(Table 2) 230Th, 230Th xs and 232Th concentrations in dissolved, particulate and total (dissolved+small particles) for all KEOPS stations, Marion Dufresne cruise MD145

In the context of the KErguelen Ocean and Plateau compared Study (KEOPS, 19 January-13 February 2005), particle dynamics were investigated using thorium isotope measurements over and off the Kerguelen plateau. Dissolved and particulate 230Th and 232Th samples were collected at nine stations. Dissolved excess 230Th concentrations (230Thxs) vary from 0.5 to 20.8 fg/kg and particulate 230Thxs concentrations from 0.1 to 10.0 fg/kg. Dissolved and particulate 232Th concentration ranges are 16.8-450.2 pg/kg and 3.8-502.8 pg/kg, respectively. The 230Thxs concentrations increase linearly with depth down to the bottom at most of the plateau stations and down to 1000 m at the off-plateau stations. This linear trend is observed down to the bottom (1550 m) at Kerfix, the open-ocean "upstream" station located west of the Kerguelen plateau. A simple reversible scavenging model applied to these data allowed the estimation of adsorption rate constant (k1~=0.2-0.8 per year), desorption rate constant (k-1~=1-8 per year) and partition coefficients (average K=0.16±0.07). Calculated particle settling velocities S deduced from this simple model are ca. 500 m/year at most of the plateau stations and 800 m/year at all the off-plateau stations. The plateau settling velocities are relatively low for such a productive site, compared to the surrounding HNLC areas. The difference might reflect the fact that lateral advection is neglected in this model. Taking this advection into account allows the reconstruction of the observed 230Thxs linear distributions, but only if faster settling velocities are considered. This implies that the 1D model strongly underestimates the settling velocity of the particles. In the deep layers, the occurrence of intense boundary scavenging along the escarpment due to bottom sediment re-suspension and interaction with a nepheloid layer, yielding a removal of ?50% of the Th stock along the northwestward transect, is suggested.

Radionuclides measured on 21 water bottle profiles during POLARSTERN cruise ANT-XXIV/3

Drake Passage is a major route for many water masses from the strong Antarctic Circumpolar Current. During the ANTXXIV-3 expedition (in 2008) the vertical distributions of dissolved and size-fractionated particulate 231Pa and thorium isotopes (230Th, 232Th and 234Th) were investigated in order to better define the scavenging regimes and the effects of the oceanic circulation on the fate of particulate material and on the Pa-Th distributions in the water column. The reversible scavenging-model applied to both 230Th and 234Th, in the upper 1500 m depth, gives estimates of the particle dynamics (settling velocities S~ 500-1300 m/y, adsorption and desorption rate constants of 0.1-0.4 1/y and 1-6 1/y respectively). Particulate 234Th/230Th activity ratio shows a depth dependence, with decreasing ratio with increasing depth in agreement with previous studies, but no relationship with particle size was found. 231Pa and thorium isotope fractionation and partition coefficients were investigated with particle size vs depth and latitude and appear to vary horizontally following a North-South gradient. This suggests that both radionuclides are mostly bound to the fine suspended particles. At Drake Passage, the 230Thxs distribution is controlled by a southward upwelling of deep water (clearly visible on the vertical section of total 230Thxs, defined as dissolved + particulate concentrations) and reversible-scavenging processes (linear increase of 230Thxs with increasing depth) with North of the Southern ACC Front, higher settling velocities and less adsorption/desorption cycles, than South of it. Distributions of dissolved and total 231Paxs also reflect the influence of the North-South upwelling but somehow this effect appears to be limited to the upper 1500 m depth of the water column. Below this depth, 231Paxs vertical profiles exhibit contrasted concentrations, with some high dissolved activities in the deep water of the stations in the northern part of the ACC and not South of the ACC. These N-S differences in dissolved 231Paxs were attributed to the different origins and scavenging history of the deep Pacific waters flowing across Drake Passage. Here at North, radionuclides-rich deep water originates from the Central Pacific, while at South, deep water derives from the Southern Pacific in which the observed low radionuclides concentrations are attributed to high opal abundance. South of the Drake Passage, high dissolved and particulate activities of 230Th and 232Th confirmed the intrusion of 230Th-rich Weddell Sea Deep Water (WSDW) close to the Antarctic Peninsula.

