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.

Benthic foraminiferal assemblage changes during interstadial 4 to 8 in ODP Site 146-893A, Santa Barbara Basin

Benthic foraminiferal assemblages from Santa Barbara Basin exhibit major faunal and ecological switches associated with late Quaternary millennial- to decadal-scale global climate oscillations. Repeated turnovers of entire faunas occurred rapidly (<40-400 yr) without extinction or speciation in conjunction with Dansgaard-Oeschger shifts in thermohaline circulation, ventilation, and climate, confirming evolutionary model predictions of Roy et al. Consistent faunal successions of dysoxic taxa during successive interstadials reflect the extreme sensitivity and adaptation of the benthic ecosystem to the rapid environmental changes that marked the late Quaternary and possibly other transitional intervals in the history of the Earth's ocean-atmosphere-cryosphere system. These data support the hypothesis that broad segments of the biosphere are well adapted to rapid climate change.

Neogene planktonic foraminifers from Wombat and Exmouth Plateau

Diverse, warm-water planktonic foraminiferal faunas prevailed on the Wombat and Exmouth plateaus during the Neogene, in spite of the northward drift of Australia across 10° to 15° latitude since the early Miocene. Invasions of cool-water species occurred during periods of global cooling in the late middle Miocene, late Miocene, and Pleistocene, and reflect periods of increased northward transport of cool surface water, probably via the West Australian Current. The sedimentary record of the Neogene on Wombat and Exmouth Plateau is interrupted by two hiatuses (lower Miocene, Zone N5, and upper middle to upper Miocene, Zones N15-N17), and one redeposited section of upper Miocene to uppermost Pliocene sediments. Mechanical erosion or nondeposition by increased deep-water flow or tilting and uplift of Wombat and Exmouth plateaus, resulting in sediment shedding, are the most likely explanations for these Miocene hiatuses, but which of these processes were actually operative on the Wombat and Exmouth plateaus is uncertain. The redeposited section of upper Miocene to uppermost Pliocene sediments in Hole 761B, however, certainly reflects a latest Pliocene period of uplift and tilting of the Wombat Plateau. An important finding was the occurrence of Zone N15-correlative sediments in Hole 762B without any representative of Neogloboquadrina. Similar findings in Java and Jamaica indicate that the earliest spreading of Neogloboquadrina acostaensis in the tropical region resulted from migration. The evolution of this species, therefore, must have taken place in higher latitudes. I suggest that Neogloboquadrina acostaensis evolved from Neogloboquadrina atlantica in the North Atlantic within Zone NN9, but how and where in the region this speciation took place is still uncertain

Palynology of the Middle to Late Miocene from ODP Hole 175-1085A off the west coast of South Africa

Aim To test whether the radiation of the extremely rich Cape flora is correlated with marine-driven climate change. Location Middle to Late Miocene in the south-east Atlantic and the Benguela Upwelling System (BUS) off the west coast of South Africa. Methods We studied the palynology of the thoroughly dated Middle to Late Miocene sediments of Ocean Drilling Program (ODP) Site 1085 retrieved from the Atlantic off the mouth of the Orange River. Both marine upwelling and terrestrial input are recorded at this site, which allows a direct correlation between changes in the terrestrial flora and the marine BUS in the south-east Atlantic. Results Pollen types from plants of tropical affinity disappeared, and those from the Cape flora gradually increased, between 10 and 6 Ma. Our data corroborate the inferred dating of the diversification in Aizoaceae c. 8 Ma. Main conclusions Inferred vegetation changes for the Late Miocene south-western African coast are the disappearance of Podocarpus-dominated Afromontane forests, and a change in the vegetation of the coastal plain from tropical grassland and thicket to semi-arid succulent vegetation. These changes are indicative of an increased summer drought, and are in step with the development of the southern BUS. They pre-date the Pliocene uplift of the East African escarpment, suggesting that this did not play a role in stimulating vegetation change. Some Fynbos elements were present throughout the recorded period (from 11 Ma), suggesting that at least some elements of this vegetation were already in place during the onset of the BUS. This is consistent with a marine-driven climate change in south-western Africa triggering substantial radiation in the terrestrial flora, especially in the Aizoaceae.

Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.

(Table 3) Contents of P2O5 and total REE in phosphorites from Pacific seamonts

Changes in concentration levels and speciation of heavy metals during sedimentation on example of a typical semi-closed bay, where bottom sediments have formed due to river run-off, are under consideration. It is shown that due to desorption of mobile manganese, zinc and copper entered the bay with river suspended matter, their total contents in bottom sediments decrease and percentages of lithogenic forms increase. Contents and speciation of iron in bottom sediments are determined by its participation in coagulation of river colloids in the mixing zone and by mechanical differentiation of sedimentary material.