Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

Grain size analyses, Ca/Ti and other selected elemental ratios from XRF core scanning of sediment cores from the Apulian Margin

An extensive, high-resolution, sedimentological-geochemical survey was done using geo-acoustics, XRF-core scans, ICP-AES, AMS 14C-dating and grain size analyses of sediments in 11 cores from the Gulf of Taranto, the southern Adriatic Sea, and the central Ionian Sea spanning the last 16 cal. ka BP. Comparable results were obtained for cores from the Gallipoli Shelf (eastern Gulf of Taranto), and the southern Adriatic Sea suggesting that the dominant provenance of Gallipoli Shelf sediments is from the western Adriatic mud belt. The 210Pb and 14C-dated high-accumulation-rate sediments permit a detailed reconstruction of climate variability over the last 16 cal. ka BP. Although, the Glacial-Interglacial transition is generally dry and stable these conditions are interrupted by two phases of increased detrital input during the Bølling-Allerød and the late Younger Dryas. The event during the Younger Dryas period is characterized by increased sediment inputs from southern Italian sources. This suggests that run-off was higher in southern- compared to northern Italy. At approximately ~ 7 cal. ka BP, increased detrital input from the Adriatic mud belt, related to sea level rise and the onset of deep water formation in the Adriatic Sea, is observed and is coincident with the end of sapropel S1 formation in the southern Adriatic Sea. During the mid-to-late Holocene we observed millennial-scale events of increased detrital input, e.g. during the Roman Humid Period, and of decreased detrital input, e.g., Medieval Warm Period. These dry/wet spells are consistent with variability in the North Atlantic Oscillation (NAO). A negative state of the NAO and thus a more advanced penetration of the westerlies into the central Mediterranean, that result in wet conditions in the research area concord with events of high detrital input e.g., during the Roman Humid Period. In contrast, a positive state of the NAO, resulting in dry conditions in the Mediterranean, dominated during events of rapid climate change such as the Medieval Warm Period and the Bronze Age.

Organic matter in sediments of ODP Site 131-808

Microscopic studies reveal a predominance of terrestrial organic matter in sediments of Site 808. Terrestrial vitrinite and inertinite are more abundant (73% to 100%) than marine organic matter (alginite, 0% to 27%), which increases from open oceanic deposits of the Shikoku Basin sediments to sediments of the outer trench wedge. The abundance of terrestrial organic matter is also reflected through carbon isotope values of -23 per mil to -25.9 per mil. Mass accumulation rates of organic carbon are low in hemipelagic sediments of the Shikoku Basin (<0.2 g/cm**2/k.y.) but increase significantly in sediments of the Nankai Trench (0.2 to 1.7 g/cm**2/k.y.). Although the organic mass accumulation is high in sediments of the Nankai Trench, a comparison of sedimentation rates and total organic carbon suggests relative dilution of organic carbon through turbidite flows. Calculated marine paleoproductivity of organic carbon is low in sediments of the open ocean (Shikoku Basin) and increases closer to the shore (Nankai Trench). Thermal evolution of organic matter is obtained from vitrinite reflectance measurements. Two populations of vitrinites have been observed between 600 and 1234 mbsf. Reflectance values change with increasing depth and temperature in both groups of vitrinite (0.3% to 0.68% in group 1; 0.6% to 1% in group 2).

Geochemistry, sediment components, and paleoproductivity reconstruction for the Miocene to early Pliocene sediments

