Contents, partition, and isotopic composition of sulphur in sediments from ODP Sites 680 and 686

We have determined (1) the abundance and isotopic composition of pyrite, monosulphide, elemental sulphur, organically bound sulphur, and dissolved sulphide; (2) the partition of ferric and ferrous iron; (3) the organic carbon contents of sediments recovered at two sites drilled on the Peru Margin during Leg 112 of the Ocean Drilling Program. Sediments at both sites are characterised by high levels of organically bound sulphur (OBS). OBS comprises up to 50% of total sedimentary sulphur and up to 1% of bulk sediment. The weight ratio of S to C in organic matter varies from 0.03 to 0.15 (mean = 0.10). Such ratios are like those measured in lithologically similar, but more deeply buried petroleum source rocks of the Monterey and Sisquoc formations in California. The sulphur content of organic matter is not limited by the availability of porewater sulphide. Isotopic data suggest that sulphur is incorporated into organic matter within a metre of the sediment surface, at least partly by reaction with polysulphides. Most inorganic Sulphur occurs as pyrite. Pyrite formation occurred within surface sediments and was limited by the availability of reactive iron. But despite highly reducing sulphidic conditions, only 35-65% of the total iron was converted to sulphide; 10-30% of the total iron still occurs as Fe(III). In surface sediments, the isotopic composition of pyrite is similar to that of both iron monosulphide and dissolved sulphide. Either pyrite, like monosulphide, formed by direct reaction between dissolved sulphide and detrital iron, and/or the sulphur species responsible for converting FeS to FeS2 is isotopically similar to dissolved sulphide. Likely stoichiometries for the reaction between ferric iron and excess sulphide imply a maximum resulting FeS2:FeS ratio of 1:1. Where pyrite dominates the pool of iron sulphides, at least some pyrite must have formed by reaction between monosulphide and elemental sulphur and/or polysulphide. Elemental sulphur (S°) is most abundant in surface sediments and probably formed by oxidation of sulphide diffusing across the sediment-water interface. In surface sediments, S° is isotopically heavier than dissolved sulphide, FeS and FeS2 and is unlikely to have been involved in the conversion of FeS to FeS2. Polysulphides are thus implicated as the link between FeS and FeS2.

Geochemistry at DSDP Leg 73 Holes

In the South Atlantic, at Sites 519 to 523, the dissolution of calcareous oozes ended in the formation of red clays rich in iron and manganese. The early authigenesis of manganese oxides and clays is described in Miocene marly calcareous oozes. The mineralogical and geochemical influences of basaltic basement weathering are shown by the occurrence of palagonite, authigenic clays, and oxides in the basal sediments. The development of red clay facies can be inhibited by local topographic and paleoceanographic changes, as at Site 520.

Radiolarians of the Celebes Sea

Two sites were drilled in the Celebes Sea as part of Ocean Drilling Program Leg 124; Site 767 and Site 770. Radiolarians are preserved in Paleogene pelagic claystones with minor occurrences in certain Neogene successions. The brown clays that immediately overlie basalt at both sites contain radiolarians of the late middle Eocene Podocyrtis chalara Zone. Late Eocene radiolarians are not found, due to dissolution and probable hiatus. The Oligocene is represented by the Theocyrtis tuberosa and Dorcadospyris ateuchus Zones. Oligocene sediments are strongly dominated by abundant and diverse radiolarians of the TristylospyrislDorcadospyris lineage. Preservation of Paleogene radiolarian assemblages ranges from good to very poor. Late Miocene radiolarians of the Didymocyrtis antepenultima Zone are found only in Site 770. Other Neogene sediments are barren of radiolarian remains, with the exception of latest Pleistocene and Holocene sediments.

