Chemistry of volcanic ash from Celebes and Sulu Sea Basins

During Leg 124, off the Philippines, volcanic material was recovered in deep-sea sediments dating from the late Oligocene in the Celebes Sea Basin, and from the early Miocene in the Sulu Sea Basin. Chemical and petrological studies of fallout ash deposits are used to characterize volcanic pulses and to determine their possible origin. All of the glass and mineral compositions belong to medium-K and high-K calc-alkaline arc-related magmatic suites including high-Al basalts, pyroxene-hornblende andesites, dacites, and rhyolites. Late Oligocene and early Miocene products may have originated from the Sunda arc or from the Sabah-Zamboanga old Sulu arc. Late early Miocene Sulu Sea tuffs originated from the Cagayan arc, whereas early late Miocene fallout ashes are attributed to the Sulu arc. A complex magmatic production is distinguished in the Plio-Quaternary with three sequences of basic to acidic lava suites. Early Pliocene strata registered an important activity in both Celebes Sea and Sulu Sea areas, from the newly born Sangihe arc (low-alumina andesite series) and from the Sulu, Zamboanga, and Negros arcs (high-alumina basalt series and high-K andesite series). In the late Pliocene and the early Pleistocene, renewal of activity affects the Sangihe-Cotobato arc as well as the Sulu and Negros arcs (same magmatic distinctions). The last volcanic pulse took place in the late Pleistocene with revival of all the present arc systems.

Chemical composition of bottom sediments and interstitial waters from DSDP Sites 252, 285, 315, 317, 336, and 386

Six Deep Sea Drilling Project (DSDP) Sites (252, 285, 315, 317, 336, 386) were examined for the chemical composition of the dissolved salts in interstitial waters, the oxygen isotopic composition of the interstitial waters, and the major ion composition of the bulk solid sediments. An examination of the concentration-depth profiles of dissolved calcium, magnesium, potassium, and H218O in conjunction with oxygen isotope mass balance calculations confirms the hypothesis that in DSDP pelagic drill sites concentration gradients in Ca. Mg. K, and H218O are largely due to alteration reactions occurring in the basalts of Layer 2 and to alteration reactions involving volcanic matter dispersed in the sediment column. Oxygen isotope mass balance calculations require substantial alteration of Layer 2 (up to 25% of the upper 1000 m). but only minor exchange of Ca, Mg, and K occurs with the overlying ocean. This implies that alteration reactions in Layer 2 are almost isochemical.

Miocene radiolarians of the Sulu Sea

Radiolarians are sporadic in sediments collected in the Sulu Sea during ODP Leg 124. Due to the generally poor preservation and low abundance of radiolarians in Sulu Sea sediments, no biostratigraphic datums are well defined, although three radiolarian zones are identified. Most samples containing radiolarians are pelagic or hemipelagic clays with varying proportions of volcanic ash. Detailed analysis of Sulu Sea radiolarians was limited to Miocene successions. Pliocene and Quaternary occurrences of radiolarians were noted but have not been zoned. The late middle Miocene of Sites 769 and 771 is represented by an assemblage of radiolarians (Diartus petterssoni Zone) that is entirely replaced by massive pyrite. This type of preservation develops only under anoxic conditions. The development of widespread anoxia in Sulu Sea waters in the late middle Miocene was probably the result of hydrologic isolation of basin waters, and may be associated with eustatic sea level fall over the silled basin. Upper lower Miocene pelagic and hemipelagic sediments that overlie pyroclastics and basalt flows in the Sulu Sea sites contain moderately to very poorly preserved radiolarians of the Calocycletta costata Zone. A thin unit of marine claystone was recovered from between the thick pyroclastics and basement rocks at Site 768. Radiolarians present in these claystones are rare and very poorly preserved. This radiolarian assemblage probably represents the C. costata Zone, although very poor preservation and low abundance make this interpretation equivocal. The radiolarian zones identified constrain the age of basin formation to late early Miocene or earlier.

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.

Mass-accumulation rates for the non-authigenic, inorganic, crystalline, eolian component of sediments recovered at DSDP Sites 62-464 to 62-466

The mass-accumulation rate (MAR) of the non-authigenic, inorganic, crystalline component of deep-sea sediments from the Pacific aseismic rises apparently reflects influx of eolian sediment. The eolian sediment usually is dominated by volcanic material, except during glacial times. Sediments from Hess Rise provide a discontinuous record of eolian MARs. During Albian to Cenomanian time, the influx of volcanic material was fairly high (0.35-0.6 g/cm**2/10**3 yr), recording the latest stages of the Albian volcanism that formed Hess Rise. From the Campanian through the Paleocene, influx of eolian sediment was low, averaging 0.03 g/cm**2/10**3 yr. None of the four Hess Rise drill sites show evidence of the Late Cretaceous volcanic episode recorded at many sites now in the equatorial to subtropical Pacific. Pliocene to Pleistocene samples record a peak in volcanic influx about 4 to 5 m.y. ago, which has been well documented elsewhere. The several-fold increase in eolian accumulation rates elsewhere which are correlated with the onset of severe northernhemisphere glaciation 2.5 m.y. ago is not obvious in the Hess Rise data.

