Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Pollen and macroremains from four profiles from site Samerberg 1

Pollen and macrofossil analysis of lake sediments revealed the complete development of vegetation from Riss late-glacial to early Würm glacial times at Samerberg (12°12' E, 47°45' N, 600 m a.s.l) on the northern border of the Alps. The pollen bearing sediments overlie three stratigraphic units, at the base a ground-moraine, then a 13 m thick layer of pollen free silt and clay, and then a younger moraine; all the sediments including the pollen bearing sediments, lie below the Würm moraine. The lake, which had developed in an older glacial basin, became extinct, when the ice of the river Inn glacier filled its basin during Würm full-glacial time at the latest. One interglacial, three interstadials, and the interdigitating treeless periods were identified at Samerberg. Whereas the cold periods cannot be distinguished from one another pollenanalytically, the interglacial and the two older interstadials have distinctive characteristics. A shrub phase with Juniperus initiated reforestation and was followed by a pine phase during the interglacial and each of the three interstadials. The further development of the interglacial vegetation proceeded with a phase when deciduous trees (mainly Quercus, oak) and hazel (Corylus) dominated, though spruce (Picea) was present at the same time in the area. A phase with abundant yew (Taxus) led to an apparently long lasting period with dominant spruce and fir (Abies) accompanied by some hornbeam (Carpinus). The vegetational development shows the main characteristics of the Riss/Würm interglacial, though certain differences in the vegetational development in the northern alpine foreland are obvious. These differences may result from the existence of an altitudinal zonation of the vegetation in the vicinity of the site and are the expression of its position at the border of the Alps. A greater age (e.g. the Holsteinian) can be excluded by reason of the vegetational development, and is also not indicated at first sight from the geological and stratigraphical data of the site. Characteristic of the Riss/Würm vegetational development in southern Germany - at least in the region between Lake Starnberg/Samerberg/Salzach - is the conspicuous yew phase. According to absolute pollen counts, yew not only displaced the deciduous species, but also displaced spruce preferentially, thus indicating climatic conditions less favourable for spruce, caused by mild winters (Ilex spreading!) and by short-term low precipitation, indicated by the reduced sedimentation rate. The oldest interstadials is bipartite, as due to the climatic deterioration the early vegetational development, culminating in a spruce phase, had been interrupted by another expansion of pine. A younger spruce-dominated period with fir and perhaps also with hornbeam and beech (Fagus) followed. An identical climatic development has been reported from other European sites with long pollen sequences (see chapter 6.7). However, different tree species are found in the same time intervals in Middle Europe during Early Würm times. Sediments of the last interglacial (Eem or Riss/Würm) have been found in all cases below the sediments of the bipartite interstadial, and in addition one more interstadial occurs in the overlying sediments. This proves that Eem and Riss/Würm of the north-european plain resp. of the alpine foreland are contemporaneous interglacials although this has been questioned by some authors. The climax vegetation of the second interstadial was a spruce forest without fir and without more demanding deciduous tree species. The vegetational development of the third interstadial is recorded fragmentary only. But it has been established that a spruce forest was present. The oldest interstadial must correspond to the danish Brørup interstadial as it is expressed in northern Germany, the second one to the Odderade interstadial. A third Early Würm interstadial, preserved fragmentarily at Samerberg, is known from other sites. The dutch Amersfoort interstadial most likely is the equivalent to the older part of the bipartite danish Brørup interstadial.

Late Cretaceous-Early Neogene oxygen and carbon isotope record of the Indian Ocean

Stable isotopic data of calcareous nannofossil, monogeneric and monospecific planktic and benthic foraminifera from five Indian Ocean DSDP sites (212, 217, 220, 237, and 253), leads to the following paleoclimatic and paleoceanographic conclusions: - The latest Cretaceous oxygen isotopic record implies a cooling (3-4°C) during the Maastrichtian. At the Cretaceous/Tertiary boundary only a minor warming (about 2°C) has been recorded. The parallel delta13C decrease of more than 1? indicates a significant decrease in productivity. - During the latest Paleocene a positive delta13C excursion was detected in Sites 217 and 237. This transient enrichment in delta13C may be due to productivity changes on continents and/or a change in the storage rate of organic matter in marginal basins or shelf areas. - The most striking feature in the oxygen isotopic record is noted at the Early/Middle Eocene transition. The shift towards more positive values (which were probably enhanced to a certain extent by a preceding diagenetic alteration) delineates a dramatic climatic deterioration at high and mid latitudes during the earlier Tertiary. - Near the Eocene/Oligocene boundary a cooling is evident within the latest Eocene interval. During the earliest Oligocene time a hiatus at Sites 217 and 253 partially obscures the climatic record. - Several climatic fluctuations have been noted during the Oligocene: a cooling at the base of Zone NP 23, a warming at the top of Zone NP 23 through NP 24, and a cooling during Zone NP 25. - The Miocene oxygen isotopic record is dominated by changes in surface and bottom water environments during Zone NN5. The decreasing and then increasing delta18O values, together with the subsequent steepening of the vertical delta18O gradient, point towards major climatic instabilities. These events coincide with the Mid-Miocene build-up of Antarctic ice-sheets. During the latest Miocene to the earliest Pliocene the delta18O record of planktic foraminifera indicates a significant warming of the Indian Ocean at mid-latitudes. - The delta13C record during the Oligocene and Miocene reveals several cycles (delta13C enrichments: NP 24, NN2, NN5, NN9, and base NN 11) which are most likely related to changes in storage rates of organic matter and biological productivity due to climatic changes and transgression/regression cycles. In addition, changes in the circulation patterns may also have influenced the carbon isotopic record.