The distribution of sulfur in oceanic crust with respect to oxidative diagenesis (Table 1)

A detailed geochemical-petrological examination of layer 2 basalts recovered during Leg 37 of the DSDP has revealed that the original distribution, form and abundance of igneous sulfide have been profoundly altered during low-grade oxidative diagenesis. The net result appears to have been a rather pervasive remobilization of igneous sulfide to form secondary pyrite accompanied by a bulk loss of sulfur equivalent to about 50-60% of the original igneous value, assuming initial saturation. It is suggested that during infiltration of seawater into the massive crystalline rock, igneous sulfide has experienced pervasive oxidation, under conditions of limited oxidation potential, to form a series of unstable, soluble sulfur species, primarily in the form of SO3[2-] and S2O3[2-]. Spontaneous decomposition of these intermediate compounds through disproportionation has resulted in partial reconstitution of the sulfur as secondary pyrite and the generation of SO4[2-] ion, which, due to its kinetic stability, has been lost from the basalt system and ultimately transferred to the ocean. This model not only satisfies the geochemical and petrological observations but also provides a suitable explanation for the highly variable delta34S values which characterize secondary sulfides in deep ocean floor basalts.

Composition of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus

Detailed data obtained on chemistry of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus that were dated at the Cenomanian/Turonian boundary and formed during Oceanic Anoxic Event 2 make it possible to calculate dissolved oxygen concentration in bottom waters of the sedimentation basin. Enrichment factors of trace elements in black shales are revised and an explanation is suggested for genesis of the rocks with regard for unusual climatic changes.

Miocene flora and paleoclimate estimations of Schrotzburg, South Germany

We present a detailed palaeoclimate analysis of the Middle Miocene (uppermost Badenian-lowermost Sarmatian) Schrotzburg locality in S Germany, based on the fossil macro- and micro-flora, using four different methods for the estimation of palaeoclimate parameters: the coexistence approach (CA), leaf margin analysis (LMA), the Climate-Leaf Analysis Multivariate Program (CLAMP), as well as a recently developed multivariate leaf physiognomic approach based on an European calibration dataset (ELPA). Considering results of all methods used, the following palaeoclimate estimates seem to be most likely: mean annual temperature ~15-16°C (MAT), coldest month mean temperature ~7°C (CMMT), warmest month mean temperature between 25 and 26°C, and mean annual precipiation ~1,300 mm, although CMMT values may have been colder as indicated by the disappearance of the crocodile Diplocynodon and the temperature thresholds derived from modern alligators. For most palaeoclimatic parameters, estimates derived by CLAMP significantly differ from those derived by most other methods. With respect to the consistency of the results obtained by CA, LMA and ELPA, it is suggested that for the Schrotzburg locality CLAMP is probably less reliable than most other methods. A possible explanation may be attributed to the correlation between leaf physiognomy and climate as represented by the CLAMP calibration data set which is largely based on extant floras from N America and E Asia and which may be not suitable for application to the European Neogene. All physiognomic methods used here were affected by taphonomic biasses. Especially the number of taxa had a great influence on the reliability of the palaeoclimate estimates. Both multivariate leaf physiognomic approaches are less influenced by such biasses than the univariate LMA. In combination with previously published results from the European and Asian Neogene, our data suggest that during the Neogene in Eurasia CLAMP may produce temperature estimates, which are systematically too cold as compared to other evidence. This pattern, however, has to be further investigated using additional palaeofloras.

Amino acid in Deep Sea Drilling Project cores

Several amino acid diagenetic reactions, which take place in the deep-sea sedimentary environment, were investigated, using various Deep Sea Drilling Project (DSDP) cores. Initially it was found that essentially all the amino acids in sediments are bound in peptide linkages; but, with increasing age, the peptide bonds undergo slow hydrolysis that results in an increasingly larger fraction of amino acids in the free state. The hydrolysis half-life in calcareous sediments was estimated to be ~1-2 million years, while in non-carbonate sediment the hydrolysis rate may be considerably slower. The amino acid compositions and the extent of racemization of several amino acids were determined in various fractions isolated from the sediments. These analyses demonstrated that the mechanism, kinetics, and rate of amino acid diagenesis are highly dependent upon the physical state (i.e., free, bound, etc.) in which the amino acids exist in the sedimentary environment. In the free state, serine and threonine were found to decompose primarily by a dehydration reaction, while in the bound state (residue or HCl-insoluble fraction) a reversible aldol-cleavage reaction is the main decomposition pathway of these amino acids. The change in amino acid composition of the residue fraction with time was suggested to be due to the hydrolysis of peptide bonds, while in foraminiferal tests the compositional changes over geological time are the result of various decomposition reactions. Reversible first-order racemization kinetics are not observed for free amino acids in sediments. The explanation for these anomalous kinetics involves a complex reaction series which includes the hydrolysis of peptide bonds and the very rapid racemization of free amino acids. The racemization rates of free amino acids in sediments were found to be many orders of magnitude faster than those predicted from elevated temperature experiments using free amino acids in aqueous solution. The racemization rate enhancement of free amino acids in sediments may be due to the catalysis of the reaction by trace metals. Reversible first-order kinetics are followed for amino acids in the residue fraction isolated from sediments; the rate of racemization in this fraction is slower than that predicted for protein-bound amino acids. Various applications of amino acid diagenetic reactions are discussed. Racemization and the decomposition reaction of serine and threonine can both be used, with certain limitations, to make rough age estimates of deep-sea sediments back to several million years. The extent of racemization in foraminiferal tests which have been dated by some other independent technique can be used to estimate geothermal gradients, and thus heat flows, and to evaluate the bottom water temperature history in certain oceanic areas.