Sr/Ca and Cd/Ca ratios of benthic foraminifera in surface deep-sea sediments

Measurements of Sr/Ca of benthic foraminifera show a linear decrease with water depth which is superimposed upon significant variability identified by analyses of individual foraminifera. New data for Cd/Ca support previous work in defining a contrast between waters shallower and deeper than ~2500 m. Measured element partition coefficients in foraminiferal calcium carbonate relative to sea water (D) have been described by means of a one-box model in which elements are extracted by Rayleigh distillation from a biomineralization reservoir that serves for calcification with a constant fractionation factor (alpha), such that D = (1 - f**alpha)/(l - f), where f is the proportion of Ca remaining after precipitation. A modification to the model recognises differences in element speciation. The model is consistent with differences between D[Sr], D[Ba], and D[Cd] in benthic but not planktonic foraminifera. Depth variations in D for Sr and Ba are consistent with the model, as are differences in depth variation of D[Cd] in calcitic and aragonitic benthic foraminifera. The shallower depth variations may reflect increasing calcification rates with increasing water depth to an optimum of about 2500 m. Observations of unusually lower DCd for some deep waters, not accompanied by similar [Sr], or D[Ba] may be because of dissolution or a calcification response to a lower carbonate saturation state.

Permeability, overburden stress and friction coefficients of ODP Hole 190-1173A and 190-1174B

Permeability measured on three samples in a triaxial cell under effective confining pressure from 0.2 to 2.5 MPa ranges from 10**-18 to 10**-19 m**2. Overall, results indicate that permeability decreases with effective confining pressure up to 1.5 MPa; however, measurements at low effective pressure are too dispersed to yield a precise general relationship between permeability and pressure. When the effective pressure is increased from 1.5 to 2.5 MPa, permeability is roughly constant (~1-4 x 10**-19 m**2). Samples deformed in the triaxial cell developed slickenlined fractures, and permeability measurements were performed before and after failure. A permeability increase is observed when the sample fails under low effective confining pressure (0.2 MPa), but not under effective pressure corresponding to the overburden stress. Under isotropic stress conditions, permeability decrease related to fracture closure occurs at a relatively high effective pressure of ~1.5 MPa. Coefficients of friction on the fractures formed in the triaxial cell are ~0.4.

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.

Sulphur contents and partition of iron in ODP Leg 112 sediments

Porewaters in site 680 Peru Margin sediments contain dissolved sulfide over a depth of approximately 70 m which, at a sedimentation rate of 0.005 cm/yr, gives a sediment exposure time to dissolved sulfide of about 1.4 Myr. Reactions with dissolved sulfide cause the site 680 sediments to show a progressive decrease in a poorly-reactive silicate iron fraction, defined as the difference between iron extracted by dithionite (FeD) at room temperature and that extracted by boiling concentrated HCl (FeH), normalised to the total iron content (FeT). Straight line plots are obtained for ln[(FeH - FeD)/FeT] against time of burial, from which a first order rate constant of 0.29 1/Myr (equivalent to a half-life of 2.4 Myr) can be derived for the sulfidation of this silicate iron. Comparable half-lives are also found for the same poorly-reactive iron fraction in the nearby site 681 and 684 sediments. This silicate Fe fraction comprises 0.8-1.0% Fe, only 30-60% of which reacts even with 1.5-3 million years exposure to dissolved sulfide. Diagenetic models based on porewater concentrations of sulfate and sulfide, and solid phase iron contents, at site 680 are consistent in indicating that this poorly-reactive iron fraction is only sulfidized on a million year time scale. Silicate iron not extracted by HCl can be regarded as unreactive towards dissolved sulfide on the time scales encountered in marine sediments.

Absorption coefficients of particulate matter and chlorophyll a concentrations at time series station OLIPAC

Spectral absorption coefficients of total particulate matter ap (lambda) were determined using the in vitro filter technique. The present analysis deals with a set of 1166 spectra, determined in various oceanic (case 1) waters, with field chl a concentrations ([chl]) spanning 3 orders of magnitude (0.02-25 mg/m**3). As previously shown [Bricaud et al., 1995, doi:10.1029/95JC00463] for the absorption coefficients of living phytoplankton a phi (lamda), the ap (labda) coefficients also increase nonlinearly with [chl]. The relationships (power laws) that link ap (lambda) and a phi (lambda) to [chl] show striking similarities. Despite large fluctuations, the relative contribution of nonalgal particles to total absorption oscillates around an average value of 25-30% throughout the [chl] range. The spectral dependence of absorption by these nonalgal particles follows an exponential increase toward short wavelengths, with a weakly variable slope (0.011 ± 0.0025/nm). The empirical relationships linking ap (lambda) to ([chl]) can be used in bio-optical models. This parameterization based on in vitro measurements leads to a good agreement with a former modeling of the diffuse attenuation coefficient based on in situ measurements. This agreement is worth noting as independent methods and data sets are compared. It is stressed that for a given ([chl]), the ap (lambda) coefficients show large residual variability around the regression lines (for instance, by a factor of 3 at 440 nm). The consequences of such a variability, when predicting or interpreting the diffuse reflectance of the ocean, are examined, according to whether or not these variations in ap are associated with concomitant variations in particle scattering. In most situations the deviations in ap actually are not compensated by those in particle scattering, so that the amplitude of reflectance is affected by these variations.

