Composition and distribution of silica in sediments of the Broken Ridge

Within a dipping sequence of middle Cretaceous to Eocene sediments on Broken Ridge, opal-A, opal-CT, and quartz occur as minor constituents in carbonate and ash-rich sediments. Biogenic opal-A is mainly derived from diatoms and radiolarians. Opal-A and almost all siliceous microfossils disappear within a narrow (<20-m-thick) transition zone below which authigenic opal-CT and quartz are present. These latter silica polymorphs occur together within a 750-m-thick interval, but the ratio of quartz/opal-CT increases with increasing age and depth within the pre-rift sediment sequence. The boundary between opal-A- and opal-CT-bearing sediments is also a physical boundary at which density, P-wave velocity, and acoustic impedance change. This physical transition is probably caused by infilling of pore space by opal-CT lepispheres.

Geochemical analysis of sediments and interstitial water in sediment cores from the North-West African continental margin and from the Central Pacific

A. Continental slope sediments off Spanish-Sahara and Senegal contain up to 4% organic carbon and up to 0.4% total nitrogen. The highest concentrations were found in sediments from water depths between 1000 and 2000 m. The regional and vertical distribution of organic matter differs significantly. Off Spanish-Sahara the organic matter content of sediment deposited during glacial times (Wuerm, Late Riss) is high whereas sediments deposited during interglacial times (Recent, Eem) are low in organic matter. Opposite distribution was found in sediments off Senegal. The sediments contain 30 to 130 ppm of fixed nitrogen. In most sediments this corresponds to 2-8 % of the total nitrogen. Only in sediments deposited during interglacial times off Spanish-Sahara up to 20 % of the total nitrogen is contained as inorganically bound nitrogen. Positive correlations of the fixed nitrogen concentrations to the amounts of clay, alumina, and potassium suggest that it is primarily fixed to illites. The amino acid nitrogen and hexosamine nitrogen account for 17 to 26 % and 1.3 to 2.4 %, respectively of the total nitrogen content of the sediments. The concentrations vary between 200 and 850 ppm amino acid nitrogen and 20 to 70 ppm hexosamine nitrogen, both parallel the fluctiations of organic matter in the sediment. Fulvic acids, humic acids, and the total organic matter of the sediments may be clearly differentiated from one another and their amino acid and hexosamine contents and their amino acid composition: a) Fulvic acids contain only half as much amino acids as humic acids b) The molar amino acid/hexosamine ratios of the fulvic acids are half those of the humic acids and the total organic matter of the sediment c) The amino acid spectra of fulvic acids are characterized by an enrichment of aspartic acid, alanine, and methionine sulfoxide and a depletion of glycine, valine, isoleucine, leucine, tyrosine, phenylalanine, lysine, and arginine compared to the spectra of the humic acids and those of the total organic matter fraction of the sediment. d) The amino acid spectra of the humic acids and those of the total organic matter fraction of the sediments are about the same with the exception that arginine is clearly enriched in the total organic matter. In general, as indicated by the amino compounds humic acids resemble closer the total organic matter composition than the low molecular fulvic acids do. This supports the general idea that during the course of diagenesis in reducing sediments organic matter stabilizes from a fulvic-like structure to humic-like structure and finally to kerogen. The decomposition rates of single aminio acids differ significantly from one another. Generally amino acids which are preferentially contained in humic acids and the total organic matter fraction show a smaller loss with time than those preferably well documented in case of the basic amino acids lysine and arginine which- although thermally unstable- are the most stable amino acids in the sediments. A favoured incorporation of these compounds into high molecular substances as well as into clay minerals may explain their relatively high "stability" in the sediment. The nitrogen loss from the sediments due to the activity of sulphate-reducing bacteria amounts to 20-40 % of the total organic nitrogen now present. At least 40 % of the organic nitrogen which is liberated by sulphate-reducing bacteria can be explained ny decomposition of amino acids alone. B. Deep-sea sediments from the Central Pacific The deep-seas sediments contain 1 to 2 orders of magnitude less organic matter than the continental slope sediments off NW Africa, i.e. 0.04 to 0.3 % organic carbon. The fixed nitrogen content of the deep-sea sediments ranges from 60 to 270 ppm or from 20 to 45 % of the total nitrogen content. While ammonia is the prevailing inorganic nitrogen compound in anoxic pore waters, nitrate predominates in the oxic environment of the deep-sea sediments. Near the sediment/water interface interstital nitrate concentrations of around 30 µg-at. N/l were recorded. These generally increase with sediment depth by 10 to 15 µg-at. NO3- N/l. This suggests the presence of free oxygen and the activity of nitrifying bacteria in the interstitial waters. The ammonia content of the interstitial water of the oxic deep-sea sediments ranges from 2 to 60 µg-at. N/l and thus is several orders of magnitude less than in anoxic sediments. In contrast to recorded nitrate gradients towards the sediments/water interface, there are no ammonia concentration gradients. However, ammonia concentrations appear to be characteristic for certain regional areas. It is suggested that this regional differentiation is caused by ion exchange reactions involving potassium and ammonium ions rather than by different decomposition rates of organic matter. C. C/N ratios All estimated C/N ratios of surface sediments vary between 3 and 9 in the deep-sea and the continental margin, respectively. Whereas the C/N ratios generally increase with depth in the sediment cores off NW Africa they decrease in the deep-sea cores. The lowest values of around 1.3 were found in the deeper sections of the deep-sea cores, the highest of around 10 in the sediments off NW Africa. The wide range of the C/N ratios as well as their opposite behaviour with increasing sediment depth in both the deep-sea and continental margin sediment cores, can be attributed mainly to the combination of the following three factors: 1. Inorganic and organic substances bound within the latticed of clay minerals tend to decrease the C/N ratios. 2. Organic matter not protected by absorption on the clay minerals tends to increase C/N ratios 3. Diagenetic alteration of organic matter by micro-organisms tends to increase C/N ratios through preferential loss of nitrogen The diagenetic changes of the microbially decomposable organic matter results in both oxic and anoxic environments in a preferential loss of nitrogen and hence in higher C/N ratios of the organic fraction. This holds true for most of the continental margin sediments off NW Africa which contain relatively high amounts of organic matter so that factors 2 and 3 predominate there. The relative low C/N ratios of the sediments deposited during interglacial times off Spanish-Sahara, which are low in organic carbon, show the increasing influence of factor 1 - the nitrogen-rich organic substances bound to clay minerals. In the deep-sea sediments from the Central Pacific this factor completely predominates so that the C/N rations of the sediments approach that of the substance absorbed to clay minerals with decreasing organic matter content. In the deeper core sections the unprotected organic matter has been completely destroyed so that the C/N ratios of the total sediments eventually fall into the same range as those of the pure clay mineral fraction.