Basal dolomitic sediments ofthe Tyrrhenian Sea

Basal dolomitic sediments were recovered at three drill sites in the Tyrrhenian Sea during Ocean Drilling Program (ODP) Leg 107 (Sites 650, 651, and 655). These sediments overlie the basaltic basement complex and are enriched in iron, and in some instances, also in manganese. The manganese enrichments, together with a very slight enrichment in trace transition elements, strongly suggest that the basal sediments have an affinity to deep-sea metalliferous deposits of hydrothermal origin. At Sites 651 and 655, the dolostones contain variable amounts of authigenic palygorskite, a Mgrich clay mineral. At Site 651, the basal sediments are 40 m thick and contain nonstoichiometric dolomite, sometimes Ca rich, but primarily Mg rich. The occurrence of Mg-rich dolomite with excess Mg up to 4% is unusual for the deep-sea environment; it may be associated with a hydrothermally driven flux of altered sea water through the directly underlying basement complex, which comprises basalt, dolerite, and serpentinized peridotite. Low-temperature alteration of the basement complex could produce solutions enriched in Mg. Oxygen-isotope equilibrium temperatures indicate that all of the studied dolomites formed under low-temperature conditions (i.e., < 70?C). The carbon-isotope compositions, together with the strong isotopic covariance, suggest that the Mg-rich dolomite precipitated more rapidly than the Carich dolomite. We suggest that the low-temperature, hydrothermal convection of Mg-rich solutions through the basal sediments in this back-arc basin environment (1) overcame kinetic problems related to the formation of massive dolostones, and (2) provided a mass-transport mechanism for dolomitization.

Nature, chemistry, and origin of late Cenozoic megascopic tephras in Legs 89 and 90 Cores from the Southwest Pacific

Several thin (1-10 cm) megascopic vitric tephras occur in the late Cenozoic calcareous oozes on Lord Howe Rise in the Tasman Sea and off eastern South Island, New Zealand. Of the 18 tephras analyzed 15 are silicic (75-78% SiO2) with abundant clear glass shards and a biotite ± hypersthene ± green hornblende ferromagnesian mineralogy. The Neogene silicic tephras were derived from the now-extinct Coromandel volcanic area in New Zealand, and the Quaternary ones from the presently active Central Volcanic Region of New Zealand. On the basis of glass chemistry and age, several of the Quaternary tephras are probably correlatives, and at least two can be matched to the major on-land Mt. Curl tephra (-0.25 m.y.). The occurrence of correlative silicic tephras both northwest and southeast of New Zealand may result from particularly violent eruptions, the ash below and above an altitude of -20 km being dispersed in opposite directions toward the Pacific Ocean and Tasman Sea, respectively. Ash drifting eastward into the southeasterly trade wind belt off northeastern New Zealand could also be carried into the central and northern Tasman Sea. Three megascopic tephras consist of altered basic shards and common labradorite crystals. They record Neogene explosive basaltic to andesitic activity from nearby ocean island or ridge sources in the Ontong-Java Plateau and Vanuatu regions. The megascopic tephras are a very incomplete and biased record of late Cenozoic explosive volcanism in the southwest Pacific because the innumerable, thin, green argillaceous layers in the cores (Gardner et al., this volume) probably represent devitrified intermediate to basic tephras derived mainly from oceanic arc volcanism along the Pacific/Australia plate boundary. In contrast to the New Zealand-derived silicic glass shards, the preservation potential of these more basic shards in Leg 90 calcareous sediments was low.

Radionuclide concentrations, ratios, and derived ages of massive sulfides from ODP Leg 139 and Leg 169 sites

Massive sulfide samples from the Bent Hill area were analyzed for 230Th/234U and 231Pa/235U disequilibria. Apparent ages calculated from these ratios are between 8.2 and >300 ka. Concordant ages were found for only three samples that originate near the surface from the clastic sulfide zone and suggest "true" ages of between 8.5 and 16.0 ka (mean of 230Th and 231Pa ages). The uranium vs. depth distribution in the Bent Hill Massive Sulfide deposit suggests an open system for uranium for the deeper part of the deposit, which was probably caused by extensive recrystallization processes inhibiting true age determinations.

Elemental and isotopic compositions of metalliferous and pelagic sediments from the Galapagos mounds area, data of DSDP Leg 70

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at a subsurface depth of ~2-20 m; Mn-oxide material is limited to the upper 2 m of these mounds. The nontronite forms intervals of up to a few metres thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. The metalliferous phases represent essentially authigenic precipitates, apparently formed in the presence of upwelling basement-derived hydrothermal solutions which dissolved pre-existent pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major-element composition between nontronitic material from varying locations within the mounds; and (2) adjacent granules from a given sample have very similar compositions and are internally homogeneous. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of solution Eh and composition during nontronite formation. The Pb-isotopic composition of the nontronite and Mn-oxide sediments indicates that they were formed from solutions which contained variable proportions of basaltic Pb, introduced into pore waters by basement-derived solutions, and of normal-seawater Pb. However, the Sr-isotopic composition of these sediments is essentially indistinguishable from the value for modern seawater. On the basis of 18O/16O ratios, formation temperatures of ~20-30°C have been estimated for the nontronites. By comparison, temperatures of up to 11.5°C at 9 m depth have been directly measured within the mounds and heat flow data suggest present basement-sediment interface temperatures of 15-25°C.

