Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.

Geochemistry of Eocene/Oligocene sediments of ODP Hole 154-925A

Paleoproductivity, nutrient burial, and carbon cycling were investigated across the Eocene/Oligocene (E/O) boundary (begin to end; 36.9-32.7 Ma at ~40 kyr resolution, timescale of Shackleton et al. (1999, doi:10.1098/rsta.1999.0407) at Ocean Drilling Program Site 925 on the Ceara Rise in the western equatorial Atlantic (3040 m present water depth; 748.26-850.70 mbsf). Downcore bulk sediment records of biogenic barium, total reactive phosphorus, biogenic silica, and calcium carbonate are interpreted to represent export production, net nutrient burial, biogenic opal production, and inorganic carbon burial, respectively. The global positive excursion in d13C subsequent to the E/O boundary is recorded at Site 925. Export production appears to have been externally forced by orbital parameters at eccentricity frequencies during the study interval, based on spectral analysis of the biogenic barium and reactive phosphorus records. Biogenic silica production or preservation increased after the Eocene/Oligocene boundary to a higher baseline, although overall productivity and nutrient burial did not increase, based on barium and reactive phosphorus records. Thus, although absolute production did not increase at this site, a shift in relative abundance of siliceous versus carbonate productivity may have resulted in a change in relative organic carbon burial. This may have contributed to the positive excursion in global oceanic d13C subsequent to the Eocene/Oligocene boundary, although the silica maximum persists after the carbon isotope excursion ends.

Oxygen microprofiles and porewater chemistry in sediments of the Skagerrak

Sediment porewater oxygen profiles were measured with micro and needle electrodes in sediment cores of 27 stations in the Skagerrak (northeastern North Sea). Oxygen penetration depth ranged from 3 to 20 mm depth. Fluxes estimated from the oxygen gradients varied from 3 to 18 mmol m**-2 d**-1. Oxygen penetration and flux depend on water depth, but possibly more on the hydrological conditions, related to the import of fresh organic matter by primary production in the water column. Oxygen fluxes were not related to the total organic carbon (TOC) content of the sediments. Stations in the eastern part of the Skagerrak showed high burial rates of TOC. At 6 stations porewater chemistry of Fe, Mn and NO3- was strongly associated with the oxygen distribution. The average relative contribution of terminal electron acceptors to carbon mineralisation was estimated at 85% for O2, 0.5% for Mn, 4.5% for [NO3]3-, 1% for Fe and 9% for [SO4]2-. At one station the occurrence of exceptionally high solid manganese oxyhydroxides was probably related to an active internal manganese cycle.

(Table 1) Pore water halogen concentrations in ODP Holes 169-1033B and 169-1034B

The entire suite of halogens was measured in the pore fluids of Hole 1033B and 1034B from Saanich Inlet: ODP Leg 169S. The fast sedimentation rates and large amount of organic carbon burial coupled with anoxia of the overlying waters promotes an advanced stage of diagenesis within the sediment column. Chloride interstitial water profiles suggest salinity variations within the waters of Saanich Inlet. Concentration profiles for iodide and bromide support the argument that they are produced through the degradation of organic matter. Although the concentration increases in I- and Br- indicate that these halides are not regenerated in similar proportions to marine organic matter, it appears that iodide and bromide are regenerated to similar degrees within the sediment column and in similar proportions to the sediment halide concentrations. Fluoride porewater values show a complicated pattern, most likely caused by secondary reactions involving complexation with Mg2+, carbonate fluorapatite precipitation, carbonate mineral diagenesis, and/or uptake into alumino-silicate minerals.

(Table 8.4, Page 220-223) Chemical composition of different growth structures of manganese nodules, SONNE cruise SO78

In the nodule field of the Peru Basin, situated south of the zone of high bioproductivity, a relatively high flux of biogenic matter explains a distinct redox boundary at about 10 cm depth separating very soft oxic surface sediments from stiffer suboxic sediments. Maximum abundance (50 kg/m**2) of diagenetic nodules is found near the calcite compensation depth (CCD), currently at 4250 m. There, the accretion rate of nodules is much higher (100 mm/Ma) than on ridges (5 mm/Ma). Highest accretion rates are found at the bottom of large nodules that repeatedly sink to a level immediately above the redox boundary. There, distinct diagenetic growth conditions prevail and layers of dense laminated Mn oxide of very pure todorokite are formed. The layering of nodules is mainly the result of organisms moving nodules within the oxic surface sediment from diagenetic to hydrogenetic environments. The frequency of such movements is much higher than that of climatic changes. Two types of nodule burial occur in the Peru Basin. Large nodules are less easily moved by organisms and become buried. Consequently, buried nodules generally are larger than surface nodules. This type of burial predominates in basins. At ridges where smaller nodules prevail, burial is mainly controlled by statistical selection where some nodules are not moved up by organisms.

