(Table 3) Concentration of Au, Pd, and Pt in the interstitial waters of ODP Leg 125 samples

Palladium, platinum, and gold were analyzed for 20 interstitial water samples from Leg 125. No Pd or Pt was detected in fluids from serpentinite muds from Conical Seamount in the Mariana forearc, indicating that low-temperature seawater-peridotite interaction does not mobilize these elements into the serpentinizing fluids to levels above 0.10 parts per billion (ppb) in solution. However, Au may be mobilized in high pH solutions. In contrast, fluids from vitric-rich clays on the flanks of the Torishima Seamount in the Izu-Bonin forearc have Pd values of between 4.0 and 11.8 nmol/L, Pt values between 2.3 and 5.0 nmol/L and Au values between 126.9 and 1116.9 pmol/L. The precious metals are mobilized, and possibly adsorbed onto clay mineral surfaces, during diagenesis and burial of the volcanic-rich clays. Desorption during squeezing of the sediments may produce the enhanced precious metal concentrations in the analyzed fluids. The metals are mobilized in the fluids probably as neutral hydroxide, bisulfide, and ammonia complexes. Pt/Pd ratios are between 0.42 and 2.33, which is much lower than many of the potential sources for Pt and Pd but is consistent with the greater solubility of Pd compared with Pt in most natural low-temperature fluids.

(Table 1) Maceral composition and organic carbon chemistry of ODP Leg 104 samples

The Cenozoic sediments sampled in ODP Leg 104 on the Vøring Plateau show a distinct variability of the total organic carbon content (TOC) and the accumulation rates of TOC. Based on the geochemical and organic-petrographic characterization of the sedimentary organic matter (OM), the allochthonous and autochthonous proportion of the OM could be quantified. The results clearly demonstrate that high TOC percentages and TOC accumulation rates in Cenozoic sediment sections display a generally high input of allochthonous organic matter. Oxidized and partly well-rounded organic particles built up the main portion of OM within the Miocene, TOC-rich sediments. The most probable source of this oxidized OM are reworked sediments from the Scandinavian shelf. Changes in the input of these organic particles are to some degree correlative with sea-level changes. The Cenozoic accumulation of autochthonous OM is low and does not reveal a clear variation during the Miocene and early Pliocene. In spite of a high accumulation rate of biogenic opal during the Early Miocene, the accumulation rate of autochthonous TOC is low. The autochthonous particle assemblage is dominated by relatively inert OM, like dinoflagellate cysts. This points to an intensive biological and/or early diagenetic degradation of the marine OM under well oxidized bottom water conditions during the last 23 Myr. Nevertheless, a continuation of marine OM degradation during later stages of diagenesis cannot be excluded. A prominent dominance of allochthonous OM over autochthonous is documented with the beginning of the Pliocene. At 2.45 Ma the episodic occurrence of ice-rafted, thermally mature OM reflects the onset of the glacial erosion of Mesozoic, coal and black shale bearing sediments on the Scandinavian and Barents Sea shelves. The first occurrence of these, in view of the actual burial depth, thermally overmature OM particles is, therefore, a marker for the beginning of the strong Scandinavian glaciation and the advance of the glacial front toward the shelves.

(Table 1) Characteristics of silicified sediments at DSDP Site 61-462 according to host-rock lithology, opal-CT-to-quartz ratio, and the origin of the quartz phase

This study deals with the mineralogical variability of siliceous and zeolitic sediments, porcellanites, and cherts at small intervals in the continuously cored sequence of Deep Sea Drilling Project Site 462. Skeletal opal is preserved down to a maximum burial depth of 390 meters (middle Eocene). Below this level, the tests are totally dissolved or replaced and filled by opal-CT, quartz, clinoptilolite, and calcite. Etching of opaline tests does not increase continously with deeper burial. Opal solution accompanied by a conspicuous formation of authigenic clinoptilolite has a local maximum in Core 16 (150 m). A causal relationship with the lower Miocene hiatus at this level is highly probable. Oligocene to Cenomanian sediments represent an intermediate stage of silica diagenesis: the opal-CT/quartz ratios of the silicified rocks are frequently greater than 1, and quartz filling pores or replacing foraminifer tests is more widespread than quartz which converted from an opal-CT precursor. As at other sites, there is a marked discontinuity of the transitions from biogenic opal via opal-CT to quartz with increasing depth of burial. Layers with unaltered opal-A alternate with porcellanite beds; the intensity of the opal-CT-to-quartz transformation changes very rapidly from horizon to horizon and obviously is not correlated with lithologic parameters. The silica for authigenic clinoptilolite was derived from biogenic opal and decaying volcanic components.

