(Table 1) Ooze/chalk cycles: frequency of occurrence at DSDP Leg 74 Sites

Shallow- to deep-water environments are represented by the sediments and rocks recovered from the Walvis Ridge- Angola Basin transect. These calcareous oozes, chalks, limestones, and volcaniclastic sedimentary rocks are used to define and correlate four lithostratigraphic units. The sediments were deposited in cycles which represent recurring tectonic or Oceanographic events and may be related to climatic fluctuations and orbital perturbations. Turbidites are the most common and easily identified sedimentary cycle. They are Late Cretaceous to Paleocene in age and are repeated in intervals ranging from thousands to tens of thousands of years. They are also found interbedded between basalt layers. Turbidites are easily distinguished from the other cycles present by their sedimentary structures, mineral composition, alteration products, and physical properties (GRAPE) data. Large-scale turbidites, debris, or slump breccias are found at or just above the Cretaceous/Tertiary boundary and indicate an event of considerable energy possibly related to intense tectonic activity. Diagenetic cycles, interpreted as small-scale dissolution cycles or sequences produced by biogenic activity, occur in early Paleocene chalks. The recurrence intervals average -20,000 y. but have a wide range of values. Variations in CaCO3 content, color, gradational boundaries, and trace fossil content characterize these sediments. These cycles reflect bottom-water conditions. Ooze-chalk cycles occur in upper Oligocene to upper Paleocene sediments and represent conditions that once existed at the sediment/water interface where they obtained their diagenetic potential. These oscillations are repeated over tens of thousands of years and may have no modern analogs. Color variations in sediments at the Cretaceous/Tertiary boundary indicate local fluctuations in oxygen content within the sediments or the water column. This situation lasted for several hundred thousand years and is not repeated elsewhere in the sequence. Large dissolution cycles are recorded in the sediments at Site 527 that are of middle Miocene and early Oligocene to middle Eocene age. During this time the seafloor at this site appears to have been located at or subsided to a depth occupied by a fluctuating CCD and lysocline.

(Table 2) Delta 14C record of sediment core Pulse-32_SMB

The D14C of surface water dissolved inorganic carbon (DIC) in the Southern California Bight was compared to D14C as recorded by the sterols in Santa Monica and Santa Barbara Basin sediments. All of the C26, C27, C28, and C29 sterols as well as dinosterol had 14C concentrations equal to surface water DIC, indicating that all of the major sterols were derived from phytoplanktonic production. There is no detectable terrestrial component. Their tracer capability was confirmed by comparing the "bomb 14C"-derived change in surface water D14CDIC with the change in D14Csterol. The "prebomb" D14CDIC was -82 per mil, and prebomb sterols averaged -75±19 per mil. The D14C value in 1996 was +71 per mil. Eighteen measurements representing eight different sterols from the sediment-water interface of both Santa Monica and Santa Barbara Basins averaged +62±23 per mil. When three of these values were eliminated because of suspected contamination, the remaining data averaged +71 ±12 per mil. The entire compound class could serve as an excellent proxy for the 14C concentration of ocean surface waters.

Analysis of Mn-deposits from Lake Eningi-Lampi

The processes of formation of iron-manganese nodules and crusts have been studied on an example of the Eningi-Lampi lake, Central Karelia, where the relationships between the source of the ore, sedimentary materials and areas of their accumulation prove relatively simple and apparent. Nodules and crusts are composed mostly by birnessite, amorphous hydrous ferric oxides and hydro-goethite. They occur, as a rule, on the surface of relatively coarse-grained sediments, at the ground-water interface. Considerably in a lesser extent are found the nodules in the upper part (0ó5 cm) of the red-brown flooded watery mud covering dark-green, black muds. The nucleus of nodules, or the basis of crusts of iron-manganese hydroxides are various, frequently altered, fragments of rocks, sometimes pieces of wood. Distribution of Mn and Fe in sediments and waters of the lake is considered. It is shown that the Mn/Fe ratio decreases considerably in waters, sediments and nodules of the lake while moving off a distance from the source. The main role in the process of formation of iron-manganese nodules belongs to the selective chemosorption interaction (with auto-catalytic oxidation) of component-bearing solutions with active surfaces.

