Stable carbon isotope record of Bahama Bank sediments

The carbon-isotopic composition (d13C) of bulk carbonates, obtained from a transect of sites drilled through platform and periplatform sediments of Holocene to Early Miocene age, has been compared to ascertain whether changes in the d13C can be correlated between sediments of equivalent ages and whether such changes can be related to global changes in the d13C of the dissolved inorganic carbon in the oceans over this time period. Five of the sites were drilled during Leg 166 of the Ocean Drilling Project (1003-1007) in a transect ranging from five km to 25 km away from the platform margin and penetrating sediments of Holocene to Oligocene age that are contained in 17 depositional sequences (A-Q). Two shallow-water sites, Clino and Unda were situated on a extension of the same transect on Great Bahama Bank in a water depth of 10-15 m. With the exception of Unda and Clino, the d13C of the carbonates ranges from +5 per mil in the younger sequences to +1 per mil in the Early Miocene. In each of the sites, the d13C is strongly positively correlated with the percentage of aragonite. As a consequence, the d13C of sequences A through F is strongly correlated, reflecting the decreasing amount of aragonite with increasing depth. In the two platform sites, the d13C is significantly lower in the younger portions of the cores as a result of the influences of meteoric diagenesis during repeated exposure during the Pleistocene. Although the d13C of the individual sequences can be correlated in most instances between the ODP holes, the changes are not related to global changes in the d13C of the oceans which in contrast to the d13C of the platform sediments become isotopically lower towards the present day. Instead variations in the d13C appear to be related to varying mixtures of d13C-rich banktop sediments and pelagic material.

Stable isotope (carbonates), organic carbon, calcium carbonate and occurrence of coccoliths at DSDP Hole 71-511

Thin but discrete pelagic limestone beds intercalated among the black mudstones near the top of the extensive Mesozoic black shale sequence of the Falkland Plateau are reminiscent of similar occurrences in the central and North Atlantic and may be cyclic in nature. They have been studied via carbonate, organic carbon, stable isotope, nannofloral, and ultrastructural analysis in an attempt to determine their mode of origin. Nannofossil diversity and preservation suggest that selective dissolution or diagenesis did not produce the interbedded coccolith-rich and coccolith-poor layers, nor did blooms of opportunistic species play a role. Stable isotope measurements of carbonate do not adequately constrain the origin of the cyclicity; however, the d13C data suggest that the more nannofossil-rich intervals may be due to higher nutrient supply and overturn of deeper waters at the site rather than influxes of well-oxygenated waters into an otherwise anoxic environment. Such an explanation is in accord with the nannofloral evidence

Geothermal measurements at ODP Leg 127 and 128 sites

Downhole temperature and thermal conductivity measurements in core samples recovered during Legs 127 and 128 in the Japan Sea resulted in five accurate determinations of heat flow through the seafloor and accurate estimates of temperature vs. depth over the drilled sections. The heat flows measured at these sites are in excellent agreement with nearby seafloor measurements. Drilling sampled basaltic rocks that form the acoustic basement in the Yamato and Japan basins and provided biostratigraphic and isotopic estimates of the age of these basins. The preliminary age estimates are compared with predicted heat flow values for two different thermal models of the lithosphere. A heat flow determination from the crest of the Okushiri Ridge yielded an anomalously high heat flow of 156 mW/m**2. This excessive heat flow value may have resulted from frictional heating on an active reverse fault that bounds the eastern side of the Ridge. Accurate estimates of sedimentation rates and temperatures in the sedimentary section combined with models of basin formation provide an opportunity to test thermochemical models of silica diagenesis. The current location of the opal-A/opal CT transition in the sedimentary section is determined primarily by the thermal history of the layer in which the transition is now found. Comparison of the ages and temperatures of the layer where the opal-A/opal-CT is found today is compatible with an activation energy of 14 to 17 kcal/mole.