Distribution of organic carbon in surface sediments covered during SONNE cruise SO184

Sediments were sampled and oxygen profiles of the water column were determined in the Indian Ocean off west and south Indonesia in order to obtain information on the production, transformation, and accumulation of organic matter (OM). The stable carbon isotope composition (d13Corg) in combination with C/N ratios depicts the almost exclusively marine origin of sedimentary organic matter in the entire study area. Maximum concentrations of organic carbon (Corg) and nitrogen (N) of 3.0% and 0.31%, respectively, were observed in the northern Mentawai Basin and in the Savu and Lombok basins. Minimum d15N values of 3.7 per mil were measured in the northern Mentawai Basin, whereas they varied around 5.4 per mil at stations outside this region. Minimum bottom water oxygen concentrations of 1.1 mL L**1, corresponding to an oxygen saturation of 16.1%, indicate reduced ventilation of bottom water in the northern Mentawai Basin. This low bottom water oxygen reduces organic matter decomposition, which is demonstrated by the almost unaltered isotopic composition of nitrogen during early diagenesis. Maximum Corg accumulation rates (CARs) were measured in the Lombok (10.4 g C m**-2 yr**-1) and northern Mentawai basins (5.2 g C m**-2 yr**-1). Upwelling-induced high productivity is responsible for the high CAR off East Java, Lombok, and Savu Basins, while a better OM preservation caused by reduced ventilation contributes to the high CAR observed in the northern Mentawai Basin. The interplay between primary production, remineralisation, and organic carbon burial determines the regional heterogeneity. CAR in the Indian Ocean upwelling region off Indonesia is lower than in the Peru and Chile upwellings, but in the same order of magnitude as in the Arabian Sea, the Benguela, and Gulf of California upwellings, and corresponds to 0.1-7.1% of the global ocean carbon burial. This demonstrates the relevance of the Indian Ocean margin off Indonesia for the global OM burial.

Lithofacies, chronostratigraphy, minerals and diagenetic silica facies at DSDP Leg 80 Holes

X-ray powder diffraction and optical and scanning-electron microscope analyses of sediment samples taken from four sites drilled in the Goban Spur area of the northeast Atlantic show variable diagenetic silicification of sediments at several stratigraphic horizons. The results are as follows: 1. The silicified sediments are middle Eocene at Site 548, Paleocene to lower Albian at Site 549, upper to lower Paleocene at Site 550, and lower Turanian at Site 551. 2. There are three types of these silicified sediments: nodular type in carbonate-rich host sediments, bedded type in clayey host sediments, and a type transitional between the other two. 3. Silica diagenesis is considered to progress as follows: dissolution of siliceous fossils; precipitation of opal CT in pore spaces and transformation of biogenic silica (opal A) to opal CT, development of opal CT cement; chalcedonic quartz precipitation in pore spaces and replacement of foraminiferal tests by chalcedonic quartz; and finally, transformation of opal CT to quartz, and cementation. But the strong influence of host-sediment types on diagenetic silica fades is recognized. Bedded-type silicified sediments in a clayey environment indicate a lower grade of silica diagenesis. Only very weak chalcedonic quartz formation is recognized, and there is no opal CT cementation, even in Lower Cretaceous bedded-type clayey silicified sediments. 4. The rf(101) spacing of opal CT shows two distinct trends of ordering or decrease with burial depth; one is a rapid change, in the case of nodular silicified sediments, and the other is a more gentle shift, found in bedded silicified sediments. 5. Diagenetic silica facies of the nodular type develop as irregular concentric zones around some nodule nuclei. Also, quartz-chert nodule formation occurs at rather shallower horizons, and is discordant with the trend of decreasing d(101) spacing in opal CT. 6. Silicified sediments at Site 551 are shallower than at the other sites. The diagenetic silica facies suggest the probable erosion of 300 m or more of sediment at this site. 7. The zeolites clinoptilolite and phillipsite were found in the sediment samples recovered on Leg 80. Clinoptilolite occurs from the shallower levels to the deepest horizons of diagenetically silicified zones, suggesting that clinoptilolite formation is related to diagenesis of biogenic silica. Phillipsite at Site 551 (Section 551-5-2) may originate from volcanogenie material.

Chert intervals in DSDP and ODP sites (Table 1)

Radiolarian cherts in the Tethyan realm of Jurassic age were recently interpreted as resulting from high biosiliceous productivity along upwelling zones in subequatorial paleolatitudes the locations of which were confirmed by revised paleomagnetic estimates. However, the widespread occurrence of cherts in the Eocene suggests that cherts may not always be reliable proxies of latitude and upwelling zones. In a new survey of the global spatio-temporal distribution of Cenozoic cherts in Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) sediment cores, we found that cherts occur most frequently in the Paleocene and early Eocene, with a peak in occurrences at ~50 Ma that is coincident with the time of highest bottom water temperatures of the early Eocene climatic optimum (EECO) when the global ocean was presumably characterized by reduced upwelling efficiency and biosiliceous productivity. Cherts occur less commonly during the subsequent Eocene global cooling trend. Primary paleoclimatic factors rather than secondary diagenetic processes seem therefore to control chert formation. This timing of peak Eocene chert occurrence, which is supported by detailed stratigraphic correlations, contradicts currently accepted models that involve an initial loading of large amounts of dissolved silica from enhanced weathering and/or volcanism in a supposedly sluggish ocean of the EECO, followed during the subsequent middle Eocene global cooling by more vigorous oceanic circulation and consequent upwelling that made this silica reservoir available for enhanced biosilicification, with the formation of chert as a result of biosilica transformation during diagenesis. Instead, we suggest that basin-basin fractionation by deep-sea circulation could have raised the concentration of EECO dissolved silica especially in the North Atlantic, where an alternative mode of silica burial involving widespread direct precipitation and/or absorption of silica by clay minerals could have been operative in order to maintain balance between silica input and output during the upwelling-deficient conditions of the EECO. Cherts may therefore not always be proxies of biosiliceous productivity associated with latitudinally focused upwelling zones.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.