Chemistry of basalts of ODP Hole 111-504B

The effect of oxygen fugacity (fO2) on the partition relationship of Mg and Fe between Plagioclase and sillicate liquid was investigated at 1 atm for basaltic samples recovered during ODP Leg 111 from Hole 504B. Samples 111-504B-143R-2 (Piece 8) and 111-504B-169R-1 (Piece 1) have Plagioclase as the liquidus phase. The distribution coefficient of Mg between Plagioclase and melt is constant at about 0.04 against the variation of fO2, whereas that of Fe (total Fe) varies from 0.3 at f(O2) = 0.2 atm to 0.03 at f(o2) = 10**-11.5 at 1200°C. The distribution coefficient of Mg is slightly higher than that calculated from the phenocryst and bulk-rock compositions, suggesting a kinetic disequilibrium effect on the distribution of Mg in Plagioclase. Because Mg, Fe, and Fe3+ have similar diffusion coefficients in silicate melt, the disequilibrium effect is greatly reduced for the exchange reaction of Mg and total Fe between Plagioclase and liquid. The exchange partition coefficient is highly dependent on fo2, with log fo2 ranging from -0.7 to - 11.5 at approximately 1200°C. Using this relationship, the f(O2) of crystallization of the magmas is estimated to be near the one defined by the fayalite-quartz-magnetite assemblage.

(Table 1) Viscosity coefficients at various temperatures of samples from ODP Hole 176-735B

Ocean Drilling Program (ODP) Hole 735B was drilled to a depth of 1.5 km in a tectonic window of gabbroic lower oceanic crust created at the Southwest Indian Ridge. The gabbros have a very stable natural remanent magnetization (NRM) of reversed polarity with most unblocking temperatures slightly below the Curie temperature of magnetite. The NRM includes a drilling-induced overprint but its intensity decays strongly towards the interior of the drill core. The demagnetization data yield no or only a very small secondary magnetization component acquired during the present Brunhes chron or an earlier normal chron, suggesting cooling through most of the blocking temperature range during chron C5r and a strong resistance against the acquisition of thermoviscous magnetization. A novel furnace has been designed to measure magnetizations and their time dependences at high temperatures (up to 580 deg C) inside a commercial SQUID magnetometer. Magnetic viscosity experiments have been conducted on the gabbros at temperatures up to 550 deg C to determine the time and temperature stability of remanent magnetization. Viscosities are generally small and increase little with temperature below the main blocking temperature, where the increase becomes almost an order of magnitude. Extrapolations to geological times infer viscous acquisitions that would be 5-25% of a thermoremanence in 100 kyr and at temperatures of 200-500 deg C. At ocean bottom temperature the predicted magnetization of one sample acquired in the present Brunhes chron should be 10% of the NRM. However, this is not recognized during NRM demagnetization and partial thermoremanent magnetization (pTRM) acquisitions at 250 deg C are also much smaller than predicted. It thus appears that the NRMs are generally magnetically harder than magnetizations acquired after heating to 570 deg C in the laboratory. Susceptibility changes during heating are small (<5%) indicating a seemingly stable magneto-mineralogy, but conspicuous minima occur after heating to 520 deg C. Also, quasi paleointensity experiments reveal characteristic patterns in the NRM/pTRM ratios and also large increases in pTRM capacity after heating to 570 deg C. Moreover, anhysteretic remanent magnetization acquisition in the low field range (<=10 mT) is strongly enhanced after heating by factors up to three. The alteration of the magneto-mineralogy is interpreted to result from the annealing of defects in magnetite that originate from tectonically induced strain. The oceanic gabbros of Hole 735B are thus ideal source layer material for marine magnetic anomalies, and secondary thermoviscous acquisition, as a possible cause for anomalous skewness, is essentially absent.