Geochemistry of planktonic foraminifera from DSDP sites in the Atlantic and Pacific Ocean

The lithium content of planktonic foraminiferal calcite has been determined to evaluate temporal variability of seawater Li concentrations over the past 116 m.y. Mean foraminiferal calcite lithium/calcium in each time interval is no more than 16% greater nor 25% less than the mean Li/Ca of all samples. Li/Ca minima are observed for samples from 50-60 m.y. and 80-90 m.y., with Li/Ca about 25% lower than in adjacent time intervals. At no time during the past 40 m.y does mean Li/Ca appear to be higher than that at present. Subject to the limitations imposed by sample coverage and diagenesis, a similar conclusion holds for the past 116 m.y. Coupled with an oceanic mass balance model for Li, these data suggest that: (1) oceanic Li concentrations and, therefore, high-temperature hydrothermal circulation fluxes during the past 40 m.y. (and perhaps the past 100 m.y.) have not been more than perhaps 30-40% greater than at present for intervals any longer than a million years at most, and (2) these fluxes were not a factor of two higher 100 m.y. ago. By inference, variations in oceanic crustal generation rates over these time periods are similarly limited. Decreases in hydrothermal circulation fluxes and crustal generation rates or fluctuations up to 20% in these rates of a few million years duration are not necessarily ruled out by the Li/Ca data. The lack of variability in Li/Ca over time is not unequivocal evidence that hydrothermal fluxes have not varied because the rates of removal processes may be linked to changes in input fluxes.

Composition of recent carbonate bottom sediments from the Guiana shelf an off the West Africa

This work was based on a study of the upper layer of recent carbonate bottom sediments of the Atlantic Ocean. Biogenic carbonate of recent sediments is represented by metastable and stable minerals. In the ocean metastable phases can exist indefinitely long, but the structure of polymorphism determines inevitability of transformation of metastable phases into stable ones. This transformation occurs in the solid phase. In the absence of a critical point between the two phases of the transition process is not available for study by microscopic methods. It is estimated indirectly by studying the nature and extent of changes in mineral and chemical compositions. With aging of sediments their mineral composition alters in direction of increasing contents of resistant minerals. Fine grained sediments and fractions are subject to more intensive effects of early diagenesis processes, rather than coarse ones; this is reflected in their mineral composition. Regularities of distribution of carbonate minerals in size fractions consistent with the direction of polymorphic transformations in calcium carbonate. Such transformations can occur in a particular dimension of grains. Concrete grain size depends on environmental conditions. This situation explains presence of metastable biogenic carbonates at different depths of the ocean and suggests presence of diagenetic calcite in sediments occurring below expected for each case depth of the transition.

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.

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Calcium concentrations and isotopic composition in carbonates and porefluids from ODP Hole 130-807A

The calcium isotopic compositions (d44Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (a_s-f) between calcite and dissolved Ca2+ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of a_s-f at equilibrium in the marine sedimentary section is 1.0000+/-0.0001, which is significantly different from the value (0.9987+/-0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ~14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in d44Ca of +0.15? for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.

Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.

Geochemistry and soil characteristics of sediment core GeoB4234

Stable isotopes of sedimentary nitrogen and organic carbon are widely used as proxy variables for biogeochemical parameters and processes in the water column. In order to investigate alterations of the primary isotopic signal by sedimentary diagenetic processes, we determined concentrations and isotopic compositions of inorganic nitrogen (IN), organic nitrogen (ON), total nitrogen (TN), and total organic carbon (TOC) on one short core recovered from sediments of the eastern subtropical Atlantic, between the Canary Islands and the Moroccan coast. Changes with depth in concentration and isotopic composition of the different fractions were related to early diagenetic conditions indicated by pore water concentrations of oxygen, nitrate, and ammonium. Additionally, the nature of the organic matter was investigated by Rock-Eval pyrolysis and microscopic analysis. A decrease in ON during aerobic organic matter degradation is accompanied by an increase of the 15N/14N ratio. Changes in the isotopic composition of ON can be described by Rayleigh fractionation kinetics which are probably related to microbial metabolism. The influence of IN depleted in 15N on the bulk sedimentary (TN) isotope signal increases due to organic matter degradation, compensating partly the isotopic changes in ON. In anoxic sediments, fixation of ammonium between clay lattices results in a decrease of stable nitrogen isotope ratio of IN and TN. Changes in the carbon isotopic composition of TOC have to be explained by Rayleigh fractionation in combination with different remineralization kinetics of organic compounds with different isotopic composition. We have found no evidence for preferential preservation of terrestrial organic carbon. Instead, both TOC and refractory organic carbon are dominated by marine organic matter. Refractory organic carbon is depleted in 13C compared to TOC.

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

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.