We reconstruct paleoproductivity at three sites in the Atlantic Ocean (Ocean Drilling Program Sites 982, 925, and 1088) to investigate the presence and extent of the late Miocene to early Pliocene 'biogenic bloom' from 9 to 3 Ma. Our approach involves construction of multiple records including benthic foraminiferal and CaCO3 accumulation rates, Uvigerina counts, dissolution proxies, and geochemical tracers for biogenic and detrital fluxes. This time interval also contains the so-called late Miocene carbon isotope shift, a well-known decrease in benthic foraminiferal d13C values. We find that the timing of paleoproductivity maxima differs among the three sites. At Site 982 (North Atlantic), benthic foraminifera and CaCO3 accumulation were both at a maximum at ~5 Ma, with smaller peaks at ~6 Ma. The paleoproductivity maximum was centered earlier (~6.6-6.0 Ma) in the tropical Atlantic (Site 925). In the South Atlantic (Site 1088), paleoproductivity increased even earlier, between 8.2 Ma and 6.2 Ma, and remained relatively high until ~5.4 Ma. We note that there is some overlap between the interval of maximum productivity between Sites 925 and 1088, as well as the minor productivity increase at Site 982. We conclude that the paleoproductivity results support hypotheses aiming to place the biogenic bloom into a global context of enhanced productivity. In addition, we find that at all three sites the d13C shift is accompanied by carbonate dissolution. This observation is consistent with published studies that have sought a relationship between the late Miocene carbon isotope shift and carbonate preservation.

Quaternary carbonate record of ODP Hole 115-709A

The CaCO3 content in Quaternary deep-sea sediments from Pacific and Atlantic oceans have been suggested to respond differently to glacial/interglacial cycles; CaCO3 contents are highest during glacials in the Pacific but highest during interglacials in the Atlantic Ocean. It is not yet clear as to whether a Pacific or an Atlantic pattern of CaCO3 fluctuations dominates the Indian Ocean. We have analyzed the Ocean Drilling Program (ODP) Site 709A from the western equatorial Indian Ocean for the last 1370 ka to determine the relationships between percentages and fluxes of CaCO3 and Quaternary paleoclimatic changes. We also analyzed the coarse (>25 µm) and fine (<25 µm) fractions of CaCO3 in an attempt at estimating the influence of differences in productivity of foraminifera and calcareous nannofossils in shaping the CaCO3 record. Carbon isotopes and Ba/Al ratios were used as indices of productivity. Percentages and fluxes of CaCO3 in the total sediment and <25 µm fraction do not show any clear relationships to glacial/interglacial cycles derived from d18O of the planktonic foraminifera Globigerinoides ruber. This indicates that CaCO3 fluctuations at this site do not show either a Pacific or an Atlantic pattern of CaCO3 fluctuations. Fluxes of CaCO3 (0.38 to 2.46 g/cm**2/ ka) in total sediment and Ba/Al ratios (0.58 to 3.93 g/cm**2/ka) show six-fold variability through the last 1370 ka, which points out that productivity changes are significant at this site. Fluxes of the fine CaCO3 component demonstrate a 26-fold change (0.02 to 0.52 g/cm**2/ka), whereas the coarse CaCO3 component exhibit eight-fold change (0.13 to 1.07 g/cm**2/ka). This suggests that productivity variations of calcareous nannofossils are greater in comparison with the foraminifera. On the other hand, mean values of coarse CaCO3 fluxes are higher compared to those of fine CaCO3, which reveals that the foraminifera contribute more to the bulk CaCO3 flux than the calcareous nannofossils in the equatorial Indian Ocean.

Physical, chemical and geological properties of sediments from the central equatorial Pacific

The solution rate of biogenic opal in near-surface sediments in the Central Equatorial Pacific is three to eight orders of magnitude lower than similar acid-cleaned samples. Iron, magnesium and calcium aluminosilicates may be the minerals which are forming on the surface of the opal and reducing its solution rate. The scale height of the system studied suggests that diffusive and not advective processes are primarily responsible for the removal of dissolved silica in sediments. Solution budget calculations for this area suggest that 90-99 per cent of the biogenic opal produced in surface waters dissolves before reaching the sediment-water interface; an additional amount dissolves within the sediment and diffuses into bottom waters leaving 0.05-0.15 per cent of the original amount of opal produced by organisms in the sedimentary record. The relative solution potential of the upper 1000 m of the water column varies by more than an order of magnitude from the Antarctic to Equator and may have a pronounced effect on the accumulation rate of biogenic opal in underlying sediments.