Coarse-fraction composition in sediments of ODP Leg 104

Coarse-fraction studies of sediments recovered during ODP Leg 104 are used to reconstruct paleoclimatic and paleoceanographic environments on a time scale of 0.1 to 0.5 m.y. for the past 20 Ma. These investigations suggest that relatively warm climates and isolated deep water conditions prevailed prior to 13.6 Ma and between 5.6-4.8 Ma. The first major deep water outflow from the Norwegian-Greenland Sea into the North Atlantic took place at about 13.6 Ma. Progressive cooling linked to increased deep water renewal in the Norwegian-Greenland Sea appears to have occurred between 13.6-5.6 Ma and 4.8-3.1 Ma. A major onset of ice-rafted debris is recorded at 2.56 Ma. Terrigenous coarsefraction components show important fluctuations with two major peaks during the past 0.8 Ma.

Organic matter and trace element concentrations in sapropels from ODP Leg 160 sites

A distinct Pliocene eastern Mediterranean sapropel (i-282), recovered from three Ocean Drilling Program (ODP) Leg 160 Sites, has been investigated for its organic and inorganic composition. This sapropel is characterized by high organic carbon (Corg) and trace element contents, and the presence of isorenieratene derivatives. The latter suggests that the base of the photic zone was sulphidic during formation of the sapropel. Combined with evidence of bottom water anoxia (preservation of laminae, high redox-sensitive trace element contents, and the abundance and isotopic composition of pyrite) this leads to the tentative conclusion that almost the entire water column may have been anoxic. This anoxia resulted from high productivity and not from stagnation, because an approximation of the trace element budget during sapropel formation shows that water exchange with the western Mediterranean is needed. Entire water column anoxia has been suggested earlier for several black shales. With regard to the depositional environment and the Corg content, however, only the Cenomanian=Turonian Boundary Event (CTBE) black shales appear to be comparable to this sapropel. The proposed trace element removal mechanism of scavenging and (co-)precipitation in an anoxic water column, is thought to be similar for both types of deposits. The ultimate trace element source for the sapropel, however, is seawater, whereas it is hydrothermal and fluvial input for CTBE black shales (because they have a larger temporal and spatial distribution). Nonetheless, the Corg-rich eastern Mediterranean Pliocene sapropel discussed here may be considered to be a younger analogue of CTBE black shales.

Composition of marine phosphorites and phosphate-bearing sediments

The book deals with behavior of phosphorus and its concentration in oceanic phosphorites. The major stages of marine geochemical cycle of phosphorus including its supply to sedimentary basins, precipitation from sea water, distribution and speciation in bottom sediments, diagenetic redistribution, and relation to other elements are under consideration. Formation of recent phosphorites as a culmination of phosphate accumulation in marine and oceanic sediments is examined. Distribution, structure, mineral and chemical compositions of major phosphorite deposits of various age on continental margins, as well as on submarine plateaus, uplifts and seamounts and some islands are described. A summary of trace element abundances in oceanic phosphorites is presented. Problems of phosphorite origin are discussed.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

Geochemistry of recent sediments of the East African continental margin, Arabian Sea