Products of chlorophyll diagenesis from DSDP Leg 57 Holes

Tetrapyrrole pigments isolated from sediments retrieved during Leg 57 include pheophytin-a, a myriad of chlorins, free-base deoxophylloerythroetioporphyrin (DPEP), as well as copper and nickel porphyrins. Their richness, both qualitatively and quantitatively, in chlorin tetrapyrroles affords a relatively complete study on the early diagenesis of chlorophyll. Our studies, coupled with those in the preceding chapter by Louda et al., point out the influence of pre- and postdepositional environments upon the mode of chlorophyll diagenesis. Formation of tetrapyrroles, collectively called "petroporphyrins," is seen to occur in only a limited set of environmental conditions (see Baker and Palmer, 1978). The more generalized route of chlorophyll diagenesis, at least in the ocean, results in removal of tetrapyrrole pigment, from the fossil record. Late diagenetic products, metalloporphyrins, are found to represent an extremely minor component of the tetrapyrrole assemblage in sediments studied from the Japan Trench. The products of chlorophyll diagenesis isolated from Japan Trench sediments allow expansion of previous diagenetic schemes (Baker and Palmer, 1978; Triebs, 1936) and indicate directions for future studies.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Sediment and pore fluid chemistry for IODP Sites 311-U1325 and 311-U1329

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Mineralogy and incipient diagenesis of Pigmy Basin sediments, DSDP Hole 96-619

Pigmy Basin sediments cored in Hole 619 of Deep Sea Drilling Project Leg 96 are silty clays composed, on the average, of < 1% sand, 37% silt, 48% clay, and 14% carbonate minerals. Except for minor grain dissolution in some silt grains, there is no distinctive variation with depth in either composition or texture of the sand- and silt-sized minerals. This suggests a constant source of sediment supply and little diagenetic alteration of these size fractions. Clay minerals are dominated by smectite or, more precisely, montmorillonite. On the average, the clay-sized fraction consists of 48% smectite and mixed layer minerals, 30% illite, and 23% total kaolinite and chlorite. There appears to be a slight decrease in smectite and concomitant increases in other clay minerals with depth. These changes are further substantiated by the variations of ammonium acetate exchangeable K+, Mg2+, and Na+ in bulk samples. Thus, incipient diagenesis of Pigmy Basin sediments is evidenced in the mineralogical and associated chemical characteristics of the clay fractions.

Geochemistry of continental slope and deep sea basin sediments off Uruguay

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement (<6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1 N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24 h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe2+. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.

Organic matter, isotopic composition of calcite veins in basement basalt and pore water at DSDP Leg 78A Holes

Sediments of the Barbados Ridge complex, cored on DSDP Leg 78A, contain low concentrations of acid-insoluble carbon (0.05-0.25%) and nitrogen (C/N 1.5-5) and dispersed C1-C6 hydrocarbons (100-800 ppb). The concentrations of organic carbon and 13C in organic carbon decrease with depth, whereas the concentration of dispersed hydrocarbons increases slightly with depth. These trends may reflect the slow oxidation of organic matter, with selective removal of 13C and slow conversion of the residual organic matter to hydrocarbons. Very minor indications of nitrogen gas were observed at about 250 meters sub-bottom at two of the drilling sites. Basement basalts have calcite veins with d13C values in the range of 2.0 to 3.2 per mil and d18O-SMOW values ranging from 28.5 to +30.6 per mil. Interstitial waters have d18O-SMOW of 0.2 to -3.5 per mil and dD-SMOW of -2 to -15 per mil. The oxygen isotopic composition of the calcite veins in the basement basalts gives estimated equilibrium fractionation temperatures in the range of 11 to 24°C, assuming precipitation from water with d18O-SMOW in the range of +0.1 to -1.0 per mil. This suggests that basalt alteration and precipitation of vein calcite occurred in contact either with warmer Campanian seawater or, later, with pore water, after burial to depths of 200- 300 meters. Pore waters from all three sites are depleted in deuterium and 18O, and dissolved sulfate is enriched in 34S at Sites 541 and 542, but not at Site 543.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.