(Table T1) Pore-water strontium content, and Sr isotope composition and ages of pore waters and sedimentary carbonates of ODP Leg 171B sites

Strontium concentrations and 87Sr/86Sr values were measured on pore-water and sedimentary carbonate samples from sediments recovered at Sites 1049-1053 on the Blake Spur during Ocean Drilling Program Leg 171B. These sites form a 40-km-long depth transect extending along the crest of the Blake Spur from near the upper edge of the Blake Escarpment (a steep cliff composed of Mesozoic carbonates) westward toward the interior of the Blake-Bahama Platform. Although these sites were selected for paleoceanographic purposes, they also form a hydrologic transect across the upper eastern flank of the Blake-Bahama Platform. Here, we use pore-water strontium concentrations and isotopes as a proxy to define patterns of fluid movement through the flanks of this platform. Pore-water strontium concentration increases with depth at all sites implying that strontium has been added during sediment burial and diagenesis. The isotopic values decrease from seawater-like values in the shallow samples (~0.70913) to values as low as 0.707342 in one of the deepest samples (~625 meters below seafloor). The change in pore-water strontium isotopic values is independent of the strontium isotopic compositions predicted from the host sediment age and measured on bulk carbonate in some samples. In most cases the difference between predicted sediment strontium isotopic composition and measured value is less than ±2 about the mean of the measured strontium value. Both the increase in concentration and the decrease in the strontium isotope values with increasing depth indicate that strontium was expelled from older carbonates. The strontium concentration and isotope profiles vary between sites according to their proximity to the Blake-Bahama Platform edge. Profiles from Site 1049 (nearest the platform edge) show the greatest amount of mixing with modern seawater, whereas the site most distal to the platform edge (Site 1052) shows the most significant influence of older, deeper carbonates on the pore-water strontium isotopic composition.

(Table 1) Concentrations of Os, Ir, Pt and 187Os/188Os ratio in ODP Hole 130-806C samples

New osmium (Os) isotope and platinum group element (PGE) concentration data are used in conjunction with published 3He and Th isotope data to determine the relative proportions of lithogenic, extraterrestrial and hydrogenous iridium (Ir) in a Pacific pelagic carbonate sequence from the Ocean Drilling Program (ODP) Site 806 on the Ontong Java Plateau (OJP). These calculations demonstrate that lithogenic and extraterrestrial contributions to sedimentary Ir budget are minor, while hydrogenous Ir accounts for roughly 85% of the total Ir. Application of analogous partitioning calculations to previously reported data from a North Pacific red clay sequence (LL44-GPC3) yields very similar results. Total Ir burial fluxes at Site 806 and LL44-GPC3 are also similar, 45 and 30 pg/cm**2/kyr, respectively. Average Ir/3He and Ir/xs230Th_initial ratios calculated from the entire Site 806 data set are similar to those reported earlier for Pacific sites. In general, down-core profiles of Ir, 3He and xs230Th_initial, are not well correlated with one another. However, all three data sets show similar variance and yield sediment mass accumulation rate estimates that agree within a factor of two. While these results indicate that Ir concentration has potential as a point-paleoflux tracer in pelagic carbonates, Ir-based paleoflux estimates are likely subject to uncertainties that are similar to those associated with Co-based paleoflux estimates. Consequently, local calibration of Ir flux in space and time will be required to fully assess the potential of Ir as a point paleoflux tracer. Measured 187Os/188Os of the OJP sediments are systematically lower than the inferred 187Os/188Os of contemporaneous seawater and a clear glacial-interglacial 187Os/188Os variation is lacking. Mixing calculations suggest Os contributions from lithogenic sources are insufficient to explain the observed 187Os/188Os variations. The difference between the 187Os/188Os of bulk sediment and that of seawater is interpreted in terms of subtle contributions of unradiogenic Os carried by particulate extraterrestrial material. Down-core variations of 187Os/188Os with Pt/Ir and Os/Ir also point to contributions from extraterrestrial particles. Mixing calculations for each set of several triplicate analyses suggest that the unradiogenic Os end member cannot be characterized by primary extraterrestrial particles of chondritic composition. It is noteworthy that in efforts aimed at determining the effect of extraterrestrial contributions, 187Os/188Os of pelagic carbonates has greater potential compared to abundances of PGE. An attempt has been made for the first time to estimate sediment mass accumulation rates based on amount of extraterrestrial Os in the OJP samples and previously reported extraterrestrial Os flux. Throughout most of the OJP record, Os isotope-based paleoflux estimates are within a factor of two of those derived using other constant flux tracers. Meaningful flux estimates cannot be made during glacial maxima because the OJP sediments do not record the low 187Os/188Os reported previously. We speculate that this discrepancy may be related to focusing of extraterrestrial particles at the OJP, as has been suggested to explain down-core 3He variations.

(Table 3) Clay mineralogy and calcium carbonate and organic carbon contents of fabric samples of ODP Leg 117

Calcium carbonate and organic carbon concentrations are from measurements made on board the JOIDES Resolution during Leg 117 (Prell, Niitsuma, et al., 1989, doi:10.2973/odp.proc.ir.117.1989). Values are for samples immdiately adjacent to fabric samples, or for Site 723 within 25 cm of the fabric sample interval. Intervals for which carbon analyses were not performed are represented by values in parenthesis which are from the nearest interval of similar lithology. Organic carbon analyses were not performed for samples below 402 mbsf at Site 731. Analyses performed on similar sediments at Sites 722 and 731 indicate the organic carbon concentration is probably <0.20%.