Chemical analyses have been carried out on 40 samples from the sediment surface and 210 samples from cores that were taken from the edge of the African continental block at the Arabian Sea (coasts of Somalia and Kenya, from Cape Guardafui to Mombasa) on the occasion of the Indian Ocean Expedition of the German research vessel "Meteor" during the years 1964/65. The carbonate content shows its maximum on the northern part of the continental shelf of Africa, where fossil reef debris furnish the detritic portion of carbonate. In the southern part of the continental shelf of Africa the portion of carbonate is low, as it is heavily diluted by the non-carbonatic detritus. It is also in the deep-sea that a lower carbonate content is encountered below the calcite compensation depth. Trace elements in the carbonates: On the shelf and in its vicinity Sr and Mg are enriched. The enrichment has been brought about by the portion of reef debris, as this latter contains aragonite (enrichment of Sr) as well as high-magnesium calcite. The greatest part of the slope contains carbonates that are poor in trace elements and mainly made up of foraminifera (and of coccoliths). Below the carbonate compensation depth another enrichment of Mg takes place in the carbonates, which is probably due to a selective dissolution of calcite in comparison to dolomite. The iron and manganese contents of the carbonates are high (iron higher in coast proximity, manganese higher in the depth), but not genuine, as they come about in the course of the extraction of the carbonates as a result of the dissolution of authigenic Mn-Fe-minerals. Non-carbonatic portion of the sediments: In coast proximity an enrichment of quartz comes about. Within the quartz-rich zone it is the elements V, Cr, Fe, Ti, and B that have been enriched in the non-carbonatic components. This enrichment must be attributed to an elevated content of heavy minerals. In the case of Ti and Fe the preliminary enrichment brought about by processes of lateritisation on the continent plays a certain role. Toward the deep-sea an enrichment of the elements Mn Ni, Cu, and Zn takes place; these enrichments must be explained by authigenic Mn-Fe-minerals. Within the Mn-rich zone a belt running parallel to the coast stands out that shows an increased Mn-enrichment. However, this increase in enrichment does not apply to the elements Ni, Cu, and Zn. It is probable that this latter increased enrichment comes about as a result of the migration of manganese to the sediment surface. (Within the sediments there prevail reductive conditions, in the presence of which Mn is capable of migration, whereas at the sediment surface its precipitation comes about under oxidizing conditions). The quantity of organic matter mainly is dependent on grain size and on the rate of sedimentation. On the shelf an impoverishment of organic matter is to be encountered, as the sediments are coarse-grained. In the depth the impoverishment must be explained on the strength of a small rate of sedimentation. Between those two ranges organic substance is enriched. P and N show an enrichment in comparison to Corg with this applying all the more the smaller the absolute quantity of Corg is. In this particular case one has to do with an enrichment coming about during the diagenetic processes of organic matter. A comparison with the sediments from the Indian and Pakistani continental border in Arabian Sea shows as follows: on the African continental border the coarse detrital material has been transported farther out to deep-sea, which has something to do with the greater inclination of the surface of sedimentation. Carbonate is found in greater abundance on the African side. Its chemical composition is influenced by reef-debris which is missing by Indian-Pakistani side. The content of organic matter is lower on the African side. Contrary to that, the enrichments of N and P compared to organic matter are of an equal order of magnitude on both sides of the Arabian Sea.

Bulk and clay mineral composition of ODP Leg 189 sites

Bulk and clay mineral investigations were conducted on ~750 samples from four sites drilled during Ocean Drilling Program Leg 189 on the western Tasmanian margin (Site 1168), the South Tasman Rise (Sites 1170 and 1171), and the East Tasman Plateau (Site 1172). The mineralogy of the bulk sediment is very similar at all sites, and major changes coincide with the boundaries of the three main lithologic units described in the Leg 189 Initial Reports volume. The clay mineral assemblages show significant regional differences, but their major variations coincide at all sites and with major changes in regional tectonics and climate.

Effective stress, porosity, p-wave velocity and mineral composition of ODP Hole 174A-1073A sediments

Porosity, permeability, and compressional (P-wave) velocity were measured as a function of stress on sediments from Ocean Drilling Program Site 1073, U.S. Mid-Atlantic continental slope. Thin sections, scanning electron microscopy, and X-ray diffraction analyses provided mineralogical characteristics of the samples. Uniaxial strain boundary conditions were imposed on the samples during consolidation tests with the maximum effective axial stress reaching 13 MPa. The maximum effective radial stress necessary to maintain uniaxial strain was 7.6 MPa. Over an effective axial stress interval of 0 to 5.2 MPa, Sample 174A-1073A-26X-2, 82-89 cm (226.65 meters below seafloor [mbsf]), exhibited the largest decrease in porosity (51% to 41%), whereas Sample 71X-1, 2-8 cm (644.70 mbsf), exhibited the smallest decrease in porosity (48% to 45%). All samples showed negligible porosity increases during unloading. The permeability (on the order of 1 x 10-17 m**2) of Sample 174A-1073A-71X-1, 2-8 cm, was twice that measured on Sample 8H-1, 23-26 cm (63.75 mbsf), even though the former was considerably deeper and older. The differences in porosity-stress behavior and permeability between shallow and deep samples is related to lithologic, mineralogic, and diagenetic differences between the sediments above and below the Pliocene-Pleistocene to Miocene unconformity. P-wave velocity for Samples 174A-1073A-41X-5, 97-103 cm (372.35 mbsf), and 71X-1, 2-8 cm, increased with decreasing porosity, but did not change significantly during unloading.