Files of figures 2, 3 and table

Certain allelochemicals of the marine dinoflagellate Alexandrium tamarense cause lysis of a broad spectrum of target protist cells but the lytic mechanism is poorly defined. We first hypothesized that membrane sterols serve as molecular targets of these lytic compounds, and that differences in sterol composition among donor and target cells may cause insensitivity of Alexandrium and sensitivity of targets to lytic compounds. We investigated Ca2+ influx after application of lytic fractions to a model cell line PC12 derived from a pheochromocytoma of the rat adrenal medulla to establish how the lytic compounds affect ion flux associated with lysis of target membranes. The lytic compounds increased permeability of the cell membrane for Ca2+ ions even during blockade of Ca2+ channels with cadmium. Results of a liposome assay suggested that the lytic compounds did not lyse such target membranes non-specifically by means of detergent-like activity. Analysis of sterol composition of isolates of A. tamarense and of five target protistan species showed that both lytic and non-lytic A. tamarense strains contain cholesterol and dinosterol as major sterols, whereas none of the other tested species contain dinosterol. Adding sterols and phosphatidylcholine to a lysis bioassay with the cryptophyte Rhodomonas salina for evaluation of competitive binding indicated that the lytic compounds possessed apparent high affinity for free sterols and phosphatidylcholine. Lysis of protistan target cells was dose-dependently reduced by adding various sterols or phosphatidylcholine. For three tested sterols, the lytic compounds showed highest affinity towards cholesterol followed by ergosterol and brassicasterol. Cholesterol comprised a higher percentage of total sterols in plasma membrane fractions of A. tamarense than in corresponding whole cell fractions. We conclude therefore that although the molecular targets of the lytic compounds are likely to involve sterol components of membranes, A. tamarense must have a complex self-protective mechanism that still needs to be addressed.

Planktonic foraminiferal stratigraphy and datum levels of ODP Leg 182 sites

Planktonic foraminifers from Ocean Drilling Program Leg 182, Holes 1126B and 1126C, 1128B and 1128C, 1130A and 1130B, 1132B, and 1134A and 1134B confirm the neritic record that during the early Miocene the Great Australian Bight region was in a cool-temperate regime with abundant Globoturborotalita woodi. Warm marine environments started to develop in the later part of the early Miocene, and the region became warm temperate to subtropical in the early middle Miocene with abundant Globigerinoides, Orbulina, and Globorotalia, corresponding to global warming at the Miocene climatic optimum. Fluctuations between cool- and warm-temperate conditions prevailed during the late Miocene, as indicated by abundant Globoconella conoidea and Menardella spp. A major change in planktonic foraminiferal assemblages close to the Miocene/Pliocene boundary not only drove many Miocene species into extinction but also brought about such new species as Globorotalia crassaformis and Globoconella puncticulata. Warm-temperate environments continued into the early and mid-Pliocene before being replaced by cooler conditions, supporting numerous Globoconella inflata and Globigerina quinqueloba. Based on data from this study and published results from the Australia-New Zealand region, we established a local planktonic foraminifer zonation scheme for separating the southern Australian Neogene (SAN) into Zones SAN1 to SAN19 characterizing the Miocene and Zones SAN20 to SAN25 characterizing the Pliocene. The Neogene sections from the Great Australian Bight are bounded by hiatuses of ~0.5 to >3 m.y. in duration, although poor core recovery in some holes obscured a proper biostratigraphic resolution. A total of 15 hiatuses, numbered 1 to 15, were identified as synchronous events from the base of the Miocene to the lower part of the Pleistocene. We believe that these are local manifestations of major third-order boundaries at about (1) 23.8, (2) 22.3, (3) 20.5, (4) 18.7, (5) 16.4, (6) 14.8, (7) 13.5, (8) 11.5, (9) 9.3, (10) 7.0, (11) 6.0, (12) 4.5, (13) 3.5, (14) 2.5, and (15) 1.5 Ma, respectively. This hiatus-bounded Neogene succession samples regional transgressions and stages of southern Australia and reveals its stepwise evolutionary history.

