Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Organic facies variations in the Mesozoic South Atlantic DSDP Holes

Visual kerogen and total organic carbon determinations indicate that there are two periods of organic enrichment events in the Mesozoic sediments of the South Atlantic. The first period, from the Late Jurassic through the late Aptian, is recorded in sediments from the Falkland Plateau, the Cape Basin, and the Angola Basin. Apparently, salinity stratification in the restricted basin, coupled with rising sea level, led to bottom water anoxia and organic enrichment. The second event, from the late Albian to the Santonian period, is recorded in sediments from the Angola Basin and the Sao Paulo Plateau. It appears to have been caused by development of an anoxic oxygen minimum zone at midwater depths. Organic matter sedimentation in the Mesozoic South Atlantic is controlled by geologic, climatic, eustatic, and Oceanographic factors.

Organofacies reconstruction and lipid geochemistry of sediments from the Galicia margin

Samples of Lower to middle Cretaceous rocks from ODP Sites 638, 640, and 641, drilled on the Galicia continental margin in the northeast Atlantic, have been investigated by organic geochemical methods (i.e., organic carbon determination, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry) to define the Organofacies types and the depositional environments of these sediments. The results of this study fit well into the general picture drawn for the depositional history of the organic matter in Cretaceous organic-carbon-rich sediments in the North Atlantic from previous DSDP investigations. During the Valanginian to Albian, terrigenous organic carbon dominated the organic matter deposited on the Galicia continental margin. Cyclic changes in total organic carbon content were probably controlled by climatic-triggered changes in the supply of terrigenous organic matter from the nearby continent. A drastic change in depositional environment must have occurred near the Cenomanian/Turonian boundary. The preservation of large amounts of marine organic carbon in these sediments was probably caused by anoxic deep-water conditions during that time, rather than high productivity. All of the primary organic matter of the sediment samples investigated is thermally immature, as indicated by very low vitrinite reflectance values.

Mineralogy and chemistry of basalts and secondary minerals from DSDP Site 417, Atlantic Ocean

Basalts from DSDP Site 417 (109 Ma) exhibit the effects of several stages of alteration reflecting the evolution of seawater-derived solution compositions and control by the structure and permeability of the crust. Characteristic secondary mineral assemblages occur in often superimposed alteration zones within individual basalt fragments. By combining bulk rock and single phase chemical analyses with detailed mineralogic and petrographic studies, chemical changes have been determined for most of the alteration stages identified in the basalts. 1) Minor amounts of saponite, chlorite, and pyrite formed locally in coarse grained portions of massive units, possibly at high temperatures during initial cooling of the basalts. No chemical changes could be determined for this stage. 2) Possible mixing of cooled hydrothermal fluids with seawater resulted in the formation of celadonite-nontronite and Fe-hydroxide-rich black halos around cracks and pillow rims. Gains of K, Rb, H20, increase of Fe 3 +/FeT and possibly some losses of Ca and Mg occurred during this stage. 3a) Extensive circulation of oxygenated seawater resulted in the formation of various smectites, K-feldspar, and Fe-hydroxides in brown and light grey alteration zones around formerly exposed surfaces. K, Rb, H20, and occasionally P were added to the rocks, Fe3+/FeT increased, and Ca, Mg, Si and occasionally Al and Na were lost. 3 b) Anoxic alteration occurred during reaction of basalt with seawater at low water-rock ratios, or with seawater that had previously reacted with basalt. Saponite-rich dark grey alteration zones formed which exhibit very little chemical change: generally only slight increases in Fe 3 +/FeT and H20 occurred. 4) Zeolites and calcite formed from seawater-derived fluids modified by previous reactions with basalt. Chemical changes involved increases of Ca, Na, H20 , and CO2 in the rocks. 5) A late stage of anoxic conditions resulted in the formation of minor amounts of Mn-calcites and secondary sulfides in previously oxidized rocks. No chemical changes were determined for this stage. Recognition of such alteration sequences is important in understanding the evolution of submarine hydrothermal systems and in interpreting chemical exchange due to seawater-basalt reactions.

Geochemistry and isotopes at DSDP Site 76-533

Concentrations and d34S and d13C values were determined on SO4, HCO3, CO2, and CH4 in interstitial water and gas samples from the uppermost 400 m of sediment on the Blake Outer Ridge. These measurements provide the basis for detailed interpretation of diagenetic processes associated with anaerobic respiration of electrons generated by organic- matter decomposition. The sediments are anaerobic at very shallow depths (<1 m) below the seafloor. Sulfate reduction is confined to the uppermost 15 m of sediment and results in a significant outflux of oxidized carbon from the sediments. At the base of the sulfate reduction zone, upward-diffusing CH4 is being oxidized, apparently in conjunction with SO4 reduction. CH4 generation by CO2 reduction is the most important metabolic process below the 15-m depth. CO2 removal is more rapid than CO2 input over the depth interval from 15 to 100 m, and results in a slight decrease in HCO3 concentration accompanied by a 40 per mil positive shift in d13C. The differences among coexisting CH4, CO2, and HCO3 are consistent with kinetic fractionation between CH4 and dissolved CO2, and equilibrium fractionation between CO2 and HCO3. At depths greater than 100 m, the rate of input of CO2 (d13C = -25 per mil) exceeds by 2 times the rate of removal of CO2 by conversion to CH4 (d13C of -60 to -65 per mil). This results in an increase of dissolved HCO3 concentration while maintaining d13C of HCO3 relatively constant at +10 per mil. Non-steady-state deposition has resulted in significantly higher organic carbon contents and unusually high (70 meq/l) pore-water alkalinities below 150 m. These high alkalinities are believed to be related more to spontaneous decarboxylation reactions than to biological processes. The general decrease in HCO3 concentration with constant d13C over the depth interval of 200 to 400 m probably reflects increased precipitation of authigenic carbonate. Input-output carbon isotope-mass balance calculations, and carbonate system equilibria in conjunction with observed CO2-CH4 ratios in the gas phase, independently suggest that CH4 concentrations on the order of 100 mmol/kg are present in the pore waters of Blake Outer Ridge sediments. This quantity of CH4 is believed to be insufficient to saturate pore waters and stabilize the CH4*6H2O gas hydrate. Results of these calculations are in conflict with the physical recovery of gas hydrate from 238 m, and with the indirect evidence (seismic reflectors, sediment frothing, slightly decreasing salinity and chlorinity with depth, and pressure core barrel observations) of gas-hydrate occurrence in these sediments. Resolution of this apparent conflict would be possible if CH4 generation were restricted to relatively thin (1-10 m) depth intervals, and did not occur uniformly at all depths throughout the sediment column, or if another methanogenic process (e.g., acetate fermentation) were a major contributor of gas.