Sedimentation and sediment redistribution on the Cocos Ridge from two seismic acquisition cruises, NEMO-3 and MV1014

We use digital seismic reflection profiles within a 1° * 1° survey area on the Cocos Ridge (COCOS6N) to study the extent and timing of sedimentation and sediment redistribution on the Cocos Ridge. The survey was performed to understand how sediment focusing might affect paleoceanographic flux measurements in a region known for significant downslope transport. COCOS6N contains ODP Site 1241 to ground truth the seismic stratigraphy, and there is a seamount ridge along the base of the ridge that forms a basin (North Flank Basin) to trap sediments transported downslope. Using the Site 1241 seismic stratigraphy and densities extrapolated from wireline logging, we document mass accumulation rates (MARs) since 11.2 Ma. The average sediment thickness at COCOS6N is 196 m, ranging from outcropping basalt at the ridge crest to ~ 400 m at North Flank Basin depocenters. Despite significant sediment transport, the average sedimentation over the entire area is well correlated to sediment fluxes at Site 1241. A low mass accumulation rate (MAR) interval is associated with the 'Miocene carbonate crash' interval even though COCOS6N was at the equator at that time and relatively shallow. Highest MAR occurs within the late Miocene-early Pliocene biogenic bloom interval. Lowest average MAR is in the Pleistocene, as plate tectonic motions caused COCOS6N to leave the equatorial productivity zone. The Pliocene and Pleistocene also exhibit higher loss of sediment from the ridge crest and transport to North Flank Basin. Higher tidal energy on the ridge caused by tectonic movement toward the margin increased sediment focusing in the younger section.

Biogenic and terrigeneous components in ODP Leg 108 holes

Five Ocean Drilling Program sites (657-661), which form a north-south transect off the western periphery of the Sahara, were selected to measure the long-term history of Saharan/Sahelian dust flux and fluvial sediment discharge and the fluxes of marine CaCO3 and opal over the last 8 m.y. Sites 658 and 659 served for high-resolution studies, and Sites 657, 660, and 661 for insights into the spatial patterns of dust flux. The nearshore mean flux of opal off Cap Blanc (21 °N) showed an abrupt increase about 3 Ma that appears to reflect the main onset of coastal upwelling fertility and enhanced trade winds. At the same time, the input of river-borne clay strongly decreased, suggesting a dry up of the central Saharan rivers. Later, marked short-lived spikes of clay and opal may indicate ongoing ephemeral pulses of fluvial runoff linked to peak interglacial stages. Given the zonal dust discharge centered near 18 °N at Site 659, the aridification of the south Sahara and Sahel increased in several steps: at 4.6, 4.3, and especially at 4.0, 3.6, and 2.1 Ma, and again, at 0.8 Ma. The late Miocene and earliest Pliocene were humid. Although the central and north Saharan climate appears to be linked to the glaciation history of the Northern Hemisphere, the long-term aridification further south followed a different schedule. The spatial distribution of quartz accumulation suggests that the dust outbreaks linked to the Intertropical Convergence Zone during summer did not shift in latitude back to 4.0 Ma, at least. The short-term variations of dust output over the last 0.5 m.y. followed orbital scale pulses with a strong precessional signal, showing a link of Sahelian humidity changes to the variation of sea-surface temperature and evaporation in the tropical Atlantic.

(Table 1) Two-way travel times and depths of picked internal reflection horizons (IRHs) of the NGRIP ice core

During the summer of 2003, a ground-penetrating radar survey around the North Greenland Icecore Project (NorthGRIP) deep ice-core drilling site (75°06' N, 42°20' W; 2957 m a.s.l.) was carried out using a shielded 250 MHz radar system. The drill site is located on an ice divide, roughly 300 km north-northwest of the summit of the Greenland ice sheet. More than 430 km of profiles were measured, covering a 10 km by 10 km area, with a grid centered on the drilling location, and eight profiles extending beyond this grid. Seven internal horizons within the upper 120 m of the ice sheet were continuously tracked, containing the last 400 years of accumulation history. Based on the age-depth and density-depth distribution of the deep core, the internal layers have been dated and the regional and temporal distribution of accumulation rate in the vicinity of NorthGRIP has been derived. The distribution of accumulation shows a relatively smoothly increasing trend from east to west from 145 kg/m**2/a to 200 kg/m**2/a over a distance of 50 km across the ice divide. The general trend is overlain by small-scale variations on the order of 2.5 kg/m**2/a/km, i.e. around 1.5% of the accumulation mean. The temporal variations of the seven periods defined by the seven tracked isochrones are on the order of +-4% of the mean of the last 400 years, i.e. at NorthGRIP ±7 kg/m**2/a. If the regional accumulation pattern has been stable for the last several thousand years during the Holocene, and ice flow has been comparable to today, advective effects along the particle trajectory upstream of NorthGRIP do not have a significant effect on the interpretation of climatically induced changes in accumulation rates derived from the deep ice core over the last 10 kyr.

