarctic Intermediate Water (AAIW) and Antarctic Bottom Water (AABW). Along the cruise track, there are potential sources (eolian dusts, marginal sediments, oceanic volcanism, and nepheloid layer) that could add external Nd to seawater and disturb the “quasi-conservative” behavior of εNd. Our results show strikingly that the Southwest Atlantic transect confirms “quasi-conservative” behavior of εNd in intermediate and deep water. Our evaluations of Nd isotopic deviations (ΔεNd) from conservative behavior show that out of 198 intermediate and deep samples, 49% of ΔεNd-values are within ± 0.25 εNd units (< analytical error: ± 0.30 εNd units) and 84% of ΔεNd-values are within ± 0.75 εNd units. Potential sources that could add external Nd to seawater from oceanic volcanism and the nepheloid layer do not show impact on seawater εNd.

Terrigenous sources of Nd (e.g. eolian dusts from Africa and Patagonia, marginal sediments from South America) show influence on surface/subsurface water εNd but this εNd signature is not transferred to intermediate and deep water. To better understand the conservative vs. non-conservative behavior of REEs in the ocean, the dissolved REE concentrations were analyzed for the 17 seawater profiles in the Southwest Meridional Atlantic Transect (GEOTRACES GA02 Leg 3). The shale-normalized REE patterns are consistent with typical seawater patterns. To investigate whether and how much REE concentrations deviate from conservative water mass mixing, the REE concentration deviations were calculated for the intermediate and deep water. It is shown that within the SAMT, the intermediate and deep water REEs generally reflect water mass mixing and nearly conservative behavior. Along this transect, the potential sources that could add external REEs to seawater are dissolution of REEs from eolian dust to the surface/subsurface water, REEs released from dissolution of Fe-Mn oxides in the oxygen depleted zone, REEs from sediments near the continental margin, and dissolution of REEs from deep sea sediments.

REEs and Nd isotopes of most intermediate and deep water masses passing the volcanic Rio Grande Rise (RGR) and Vitória-Trindade Ridge (VTR) do not show influence from RGR and VTR. REEs and Nd isotopes of the bottom water Lower Circumpolar Deep Water (LCDW) and AABW passing the RGR are influenced by dissolved REEs from the deep sea sediments. LCDW and AABW passing the VTR are influenced by dissolved REEs from the deep sea sediments as well as the volcanic VTR. In order to better understand the oceanic Nd cycling in the North Pacific, its sources and sinks in seawater must be better characterized. The high εNd of North Pacific Deep Water (NPDW, ~ −4) has been difficult to reconcile with the eolian inputs as reflected in surface waters (e.g. Jones et al., 2008), which have much lower εNd (~ −10), indicating potential addition of a component from Pacific volcanism. In order to constrain the REE sources in the North Pacific, we measured εNd and REEs of seawater from five stations across the subarctic North Pacific sampled by the Innovative North Pacific Experiment (INOPEX) Cruise SO202 (2009).

In the surface water (~10 m), the highest εNd is observed at the station closest to the Aleutian-Kamchatka volcanic margin (Northwest station SO202-5), suggesting higher contribution of external REEs from volcanic ashes compared to the other stations. In the shallow water (100-400 m, depending on location), remineralization of REEs from volcanic ashes prevails over Asian dusts at Northwest station SO202-5 and near Japan stations SO202-44, 41, and 39, whereas remineralization of REEs from Asian dusts prevails over volcanic ashes at the Northeast station SO202-32 in the open ocean of the Alaska Peninsula. From the depths of North Pacific Intermediate Water (NPIW) to NPDW, seawater εNd and REEs show conservative water mass mixing of NPIW-NPDW. They also show conservative behavior along the water mass transport paths of NPIW and NPDW. Below the depths of NPDW, addition of external REEs is observed in the vertical profiles of εNd and REEs as well as along the transport path of LCDW. The potential sources that add external REEs to the bottom water are (1) sediments on the Kuril-Kamchatka-Aleutian volcanic margin along the LCDW transport path, and (2) sediments on the seafloor, both of which could interact with seawater and modify the seawater εNd and REE signatures.