ALBERT

Description: The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters. For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific εNd and εHf both decrease with water depth. Similarly, εNd and εHf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable. The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific. Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.

Description: Time series of lead (Pb) and neodymium (Nd) isotope compositions were measured on three ferromanganese crusts recording the evolution of NE Atlantic water masses over the past 15 Ma. The crusts are distributed along a depth profile (∼700–4600 m) comprising the present-day depths of Mediterranean Outflow Water and North East Atlantic Deep Water. A pronounced increase of the 206Pb/204Pb in the two deeper crusts starting at ∼4 Ma and a decrease in 143Nd/144Nd in all three crusts took place between ∼6–4 Ma and the present. These patterns are similar to isotope time series in the western North Atlantic basin and are consistent with efficient mixing between the two basins. However, the changes occurred 1–3 Ma earlier in the eastern basin indicating that the northeastern Atlantic led the major change in Pb and Nd isotope composition, probably due to a direct supply of Labrador Seawater via a northern route. The Pb isotope evolution during the Pliocene-Pleistocene can generally be explained by mixing between two end-members corresponding to Mediterranean Outflow Water and North East Atlantic Deep Water, but external sources such as Saharan dust are likely to have played a role as well. The Pb isotope composition of the shallowest crust that grew within the present-day Mediterranean Outflow Water does not show significant Pb isotope changes indicating that it was controlled by the same Pb sources throughout the past 15 Ma.

Description: The application of radiogenic isotopes to the study of Cenozoic circulation patterns in the South Pacific Ocean has been hampered by the fact that records from only equatorial Pacific deep water have been available. We present new Pb and Nd isotope time series for two ferromanganese crusts that grew from equatorial Pacific bottom water (D137-01, “Nova,” 7219 m water depth) and southwest Pacific deep water (63KD, “Tasman,” 1700 m water depth). The crusts were dated using 10Be/9Be ratios combined with constant Co-flux dating and yield time series for the past 38 and 23 Myr, respectively. The surface Nd and Pb isotope distributions are consistent with the present-day circulation pattern, and therefore the new records are considered suitable to reconstruct Eocene through Miocene paleoceanography for the South Pacific. The isotope time series of crusts Nova and Tasman suggest that equatorial Pacific deep water and waters from the Southern Ocean supplied the dissolved trace metals to both sites over the past 38 Myr. Changes in the isotopic composition of crust Nova are interpreted to reflect development of the Antarctic Circumpolar Current and changes in Pacific deep water circulation caused by the build up of the East Antarctic Ice Sheet. The Nd isotopic composition of the shallower water site in the southwest Pacific appears to have been more sensitive to circulation changes resulting from closure of the Indonesian seaway.

Description: The intensity of North Atlantic Deep Water (NADW) production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate. Here we present a new approach to reconstruct the overall strength of NADW export from the North Atlantic to the Southern Ocean over the past 14 Myr applying the deep water Nd and Pb isotope composition as recorded by ferromanganese crusts and nodules. We present the first long-term Nd and Pb isotope time series for deep Southern Ocean water masses, which are compared with previously published time series for NADW from the NW Atlantic Ocean. These data suggest a continuous and strong export of NADW, or a precursor of it, into the Southern Ocean between 14 and 3 Ma. An increasing difference in Nd and Pb isotope compositions between the NW Atlantic and the Southern Ocean over the past 3 Myr gives evidence for a progressive overall reduction of NADW export since the onset of Northern Hemisphere glaciation (NHG). The Nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37% depending on location.