Production of biogenic silica during the EBENE cruise, Equatorial Pacific

During the EBENE cruise (November 1996), distributions of biogenic silica concentration and production rates were investigated in the surface waters of the equatorial Pacific (180°W, from 8°S to 8°N), with particular emphasis on the limitation of the biogenic silica production by ambient silicic acid concentrations. Integrated over the depth of the euphotic layer, concentrations of biogenic silica and production rates were maximum at the Equator (8.0 and 2.6 mmol/m**2/d) and decreased more or less symmetrically polewards. Contribution of diatoms to the new production was estimated indirectly, comparing biogenic silica production rates and available data of new and export production in the same area. This comparison shows that new production in the equatorial area could mostly be sustained by diatoms, accounting for the major part of the exported flux of organic carbon. Kinetics experiments of silicic acid enrichment were performed. Half saturation constants were 1.57 µM at 3°S and 2.42 µM at the Equator close to the ambient concentrations. The corresponding Vmax values for Si uptake were 0.028/h at 3°S and 0.052/h at the equator. Experiments also show that in situ rates were restricted to 13-78% of Vmax, depending on ambient silicic acid concentrations. This work provides the first direct evidence that the rate of Si uptake by diatom populations of the equatorial Pacific is limited by the ambient concentration of silicic acid. However, such Si limitation might not be sufficient in itself to explain the low diatom growth rates observed, and additional limitation is suggested. One hypothesis that is consistent with the results of Fe limitation studies is that Fe and Si limitations may interact, rather than just being a mutually exclusive explanation for the HNLC character of the system.

Petrology and relict mineralogy of serpentinites at DSDP Leg 84 Holes

Eleven serpentine samples from DSDP Leg 84 and four serpentinized ultramafic samples from Costa Rica and Guatemala were described and their relict mineral compositions measured by electron microprobe to try to determine the origin of the Leg 84 serpentinites and their relationship to the ultramafic rocks of the onshore ophiolites. The Leg 84 samples comprise more than 90% secondary minerals, principally serpentine, with hematitic and opaque oxides, and minor talc and smectites. Four distinct textural types can be identified according to the distribution of opaque phases and smectite. Remnants of spinel, olivine, orthopyroxene, and clinopyroxene occur variously in the samples; spinal occurs in all the samples. Textural evidence suggests that the serpentinites were originally clinopyroxene-bearing harzburgites. Relict mineral compositions are refractory and relatively uniform: olivine, Fo90.6-90.9; orthopyroxene, En90-91; clinopyroxene, Wo47 En50 Fs3; spinels, Cr/Cr + Al = 0.4-0.6. 567A-29-2, 30-35 cm has slightly more magnesian olivines (Fo92) and orthopyroxene, and more aluminous spinels (Cr/Cr + Al = 0.3). These compositions are similar to those inferred for refractory upper-mantle materials and also fall within the range of compositions for relict minerals in abyssal peridotites. They could be of oceanic origin. The onshore samples include serpentinites, a clinopyroxene-bearing harzburgite, and a clinopyroxenite. They too have magnesium-rich silicate assemblages, but relative to the drilled samples have more iron-rich olivines (Fogo) and more aluminous and sodic pyroxenes; spinels which are clearly relicts are very aluminum-rich (Cr/Cr + Al = 0.1-0.25). These samples are most likely mantle materials, but significantly less depleted. Their relationship to the drilled samples is unclear. Serpentinites were the most common basement materials recovered during Leg 84, and there appears to be a bimodal assemblage (basalt/diabase and serpentine) of igneous rocks sampled from the trench slope. Diapirism of serpentine throughout the trench slope and forearc is suggested as an explanation for this distribution of samples.

Seawater carbonate chemistry during experiments with Stylophora pistillata, 2008

The decrease in the saturation state of seawater, following seawater acidification, is believed to be the main factor leading to a decrease in the calcification of marine organisms. To provide a physiological explanation for this phenomenon, the effect of seawater acidification was studied on the calcification and photosynthesis of the scleractinian tropical coral Stylophora pistillata. Coral nubbins were incubated for 8 days at three different pH (7.6, 8.0, and 8.2). To differentiate between the effects of the various components of the carbonate chemistry (pH, CO32, HCO3, CO2), tanks were also maintained under similar pH, but with 2-mM HCO3 added to the seawater. The addition of 2-mM bicarbonate significantly increased the photosynthesis in S. pistillata, suggesting carbon-limited conditions. Conversely, photosynthesis was insensitive to changes in pH and pCO2. Seawater acidification decreased coral calcification by ca. 0.1-mg CaCO3 g-1 d-1 for a decrease of 0.1 pH units. This correlation suggested that seawater acidification affected coral calcification by decreasing the availability of the CO32 substrate for calcification. However, the decrease in coral calcification could also be attributed either to a decrease in extra- or intracellular pH or to a change in the buffering capacity of the medium, impairing supply of CO32 from HCO3.