Organic matter based proxies from surface sediments along three transects on the Pakistan continental margin

A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Structure and chemistry of TECHNO encrustations

Using as a starting point the results giving 'traditional' growth rates as determined by the decrease of radioelements (part I) and the hypothesis of rapid formation, the different mineralogical, structure and chemical characteristics of the sample have been studied to try to understand the possible mode of formation of this encrustation. A rapid formation would account for (1) the very peculiar structure of the sample composed of oriented botryoids and the bundle-like structure of the outermost oxide layer; (2) the fact that this sample represents a substitution of a preexisting hyaloclastite; (3) the different chemical gradients, mainly iron, thorium and uranium; (4) the fact that this sample which cannot have been maintained at the sediment-water interface by bioturbation is not covered by a great thickness of sediments. On the other hand, an unsolved problem remains: Why different radionuclides used for dating give growth rates of the same order of magnitude and different 'exposition ages'.

Carbon and nitrogen content of marine pore waters

We have developed sampling methods and an analytical system to determine the concentration of dissolved organic C (DOC) in marine pore waters. Our analytical approach is a modification of recently developed high-temperature, Pt-catalyzed oxidation methods; it uses Chromatographic trapping of the DOC-derived CO2 followed by reduction to CH4 and flame ionization detection. Sampling experiments with nearshore sediments indicate that pore-water separation by whole-core squeezing causes artificially elevated DOC concentrations, while pore-water recovery by sectioning and centrifugation does not appear to introduce DOC artifacts. Results from a set of northwestern Atlantic continental slope cores suggest that net DOC production accounts for >50% of the organic C that is recycled at the sediment-water interface.

(Table 2) Oxygen isotope composition of authigenic and detrital phosphates from ODL Leg 201 sites

Many (bio)geochemical processes that bring about changes in sediment chemistry normally begin at the sediment-water interface, continue at depth within the sediment column and may persist throughout the lifetime of sediments. Because of the differential reactivity of sedimentary phosphate phases in response to diagenesis, dissolution/precipitation and biological cycling, the oxygen isotope ratios of phosphate (d18OP) can carry a distinct signature of these processes, as well as inform on the origin of specific P phases. Here, we present results of sequential sediment extraction (SEDEX) analyses combined with d18OP measurements, aimed at characterizing authigenic and detrital phosphate phases in continental margin sediments from three sites (Sites 1227, 1228 and 1229) along the Peru Margin collected during ODP Leg 201. Our results show that the amount of P in different reservoirs varies significantly in the upper 50 m of the sediment column, but with a consistent pattern, for example, detrital P is highest in siliciclastic-rich layers. The d18OP values of authigenic phosphate vary between 20.2 per mil and 24.8 per mil and can be classified into at least two major groups: authigenic phosphate precipitated at/near the sediment-water interface in equilibrium with paleo-water oxygen isotope ratios (d18Ow) and temperature, and phosphate derived from hydrolysis of organic matter (Porg) with subsequent incomplete to complete re-equlibration and precipitated deeper in the sediments column. The d18OP values of detrital phosphate, which vary from 7.7-15.4 per mil, suggest two possible terrigenous sources and their mixtures in different proportions: phosphate from igneous/metamorphic rocks and phosphate precipitated in source regions in equilibrium with d18Ow of meteoric water. More importantly, original isotopic compositions of at least one phase of authigenic phosphates and all detrital phosphates are not altered by diagenesis and other biogeochemical changes within the sediment column. These findings help to understand the origin and provenance of P phases and paleoenvironmental conditions at/near the sediment-water interface, and to infer post-depositional activities within the sediment column.

Shell preservation of Limacina inflata in surface sediments of the Central and South Atlantic

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive "metabolic" aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and delta13C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO2 release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.

(Table 19, page 199) Minor constituents of one of the San Clemente iron concretions and its metallic core

The chemical and mineralogical composition of pelagic sediments from the East Pacific Ocean has been determined with the aim of defining the ultimate sources and the mechanisms of formation of the solid phases. The distribution of elements between sea-water, the pore solution and the various solid components of the sediments permits interpretations of the variations in time and space of the gross chemical composition of pelagic clays. For example, manganese, present in sea-water in a divalent form, is apparently oxidized at the sediment-water interface to tetravalent species which subsequently become a part of the group of ferromanganese oxide minerals which are found in the marine environment. It is suggested the rate of manganese accumulation in sediments is some function of the length of time the sediment surface is in contact with sea-water. The contribution of chemical species from the different geospheres is considered. The quantitative importance of pelagic clays in the major sedimentary cycle is studied on the basis of the distribution of the weathered igneous rock products between continental and pelagic deposits and sea-water. These analyses of a wide variety of pelagic clays allow a reformulation of the geochemical balance and it is concluded that pelagic clays account for approximately 13 per cent of the total mass of sediments produced over geologic time.