Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Pollen distribution in marine sediment samples along the south-western African coast

The distribution of pollen in marine sediments is used to reconstruct pathways of terrigenous input to the oceans and provides a record of vegetation change on adjacent continents. The wind transport routes of aeolian pollen is comprehensively illustrated by clusters of trajectories. Isobaric, 4-day backward trajectories are calculated using the modelled wind-field of ECHAM3, and are clustered on a seasonal basis to estimate the main pathways of aeolian particles to sites of marine cores in the south-eastern Atlantic. Trajectories and clusters based on the modelled wind-field of the Last Glacial Maximum hardly differ from those of the present-day. Trajectory clusters show three regional, and two seasonal patterns, determining the pathways of aeolian pollen transport into the south-eastern Atlantic ocean. Mainly, transport out of the continent occurs during austral fall and winter, when easterly and south-easterly winds prevail. South of 25°S, winds blow mostly from the west and southwest, and aeolian terrestrial input is very low. Generally, a good latitudinal correspondence exists between the distribution patterns of pollen in marine surface sediments and the occurrence of the source plants on the adjacent continent. The northern Angola Basin receives pollen and spores from the Congolian and Zambezian forests mainly through river discharge. The Zambezian vegetation zone is the main source area for wind-blown pollen in sediments of the Angola Basin, while the semi-desert and desert areas are the main sources for pollen in sediments of the Walvis Basin and on the Walvis Ridge. A transect of six marine pollen records along the south-western African coast indicates considerable changes in the vegetation of southern Africa between glacial and interglacial periods. Important changes in the vegetation are the decline of forests in equatorial Africa and the north of southern Africa and a northward shift of winter rain vegetation along the western escarpment.

Geochemical composition and crystallization conditions of melts from the Mid Atlantic Ridge near Ascension Island (7-11°S)

Phase equilibria simulations were performed on naturally quenched basaltic glasses to determine crystallization conditions prior to eruption of magmas at the Mid-Atlantic Ridge (MAR) east of Ascension Island (7°11°S).The results indicate that midocean ridge basalt (MORB) magmas beneath different segments of the MAR have crystallized over a wide range of pressures (100-900MPa). However, each segment seems to have a specific crystallization history. Nearly isobaric crystallization conditions (100-300MPa) were obtained for the geochemically enriched MORB magmas of the central segments, whereas normal (N)-MORB magmas of the bounding segments are characterized by polybaric crystallization conditions (200-900MPa). In addition, our results demonstrate close to anhydrous crystallization conditions of N-MORBs, whereas geochemically enriched MORBs were successfully modeled in the presence of 0.4-1wt% H2O in the parental melts.These estimates are in agreement with direct (Fourier transform IR) measurements of H2O abundances in basaltic glasses and melt inclusions for selected samples. Water contents determined in the parental melts are in the range 0.04-0.09 and 0.30-0.55 wt% H2O for depleted and enriched MORBs, respectively. Our results are in general agreement (within ±200MPa) with previous approaches used to evaluate pressure estimates in MORB. However, the determination of pre-eruptive conditions of MORBs, including temperature and water content in addition to pressure, requires the improvement of magma crystallization models to simulate liquid lines of descent in the presence of small amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation

Responses of the Emiliania huxleyi Proteome to Ocean Acidification

Ocean acidification due to rising atmospheric CO2 is expected to affect the physiology of important calcifying marine organisms, but the nature and magnitude of change is yet to be established. In coccolithophores, different species and strains display varying calcification responses to ocean acidification, but the underlying biochemical properties remain unknown. We employed an approach combining tandem mass-spectrometry with isobaric tagging (iTRAQ) and multiple database searching to identify proteins that were differentially expressed in cells of the marine coccolithophore species Emiliania huxleyi (strain NZEH) between two CO2 conditions: 395 (~current day) and ~1340 p.p.m.v. CO2. Cells exposed to the higher CO2 condition contained more cellular particulate inorganic carbon (CaCO3) and particulate organic nitrogen and carbon than those maintained in present-day conditions. These results are linked with the observation that cells grew slower under elevated CO2, indicating cell cycle disruption. Under high CO2 conditions, coccospheres were larger and cells possessed bigger coccoliths that did not show any signs of malformation compared to those from cells grown under present-day CO2 levels. No differences in calcification rate, particulate organic carbon production or cellular organic carbon: nitrogen ratios were observed. Results were not related to nutrient limitation or acclimation status of cells. At least 46 homologous protein groups from a variety of functional processes were quantified in these experiments, of which four (histones H2A, H3, H4 and a chloroplastic 30S ribosomal protein S7) showed down-regulation in all replicates exposed to high CO2, perhaps reflecting the decrease in growth rate. We present evidence of cellular stress responses but proteins associated with many key metabolic processes remained unaltered. Our results therefore suggest that this E. huxleyi strain possesses some acclimation mechanisms to tolerate future CO2 scenarios, although the observed decline in growth rate may be an overriding factor affecting the success of this ecotype in future oceans.