Sedimentology of cores from the Iberian margin

Bioturbation in marine sediments has basically two aspects of interest for palaeo-environmental studies. First, the traces left by the burrowing organisms reflect the prevailing environmental conditions at the seafloor and thus can be used to reconstruct the ecologic and palaeoceanographic situation. Traces have the advantage over other proxies of practically always being preserved in situ. Secondly, for high- resolution stratigraphy, bioturbation is a nuisance due to the stirring and mixing processes that destroy the stratigraphic record. In order to evaluate the applicability of biogenic traces as palaeoenvironmental indicators, a number of gravity cores from the Portuguese continental slope, covering the period from the last glacial to the present were investigated through X-ray radiographs. In addition, physical and chemical parameters were determined to define the environmental niche in each core interval. A number of traces could be recognized, the most important being: Thalassinoides, Planolites, Zoophycos, Chondrites, Scolicia, Palaeophycus, Phycosiphon and the generally pyritized traces Trichichnus and Mycellia. The shifts between the different ichnofabrics agree strikingly well with the variations in ocean circulation caused by the changing climate. On the upper and middle slope, variations in current intensity and oxygenation of the Mediterranean Outflow Water were responsible for shifts in the ichnofabric. Larger traces such as Planolites and Thalassinoides dominated in coarse, well oxygenated intervals, while small traces such as Chondrites and Trichichnus dominated in fine grained, poorly oxygenated intervals. In contrast, on the lower slope where calm steady sedimentation conditions prevail, changes in sedimentation rate and nutrient flux have controlled variations in the distribution of larger traces such as Planolites, Thalassinoides, and Palaeophycus. Additionally, distinct layers of abundant Chondrites correspond to Heinrich events 1, 2, and 4, and are interpreted as a response to incursions of nutrient rich, oxygen depleted Antarctic waters during phases of reduced thermohaline circulation. The results clearly show that not one single factor but a combination of several factors is necessary to explain the changes in ichnofabric. Furthermore, large variations in the extent and type of bioturbation and tiering between different settings clearly show that a more detailed knowledge of the factors governing bioturbation is necessary if we shall fully comprehend how proxy records are disturbed. A first attempt to automatize a part of the recognition and quantification of the ichnofabric was performed using the DIAna image analysis program on digitized X-ray radiographs. The results show that enhanced abundance of pyritized microburrows appears to be coupled to organic rich sediments deposited under dysoxic conditions. Coarse grained sediments inhibit the formation of pyritized burrows. However, the smallest changes in program settings controlling the grey scale threshold and the sensitivity resulted in large shifts in the number of detected burrows. Therefore, this method can only be considered to be semi-quantitative. Through AMS-^C dating of sample pairs from the Zoophycos spreiten and the surrounding host sediment, age reversals of up to 3,320 years could be demonstrated for the first time. The spreiten material is always several thousands of years younger than the surrounding host sediment. Together with detailed X-ray radiograph studies this shows that the trace maker collects the material on the seafloor, and then transports it downwards up to more than one meter in to the underlying sediment where it is deposited in distinct structures termed spreiten. This clearly shows that age reversals of several thousands of years can be expected whenever Zoophycos is unknowingly sampled. These results also render the hitherto proposed ethological models proposed for Zoophycos as largely implausible. Therefore, a combination of detritus feeding, short time caching, and hibernation possibly combined also with gardening, is suggested here as an explanation for this complicated burrow.

Age control points and sedimentation rates of ODP Hole 145-887B (Table 1)

Hole 887B of the Ocean Drilling Program (ODP) comprises a 44 m (750 kyr) long continuous section recovered from the Patton-Murray Rise, an elevated plateau that is largely isolated from turbidite deposition. The Patton-Murray area is centered under the Alaska Gyre, a region characterized by the domal upwelling of nutrient-rich waters. Marked increases in productivity and rapid settling of biogenic matter are suggested throughout the section by the episodic accumulation of diatomaceous oozes up to ~1 m thick that are accompanied by barium enrichments. Significant delta13Corg maxima in the major diatomaceous bands suggest that mixedlayer [CO2(aq)] may have been drawn down significantly during some of the productivity events. The episodes of enhanced productivity at Site 887 occur synchronously with short-lived minima in planktonic foram delta18O, suggesting a direct link to low salinity, or less likely, warming, events in the Gulf of Alaska. There is no obvious explanation for the events, but they may be related to seasonal incursions of meltwater from Alaska. We speculate that episodic input of meltwater- or dust-borne iron from Asian or Alaskan sources may have promoted the extraordinary diatom production events recorded in the sedimentary record.