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

(Table 1) Helium concentration and flux in DSDP Hole 94-607 samples

Most of the helium-3 in oceanic sediments conies from interplanetary dust particles (IDPs), and can therefore be used to infer the accretion rate of dust to the Earth through time (Ozima et al., 1984, doi:10.1038/311448a0; Takayanagi and Ozima, 1987, doi:10.1029/JB092iB12p12531; Farley, 1995, doi:10.1038/376153a0). 3He records from slowly accumulating pelagic clays indicate that the accretion rate varies considerably over millions of years, probably owing to cometary and asteroidal break-up events3. Muller and MacDonald have proposed (Muller and MacDonald, 1995, doi:10.1038/377107b0) that periodic changes in this accretion rate due to a previously unrecognized 100-kyr periodicity in the Earth's orbital inclination might account for the prominence of this frequency in climate records of the past million years (Imbrie et al., 1993, doi:10.1029/93PA02751). Here we report variations in the 3He flux to the sea floor that support this idea. We find that the flux recorded in rapidly accumulating Quaternary sediments from the Mid-Atlantic Ridge oscillates with a period of about 100 kyr. We cannot yet say, however, whether the 100-kyr climate cycle is a consequence of, a cause of, or an effect independent of these periodic changes in the rate of delivery of interplanetary dust to the sea floor.

Sediment investigations in the Kara Sea

AMS-14C dated sediment cores from the Ob and Yenisei estuaries and the adjacent inner Kara Sea were investigated to determine the siliclastic and organic carbon fluxes and their relationship to paleoenvironmental changes. The variability of sediment fluxes during Holocene times is related to the post-glacial sea-level rise and changes in river discharge and coastal erosion input. Whereas during the late/middle Holocene most of the terrigenous sediments were deposited in the estuaries and the areas directly off the estuaries, huge amounts of sediments accumulated on the Kara Sea shelf farther north during the early Holocene before about 9 Cal. kyrs. BP. The maximum accumulation at that time is related to the lowered sea level, increased coastal erosion, and increased river discharge due to the final stage of mountain deglaciation of the Putoran Massif. Increased supply of Yenisei-derived material indicated by peak magnetic susceptibility values probably occurred in climate-related pulses culminating near 11, 10, and 9 Cal. kyrs. BP. As sea level rose, the main Holocene depocenter migrated southward. Based on hydrogen index values and n-alkanes, the organic matter is predominantly of terrigenous origin. Maximum accumulation rates of 1.5 to more than 6 g/cm**2/y occurred in the early Holocene sediments, suggesting more humid climatic conditions with an increased vegetation cover in the source area at that time. In general, high organic carbon accumulation rates characterize the estuaries and the inner Kara Sea as important sink for terrigenous organic carbon. A high-resolution record of Holocene variability of magnetic susceptibility (MS) in an AMS14C-dated sediment core from the northern Yenisei estuary may indicate natural variability of Arctic climate change and river discharge on a centennial to millenial time scale. Short-term maxima in MS probably related to warmer climate, enhanced precipitation, intensified weathering/erosion and increased river discharge, display a frequency of about 300 to 700 years.

