Description: Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z 〉 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Description: The ability to reconstruct past ocean currents is essential for determining ocean circulation's role in global heat transport and climate change. Our understanding of the relationship between circulation and climate in the past allows us to predict the impact of future climate-driven circulation changes. One proposed tracer of past ocean circulation is the neodymium isotope composition (epsilon-Nd) of ancient water masses. However, ambiguities in what governs the epsilon-Nd distribution in the modern ocean hamper interpretations of this tracer. Here we present epsilon-Nd values for marine pore fluids, sediments, and the overlying water column for three sites in the North Pacific. We find that ocean bottom water epsilon-Nd (epsilon-NdBW) in the northeast Pacific lies between the value expected for the water mass (-3.3) and the measured epsilon-Nd of sediment pore fluid (epsilon-NdPW; -1.8). Moreover, epsilon-NdPW resembles the epsilon-Nd of the sediment. Combined, these findings are consistent with recent assessments that sediment pore fluids may be a major source of rare earth elements to the ocean and suggest that the benthic flux of Nd from pore fluids exerts the primary control over the deep ocean distribution of epsilon-Nd.

Description: Because ocean circulation impacts global heat transport, understanding the relationship between deep ocean circulation and climate is important for predicting the ocean's role in climate change. A common approach to reconstruct ocean circulation patterns employs the neodymium isotope compositions of authigenic phases recovered from marine sediments. In this approach, mild chemical extractions of these phases is thought to yield information regarding the epsilon-Nd of the bottom waters that are in contact with the underlying sediment package. However, recent pore fluid studies present evidence for neodymium cycling within the upper portions of the marine sediment package that drives a significant benthic flux of neodymium to the ocean. This internal sedimentary cycling has the potential to obfuscate any relationship between the neodymium signature recovered from the authigenic coating and the overlying neodymium signature of the seawater. For this manuscript, we present sedimentary leach results from three sites on the Oregon margin in the northeast Pacific Ocean. Our goal is to examine the potential mechanisms controlling the exchange of Nd between the sedimentary package and the overlying water column, as well as the relationship between the epsilon-Nd composition of authigenic sedimentary coatings and that of the pore fluid. In our comparison of the neodymium concentrations and isotope compositions from the total sediment, sediment leachates, and pore fluid we find that the leachable components account for about half of the total solid-phase Nd, therefore representing a significant reservoir of reactive Nd within the sediment package. Based on these and other data, we propose that sediment diagenesis determines the epsilon-Nd of the pore fluid, which in turn controls the epsilon-Nd of the bottom water. Consistent with this notion, despite having 1 to 2 orders of magnitude greater Nd concentration than the bottom water, the pore fluid is still 〈0.001% of the total Nd reservoir in the upper sediment column. Therefore, the pore fluid reservoir is too small to maintain a unique signature, and instead must be controlled by the larger reservoir of Nd in the reactive coatings. In addition, to achieve mass balance, we find it necessary to invoke a cryptic radiogenic (epsilon-Nd of +10) trace mineral source of neodymium within the upper sediment column at our sites. When present, this cryptic trace metal results in more radiogenic pore fluid.

Description: We determined pore fluid rare earth element (REE) concentrations in near-surface sediments retrieved from the continental margin off Oregon and California (USA). These sites represent shelf-to-slope settings, which lie above, within, and below the oxygen minimum zone of the Northeast Pacific. The sediments are characterized by varying degrees of net iron reduction, with pore fluids from the shelf sites being generally ferruginous, and the slope sediments having less-pronounced iron reduction zones that originate deeper in the sediment package. REE concentrations show maxima in shallow (upper 2-10 cm) subsurface pore fluids across all sites with concentrations that rise more than two orders of magnitude higher than seawater. These pore fluid enrichments highlight the importance of a sedimentary source of REEs to the ocean's water column. Here we use our measurements to estimate the diffusive flux of Nd out of ocean sediments resulting in a global flux between 18 and 110 × 10**6 mol Nd/yr. While we do assume that our pore fluid profiles as well as the very limited data previously published are representative of a wide array of ocean environments, this calculated flux can account for the modeled missing Nd source flux (76 × 10**6 mol Nd/yr) in global budgets (Arsouze et al., 2009). Pore fluid normalized REE patterns show distinct variation in the middle REE and heavy REE enrichments with sediment depth and amongst sites. These patterns show that the heavy REE enrichment of pore fluids at our deep slope site (3000 m water depth) is closest to the heavy REE enrichment of seawater. This observation supports the view that REE cycling within the upper ten centimeters of deep-sea marine sediments, as opposed to shallower continental shelf and slope sediments, plays a significant role in controlling the integrated global REE flux from the pore fluids and consequently the broad-scale REE pattern in seawater.

Description: Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANT-XXIV/3 and ANT-XXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (〈0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labelled by terrigenous inputs. Near South Africa Nd isotope values as low as epsilon-Nd = -18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to epsilon-Hf = 6.1 and epsilon-Nd = -4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (epsilon-Nd ~ -8 to -8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Pasage. The Hf isotope compositions in the entire study area only show a small range between epsilon-Hf = +6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from epsilon-Nd = -18.9 to -4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.