Description: The sources of non-anthropogenic Pb in seawater have been the subject of debate. Here we present Pb isotope time-series that indicate that the non-anthropogenic Pb budget of the northernmost Pacific Ocean has been governed by ocean circulation and riverine inputs, which in turn have ultimately been controlled by tectonic processes. Despite the fact that the investigated locations are situated within the Asian dust plume, and proximal to extensive arc volcanism, eolian contributions have had little impact. We have obtained the first high-resolution and high-precision Pb isotope time-series of North Pacific deep water from two ferromanganese crusts from the Gulf of Alaska in the NE Pacific Ocean, and from the Detroit Seamount in the NW Pacific Ocean. Both crusts were dated applying 10Be/9Be ratios and yield continuous time-series for the past 13.5 and 9.6 Myr, respectively. Lead isotopes show a monotonic evolution in 206Pb/204Pb from low values in the Miocene (≤18.57) to high values at present day (≥18.84) in both crusts, even though they are separated by more than 3000 km along the Aleutian Arc. The variation exceeds the amplitude found in Equatorial Pacific deep water records by about three-fold. There also is a striking similarity in 207Pb/204Pb and 208Pb/204Pb ratios of the two crusts, indicating the existence of a local circulation cell in the sub-polar North Pacific, where efficient lateral mixing has taken place but only limited exchange (in terms of Pb) with deep water from the Equatorial Pacific has occurred. Both crusts display well-defined trends with age in Pb–Pb isotope mixing plots, which require the involvement of at least four distinct Pb sources for North Pacific deep water. The Pb isotope time-series reveal that eolian supplies (volcanic ash and continent-derived loess) have only been of minor importance for the dissolved Pb budget of marginal sites in the deep North Pacific over the past 6 Myr. The two predominant sources have been young volcanic arcs, one located in the northeastern part and one located in the northwestern part of the Pacific margin, from where material has been eroded and delivered to the ocean, most likely via riverine pathways.

Description: Ferromanganese crusts provide records of long term change in ocean circulation and continental weathering. However, calibrating their age prior to 10 Ma has been entirely based on empirical growth rate models using Co concentrations, which have inherently large uncertainties and fail to detect hiatuses and erosional events. We present a new method for dating these crusts by measuring their osmium (Os) isotope record and matching it to the well-known marine Os isotope evolution of the past 80 Ma. The well-characterised crust CD29-2 from the central Pacific, was believed to define a record of paleooceanographic change from 50 Ma. Previous growth rate estimates based on the Co method are consistent with the new Os isotope stratigraphy but the dating was grossly inaccurate due to long hiatuses that are now detectable. The new chronology shows that it in fact started growing prior to 70 Ma in the late Cretaceous and stopped growing or was eroded between 13.5 and 47 Ma. With this new technique it is now possible to exploit the full potential of the oceanographic and climatic records stored in Fe–Mn crusts.

Description: A unique set of ferromanganese crusts and nodules collected from Shatsky Rise (SR), NW Pacific, were analyzed for mineralogical and chemical compositions, and dated using Be isotopes and cobalt chronometry. The composition of these midlatitude, deep-water deposits is markedly different from northwest-equatorial Pacific (PCZ) crusts, where most studies have been conducted. Crusts and nodules on SR formed in close proximity and some nodule deposits were cemented and overgrown by crusts, forming amalgamated deposits. The deep-water SR crusts are high in Cu, Li, and Th and low in Co, Te, and Tl concentrations compared to PCZ crusts. Thorium concentrations (ppm) are especially striking with a high of 152 (mean 56), compared to PCZ crusts (mean 11). The deep-water SR crusts show a diagenetic chemical signal, but not a diagenetic mineralogy, which together constrain the redox conditions to early oxic diagenesis. Diagenetic input to crusts is rare, but unequivocal in these deep-water crusts. Copper, Ni, and Li are strongly enriched in SR deep-water deposits, but only in layers older than about 3.4 Ma. Diagenetic reactions in the sediment and dissolution of biogenic calcite in the water column are the likely sources of these metals. The highest concentrations of Li are in crust layers that formed near the calcite compensation depth. The onset of Ni, Cu, and Li enrichment in the middle Miocene and cessation at about 3.4 Ma were accompanied by changes in the deep-water environment, especially composition and flow rates of water masses, and location of the carbonate compensation depth. Key Points - Fe-Mn crusts can have a diagenetic component - Mid-latitude N. Pacific deep-water Fe-Mn crusts are uniquely enriched in Cu, Th, Li - Temporal changes in deep-ocean geochemical processes are recorded