Description: The isotopic composition of neodymium (epsilon-Nd) extracted from sedimentary Fe-Mn oxyhydroxide offers potential for reconstructing paleo-circulation, but its application depends on extraction methodology and the mechanisms that relate authigenic epsilon-Nd to bottom water. Here we test methods to extract authigenic epsilon-Nd from Gulf of Alaska (GOA) sediments and assess sources of leachate Nd, including potential contamination from trace dispersed volcanic ash. We show that one dominant phase is extracted via leaching of core-top sediments. Major and trace element geochemistry demonstrate that this phase is authigenic Fe-Mn oxyhydroxide. Contamination of leachate (authigenic) Nd from detrital sources is insignificant (〈1%); our empirical results are consistent with established kinetic mineral dissolution rates and theory. Contamination of extracted epsilon-Nd from leaching of volcanic ash is below analytical uncertainty. However, the epsilon-Nd of core-top leachates in the GOA is consistently more radiogenic than bottom water. We infer that authigenic phases record pore water epsilon-Nd, and the relationships of epsilon-Nd among bottom waters, pore waters, authigenic phases and detrital sediments are primarily governed by the exposure time of bottom water to sea-floor sediments, rate of exchange across the sediment-water interface and the reactivity and composition of detrital sediments. We show that this conceptual model is applicable on the Pacific basin scale and provide a new framework to understand the role of authigenic phases in both modern and paleo-applications, including the use of authigenic epsilon-Nd as a paleo-circulation tracer.

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: 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: 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: Here we report the neodymium isotope compositions of sedimentary authigenic Fe-Mn oxyhydroxide and bulk sediment in the Gulf of Alaska, Northeast Pacific. These records span the last 22,000 years. We use these records to reconstruct deglacial North Pacific circulation.

Description: We integrate micropaleontological and geochemical records (benthic stable isotopes, neodymium isotopes, benthic foraminiferal abundances and XRF-scanner derived elemental data) from well-dated Pacific Ocean successions(15-12.7Ma) to monitor circulation changes during the middle Miocene transition into a colder climate mode with permanent Antarctic ice cover. Together with previously published records, our results show improvement in deepwater ventilation and strengthening of the meridional overturning circulation following major ice expansion at 13.9 Ma. Neodymium isotope data reveal, however, that the provenance of intermediate and deepwater masses did not change markedly between 15 and 12.7 Ma. We attribute the increased d13C gradient between Pacific deep and intermediate water masses between 13.6 and 12.7 Ma to more vigorous entrainment of PacificCentral Water into the wind-driven ocean circulation due to enhanced production of intermediate and deep waters in the Southern Ocean. Prominent 100 kyr ventilation cycles after 13.9 Ma reveal that the deep Pacific remained poorly ventilated during warmer intervals at high eccentricity, whereas colder periods (low eccentricity) were characterized by a more vigorous meridional overturning circulation with enhanced carbonate preservation. The long-term d13C decline in Pacific intermediate and deepwater sites between 13.5 and 12.7 Ma reflects a global trend, probably related to a re-adjustment response of the global carbon cycle following the last 400 kyr carbon maximum (CM6) of the ''Monterey Excursion''.

Description: The assemblages of marine sediments on the SW Iberian shelf have been controlled by contributions from distinct sources, which have varied in response to environmental changes since the Last Glacial Maximum (LGM). The rapid, decadal scale Mediterranean overturning circulation permits mixing of suspended particles from the entire Mediterranean Sea. They are entrained into the suspended particulate matter (SPM) carried by Mediterranean Outflow Water (MOW), which enters the eastern North Atlantic through the Strait of Gibraltar and spreads at intermediate depths in the Gulf of Cadiz and along the Portuguese continental margin. Other major sediment sources that have contributed to the characteristics and budget of SPM along the flow path of MOW on the SW Iberian shelf are North African dust and river-transported particles from the Iberian Peninsula. To reconstruct climate- and circulation-driven changes in the supply of sediments over the past ~23000 cal yr B.P., radiogenic Nd, Sr and Pb isotope records of the clay-size sediment fraction were obtained from one gravity core in the Gulf of Cadiz (577 m water depth) and from two gravity cores on the Portuguese shelf (1745 m, 1974 m water depth). These records are supplemented by time series analyses of clay mineral abundances from the same set of samples. Contrary to expectations, the transition from the LGM to the Holocene was not accompanied by strong changes in sediment provenance or transport, whereas Heinrich Event 1 (H1) and the African Humid Period (AHP) were marked by significantly different isotopic signatures reflecting changes in source contributions caused by supply of ice rafted material originating from the North American craton during H1 and diminished supply of Saharan dust during the AHP. The data also reveal that the timing of variations in the clay mineral abundances was decoupled from that of the radiogenic isotope signatures.

Description: We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Description: Lead (Pb), neodymium (Nd), and strontium (Sr) isotopic analyses were carried out on sediment leachates (reflecting the isotope composition of past seawater) and digests of the bulk residues (reflecting detrital continental inputs) of Integrated Ocean Drilling Program (IODP) Leg 302 and core PS2185 from the Lomonosov Ridge (Arctic Ocean). Our records are interpreted to reflect changes in continental erosion and oceanic circulation, driven predominantly by tectonic forcing on million-year timescales in the older (pre-2 Ma) part of the record and by climatic forcing of weathering and erosion of the Eurasian continental margin on thousand-year timescales in the younger (post-2 Ma) part. These data, covering the past ~15 Ma, show that continental inputs to the central Arctic Ocean have been more closely linked to glacial and hydrological processes occurring on the Eurasian margin than on continental North America and Greenland. The constancy of the detrital input signatures supports the early existence of an Arctic sea ice cover, whereas the major initiation of Northern Hemisphere glaciation at 2.7 Ma appears to have had little impact on the weathering regime of the Eurasian continental margin.

Description: Mediterranean Outflow Water (MOW) is characterised by higher temperatures and salinities than other ambient water masses. MOW spreads at water depths between 500 and 1500 m in the eastern North Atlantic and has been a source of salinity for the Atlantic Meridional Overturning Circulation in the North Atlantic. We used high-resolution Nd and Pb isotope records of past ambient seawater obtained from authigenic ferromanganese coatings of sediments in three gravity cores at 577, 1745 and 1974 m water depth in the Gulf of Cadiz and along the Portuguese margin complemented by a selection of surface sediments to reconstruct the extent and pathways of MOWover the past 23 000 years. The surface and downcore Nd isotope data from all water depths exhibit only a very small variability close to the present day composition of MOW but do not reflect the present day Nd isotopic stratification of the water column as determined from a nearby open ocean hydrographic station. In contrast, the Pb isotope records show significant and systematic variations, which provide evidence for a significantly different pattern of the MOW pathways between 20 000 and 12 000 years ago compared with the subsequent period of time.