Iron and carbon geochemistry of sediment core GeoB1401-4

Iron speciation was determined in hemiplegic sediments from a high productivity area to investigate systematically the early diagenetic reactivity of Fe. A combination of various leaching agents (1 M HCI, dithionite buffered in citrate/acetic acid, HF/H2SO4, acetic Cr(II)) was applied to sediment and extracted more than 80% of total Fe. Subsequent Fe species determination defined specific mineral fractions that are available for Fe reduction and fractions formed as products of Fe diagenesis. To determine the Fe speciation of (sheet) silicates we explored an extraction procedure (HF/H2SO4) and verified the procedure by application to standard rocks. Variations of Fe speciation of (sheet) silicates reflect the possible formation of Fe-bearing silicates in near surface sediments. The same fraction indicates a change in the primary input at greater depth, which is supported by other parameters. The Fe(II)/ Fe(III) -ratio of total sediment determined by extractions was compared with Mössbauer-spectroscopy ] at room temperature and showed agreement within 10%. M6ssbauer-spectroscopy indicates the occurrence of siderite in the presence of free sulfide and pyrite, supporting the importance of microenvironments during mineral formation. The occurrence of other Fe(II) bearing minerals such as ankerite (Ca-, Fe-, Mg-carbonate) can be presumed but remains speculative.

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.

Orbitally tuned time scale and astronomical forcing in the middle Eocene to early Oligocene determined on ODP and IODP sediment cores

Deciphering the driving mechanisms of Earth system processes, including the climate dynamics expressed as paleoceanographic events, requires a complete, continuous, and high-resolution stratigraphy that is very accurately dated. In this study, we construct a robust astronomically calibrated age model for the middle Eocene to early Oligocene interval (31-43 Ma) in order to permit more detailed study of the exceptional climatic events that occurred during this time, including the Middle Eocene Climate Optimum and the Eocene/Oligocene transition. A goal of this effort is to accurately date the middle Eocene to early Oligocene composite section cored during the Pacific Equatorial Age Transect (PEAT, IODP Exp. 320/321). The stratigraphic framework for the new time scale is based on the identification of the stable long eccentricity cycle in published and new high-resolution records encompassing bulk and benthic stable isotope, calibrated XRF core scanning, and magnetostratigraphic data from ODP Sites 171B-1052, 189-1172, 199-1218, and 207-1260 as well as IODP Sites 320-U1333, and -U1334 spanning magnetic polarity Chrons C12n to C20n. Subsequently we applied orbital tuning of the records to the La2011 orbital solution. The resulting new time scale revises and refines the existing orbitally tuned age model and the Geomagnetic Polarity Time Scale from 31 to 43 Ma. Our newly defined absolute age for the Eocene/Oligocene boundary validates the astronomical tuned age of 33.89 Ma identified at the Massignano (Italy) global stratotype section and point. Our compilation of geochemical records of climate-controlled variability in sedimentation through the middle-to-late Eocene and early Oligocene demonstrates strong power in the eccentricity band that is readily tuned to the latest astronomical solution. Obliquity driven cyclicity is only apparent during very long eccentricity cycle minima around 35.5 Ma, 38.3 Ma and 40.1 Ma.

Seawater carbonate chemistry and growth rate during experiments with phylotypes of Symbiodinium (Dinophyceae), 2011

We investigated the effect of elevated partial pressure of CO2 (pCO2) on the photosynthesis and growth of four phylotypes (ITS2 types A1, A13, A2, and B1) from the genus Symbiodinium, a diverse dinoflagellate group that is important, both free-living and in symbiosis, for the viability of cnidarians and is thus a potentially important model dinoflagellate group. The response of Symbiodinium to an elevated pCO2 was phylotype-specific. Phylotypes A1 and B1 were largely unaffected by a doubling in pCO2 in contrast, the growth rate of A13 and the photosynthetic capacity of A2 both increased by ~ 60%. In no case was there an effect of ocean acidification (OA) upon respiration (dark- or light-dependent) for any of the phylotypes examined. Our observations suggest that OA might preferentially select among free-living populations of Symbiodinium, with implications for future symbioses that rely on algal acquisition from the environment (i.e., horizontal transmission). Furthermore, the carbon environment within the host could differentially affect the physiology of different Symbiodinium phylotypes. The range of responses we observed also highlights that the choice of species is an important consideration in OA research and that further investigation across phylogenetic diversity, for both the direction of effect and the underlying mechanism(s) involved, is warranted.