Methane concentration profiles and isotopic composition of sediment cores from the Black Sea

We present high resolution profiles for the methane concentration and the carbon isotope composition of methane from surface sediments and from the sediment-water transition in the Black Sea. At shallow water sites methane migrates from the sediment into the water column, and the magnitude of this upward migrating flux depends on the depth of the sulfate-methane transition (SMT) in the sediment. The isotope data reveal that the sediments at shallow water sites are a source for methane depleted in 13C relative to the isotope composition of methane in the water column. At deep water sites the methane concentration first decreases with depth in the sediment to reach lowest values at the Unit I to Unit II transition. Below this transition the concentration increases again. Numerical modeling of methane concentration and isotope data shows that high methane oxidation rates occur in the surface sediment layer, indicating that the removal of methane in the surface sediments is not related to the anaerobic oxidation of methane coupled to sulfate reduction that occurs a few meters deep in the sediment, at the SMT. Instead, near-surface methane consumption in the euxinic Black Sea sediments appears to be related to lithological stratification. Furthermore, a map of the diffusive methane fluxes in the Black Sea surface sediments indicates that approximately half of the Black Sea seafloor acts as a sink for methane and thus limits the flux of methane to the atmosphere.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Contents of 230Th, Fe2O3, MnO and P2O5 in bottom sediments from the Tropical Pacific

Shape of the 230Th vertical distribution curve ideally close to exponential is studied to determine isotopic age of deep-sea sediments. In practice such ideal 230Th vertical distribution curve is rarely occur; secondary maxima and minima often appear on it. It has been shown that oxyhydroxides of Fe, Mn, and also Corg and P are of prime importance for 230Th concentration. A method is offered for normalizing the vertical distribution curve of 230Th based on taking into account content of these elements in sediment.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

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.

Benthic foraminifera of surface sediments from the continental slope off Sierra Leone, North-West Africa

On "Meteor" cruise 30 (1973) 22 piston-cores were collected off Sierra Leone from water-depths between about 5000 m (Sierra Leone Basin) and 500 m (upper continental slope) with the objective to study the sediment composition and age as well as processes of sedimentation on the continental slope in a tropical humid region. Granulometric analysis and determinations of the carbonate contents of the sediment samples were carried out, as well as qualitative and quantitative analysis of the components of the grain size fractions > 63 µm and of the planktonic and benthonic foraminifera > 160 µm. Presently, the cold Canary Current influences the composition of the planktonic foraminifera within the northwestern area of investigation (profile A), whereas the planktonic fauna of the eastern area (profile C) seems to be truly tropical. In all Quaternary sediments from the continental slope off Sierra Leone, species of Globorotalia are less abundant than in truly pelagic sediments. For that reason, the zonation of the Pleistocene sediments based on the presence or absence of Globorotalia cultrata does not always agree with the climatic changes reflected in the sediments. Concerning past climates better results can be obtained by using the changes in percentage abundances of Globigerina sp. sp. and Globigerinoides sp. sp. as indicators for cool and warm temperatures. The Tertiary sediments contain a pelagic foraminiferal assemblage. In the Holocene sediments the benthonic foraminifera do not only serve as good paleodepth indicators, but their communities are also restricted to defined water masses, which change their positions in accordance with climatic changes. Thus, Cassidulina carinata in the area of investigation is an excellent indicator for sediments deposited during times, which were cooler than today; this is true for all cores from the continental slope off Sierra Leone independent of water-depth although this species presently abounds at water-depths around 600 m. The cores from the continental rise and from the Sierra Leone Basin (M30-261, M30-146, M30-147) were deposited below the calcium carbonate compensation depth. Only small sections of the cores consist of the original carbonate-free sediments, whereas the main part of the sediment column is redeposited material, rich in foraminifera, which normally live on the upper continental slope, or even on the shelf. From these cores only M30-261 can be subdivided into biostratigraphic zones ranging from zone V to zone Y. In all cores from the middle and upper continental slope of the eastern area of investigation (profile C; KL 230, 209-204) and in cores KL 183 and KL 184 from the northwestern area (profile A) we observed an undisturbed succession of sediments from the biostratigraphic zones X (partly), Y and Z. All cores from the central area (M30-181, M30-182, M30-262 to 264) and M30-187 from the upper slope of profile A show variable hiatuses in the sedimentary record. Locally, high velocity bottom currents were probably responsible for erosion, nondeposition or minimal sedimentation rates. These currents might have been initiated partly by the somewhat exposed position of this part of the continental slope, where the shelf edge bends from a northwest towards an eastern direction, and partly by very young tectonic movements. Fracture zones with vertically displaced fault blocs are frequent at Sierra Leone continental margin. According to seismic measurements by McMaster et al. (1975) the sites of the central area are located on an uplifted fault bloc explaining the reduced sediment rates or erosion. Unlike the central area, the eastern area (profile C) is situated on a downfaulted bloc with high sediment rates. The sediments from the cores of profile B as well as the turbiditic deep-sea sediments were deposited under a higher flow regime; therefore they are coarser than the extremely fine-grained sediments of the cores from profile C. Since the sand fraction (> 63 µm) is mainly composed of foraminifera, besides pteropods and light-colored fecal pellets, the carbonate content increases with the increasing percentage of the coarse grain fraction. Higher concentrations of quartz were only observed in core sections with considerable carbonate dissolution (mainly in the X-Zone), and, in general, in all sediments from the eastern area with higher terrigenous input including larger concentration of mica. Especially during times transitional between glacials and interglacials (or interstadials) the bottom currents were intensified. The percentages of coarse fraction and carbonate increase with increasing current velocities. Calcium carbonate dissolution becomes important in water depths > 3500 m. During cooler times the lysokline is depressed. Light-colored fecal pellets were redeposited from Late Neogene sediments (M30-187, M30-181). In the area of investigation they occur in the Holocene and mainly the Pleistocene sediments of the cores from the northwestern and central area because only here Tertiary sediments have been eroded at the uppermost continental slope. In the central area there are at least two periods of non-sedimentation and/or erosion which can be confined as being (1) not older than middle Pliocene and not younger than zone V and (2) younger than zone W. The local character of the erosion is documented by the fact that a complete Late Quaternary section is present in the cores of the northwestern and eastern area, each within less than 100 km from incomplete cores from the central area.