Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Trace element abundance, and Sr and Nd isotope ratios of dust samples in the Pacific Ocean (Table 2)

Eolian dust preserved in deep-sea sediment cores provides a valuable indicator of past atmospheric circulation and continental paleoclimate. In order to identify the provenance of eolian dust, Nd and Sr isotopic compositions and Rb, Sr and rare earth element (REE) concentrations have been determined for the silicate fractions of deep-sea sediments from the north and central Pacific Ocean. Different regions of the Pacific Ocean are characterized by distinct air-borne inputs, producing a large range in epsolin-Nd (-10 to +1), 87Sr/86Sr (0.705-0.721), La/Yb (5-15), EuN/EuN* (0.6-1.0) and Sr/Nd (4-33). The average Nd isotopic composition of Pacific deep-sea sediments (epsilon-Nd = -6), is more radiogenic than the average from the Atlantic (epsilon-Nd = -8). In contrast, the average147Sm/144Nd ratio for Pacific sediments (0.114) is identical to that of Atlantic sediments and to that of global average riverine suspended material. The values of epsilon-Nd and147Sm/144Nd are positively correlated for the Pacific samples but negatively correlated for Atlantic samples, reflecting a fundamental difference between the dominant components in the end members with radiogenic Nd (island-arc components in the Pacific and LREE-enriched intraplate ocean island components in the Atlantic). Samples from the north central Pacific have distinctive unradiogenic epsilon-Nd values of -10, 87Sr/86Sr > 0.715, high La/Yb (> 12), and low EuN/EuN* (0.6) and Sr/Nd (3-6). These data are virtually identical to the values for loess from Asia and endorse the use of these sediments as indicators of Asian paleoclimate and paleowind directions. Island-arc contributions appear to dominate in the northwest Pacific, resulting in higher epsilon Nd (-1 to +1) and lower 87Sr/86Sr (~ 0.705) and La/Yb (~ 5). Sediments from the eastern Pacific tend to have intermediate Sr and Nd isotopic compositions but regionally variable Sr/Nd and REE patterns; they appear to be derived from the west margin of the North and South American continents, rather than from Asia. Our results confirm that dust provenance can be constrained by isotopic and geochemical analyses, which will facilitate reconstructions of past atmospheric circulation and continental paleoclimate.

Revised chronology of Neogene DSDP holes from the World Ocean

After nearly 30 years of growth in geochronologic knowledge, the originally published age models for many older deep sea marine sections have become badly outdated. In this report we present newly revised age models for Neogene sediments from 94 DSDP holes. Biostratigraphic data for planktonic foraminifers, calcareous nannofossils, diatoms and radiolarians, paleomagnetic and other stratigraphic data were compiled from the original Initial Reports volumes of DSDP. The Berggren et al. (1985 doi:10.1130/0016-7606(1985)96<1407:CG>2.0.CO;2) scale was used for the age of magnetic reversals, and a variety of recent papers were used to establish a standard modern set of calibrations for marine microfossil events to the magnetic reversal scale. New age vs depth plots were made for each hole, and for each a new line of correlation was created. All tabulated stratigraphic data, new age models, and age depth plots are given as appendices to the report.