Stable oxygen isotope record and lithogenic composition of ODP Hole 117-722B

The upper 38 m of Hole 722B sediments (Owen Ridge, northwest Arabian Sea) was sampled at 20 cm intervals and used to develop records of lithogenic percent, mass accumulation rate, and grain size spanning the past 1 m.y. Over this interval, the lithogenic component of Owen Ridge sediments can be used to infer variability in the strength of Arabian Sea summer monsoon winds (median grain size) and the aridity of surrounding dust source-areas (mass accumulation rate; MAR in g/cm**2/k.y). The lithogenic MAR has strong 100, 41, and 23 k.y. cyclicities and is forced primarily by changes in source-area aridity associated with glacial-interglacial cycles. The lithogenic grain size, on the other hand, exhibits higher frequency variability (23 k.y.) and is forced by the strength of summer monsoon winds which, in turn, are forced by the effective sensible heating of the Indian-Asian landmass and by the availability of latent heat from the Southern Hemisphere Indian Ocean. These forcing mechanisms combine to produce a wind-strength record which has no strong relationship to glacial-interglacial cycles. Discussion of the mechanisms responsible for production of primary Milankovitch cyclicities in lithogenic records from the Owen Ridge is presented elsewhere (Clemens and Prell, 1990, doi:10.1029/PA005i002p00109). Here we examine the 1 m.y. record from Hole 722B focusing on different aspects of the lithogenic components including an abrupt change in the monsoon wind-strength record at 500 k.y., core-to-core reproducibility, comparison with magnetic susceptibility, coherency with a wind-strength record from the Pacific Ocean, and combination frequencies in the wind-strength record. The Hole 722B lithogenic grain-size record shows an abrupt change at 500 k.y. possibly indicating decreased monsoon wind-strength over the interval from 500 k.y. to present. The grain-size decrease appears to be coincident with a loss of spectral power near the 41 k.y. periodicity. However, the grain-size decrease is not paralleled in the Globigerina bulloides upwelling record, an independent record of summer monsoon wind-strength (Prell, this volume). These observations leave us with competing hypotheses possibly involving: (1) a decrease in the sensitivity of monsoon windstrength to obliquity forcing, (2) decoupling of the grain size and G. bulloides records via a decoupling of the nutrient supply from wind-driven upwelling, and/or (3) a change in dust source-area or the patterns of dust transporting winds. Comparison of the lithogenic grain size and weight percent records from Hole 722B with those from a nearby core shows that the major and most minor events are well replicated. These close matches establish our confidence in the lithogenic extraction techniques and measurements. Further, reproducibility on a core-to-core scale indicates that the eolian depositional signal is regionally strong, coherent, and well preserved. The lithogenic weight percent and magnetic susceptibility are extremely well correlated in both the time and frequency domains. From this we infer that the magnetically susceptible component of Owen Ridge sediments is of terrestrial origin and transported to the Owen Ridge via summer monsoon winds. Because of the high correlation with the lithogenic percent record, the magnetic susceptibility record can be cast in terms of lithogenic MAR and used as a high resolution proxy for continental aridity. In addition to primary Milankovitch periodicities, the Hole 722B grain-size record exhibits periodicity at 52 k.y. and at 29 k.y. Both periodicities are also found in the grain-size record from piston core RC11-210 in the equatorial Pacific Ocean. Comparison of the two grain-size records shows significant coherence and zero phase relationships over both the 52 and 29 k.y. periodicities suggesting that the strengths of the Indian Ocean monsoon and the Pacific southeasterly trade winds share common forcing mechanisms. Two possible origins for the 52 and 29 k.y. periodicities in the Hole 722B wind-strength record are (1) direct Milankovitch forcing (54 and 29 k.y. components of obliquity) and (2) combination periodicities resulting from nonlinear interactions within the climate system. We find that the 52 and 29 k.y. periodicities show stronger coherency with crossproducts of eccentricity and obliquity (29 k.y.) and precession and obliquity (52 k.y.) than with direct obliquity forcing. Our working hypothesis attributes these periodicities to nonlinear interaction between external insolation forcing and internal climatic feedback mechanisms involving an interdependence of continental snow/ice-mass (albedo) and the hydrological cycle (latent heat availability).