Black shales from the Upper Aptian and Lower Albanian of the Volcontian Basin

Calcareous nannoplankton, palynomorph, benthic foraminifera, and oxygen isotope records from the supraregionally distributed Niveau Paquier (Early Albian age, Oceanic Anoxic Event 1b) and regionally distributed Niveau Kilian (Late Aptian age) black shales in the Vocontian Basin (SE France) exhibit variations that reflect paleoclimatic and paleoceanographic changes in the mid-Cretaceous low latitudes. To quantify surface water productivity and temperature changes, nutrient and temperature indices based on calcareous nannofossils were developed. The nutrient index strongly varies in the precessional band, whereas variations of the temperature index reflect eccentricity. Since polar ice caps were not present during the mid-Cretaceous, these variations probably result from feedback mechanisms within a monsoonal climate system of the mid-Cretaceous low latitudes involving warm/humid and cool/dry cycles. A model is proposed that explains the formation of mid-Cretaceous black shales through monsoonally driven changes in temperature and evaporation/precipitation patterns. The Lower Albian Niveau Paquier, which has a supraregional distribution, formed under extremely warm and humid conditions when monsoonal intensity was strongest. Bottom water ventilation in the Vocontian Basin was diminished, probably due to increased precipitation and reduced evaporation in regions of deep water formation at low latitudes. Surface water productivity in the Vocontian Basin was controlled by the strength of monsoonal winds. The Upper Aptian Niveau Kilian, which has a regional distribution only, formed under a less warm and humid climate than the Niveau Paquier. Low-latitude deep water formation was reduced to a lesser extent and/or on regional scale only. The threshold for the formation of a supraregional black shale was not reached. The intensity of increases in temperature and humidity controlled whether black shales developed on a regional or supraregional scale. At least in the Vocontian Basin, the increased preservation of organic matter at the sea floor was more significant in black shale formation than the role of enhanced productivity.

Carbonate, organic carbon and nitrogen, bitumen and rock-eval pyrolysis at DSDP Leg 79 Holes

The lipids and kerogens of 15 sediment samples from Site 547 (ranging from Pleistocene to Early Jurassic/Triassic) and 4 from Site 545 (Cretaceous) have been analyzed. A strong terrestrial contribution of organic matter was found, and significant autochthonous inputs were also present, especially at Site 545. Both strongly reduced and highly oxidized sediments have been found in the Cenozoic and Jurassic samples of Site 547. On the contrary, all the Cretaceous sections of Sites 547 and 545 are anoxic. Sediments from anoxic paleoenvironments are immature and have a high content of sterenes, diasterenes, steradienes, hopenes, and ßß hopanes. Samples from oxic paleoenvironments are mainly mature and their content of hopenes and steriod structures is below the detection level. Nevertheless, their hopane distributions have the immature ßß homologs as the predominant molecular markers. For Site 545 the most abundant molecular markers are ring A monoaromatic steranes, and their presence is attributed to microbial and chemical transformations during early diagenesis.

Sapropel cycles in the Mediterranean Sea

Water column stratification increased at climatic transitions from cold to warm periods during the late Quaternary and led to anoxic conditions and sapropel formation in the deep eastern Mediterranean basins. High-resolution data sets on sea-surface temperatures (SST) (estimated from UK'37 indices) and d18O of planktonic foraminifer calcite (d18Ofc) across late Pleistocene sapropel intervals show that d18Ofc decreased (between 1 and 4.6 per mil) and SST increased (between 0.7° and 6.7°C). Maximal d18Oseawater depletion of eastern Mediterranean surface waters at the transition is between 0.5 and 3.0 per mil, and in all but one case exceeded the depletion seen in a western Mediterranean core. The depletion in d18Oseawater is most pronounced at sapropel bases, in agreement with an initial sudden input of monsoon-derived freshwater. Most sapropels coincide with warming trends of SST. The density decrease by initial freshwater input and continued warming of the sea surface pooled fresh water in the surface layer and prohibited deep convection down to ageing deep water emplaced during cold and arid glacial conditions. An exception to this pattern is "glacial" sapropel S6; its largest d18Oseawater depletion (3 per mil) is almost matched by the depletion in the western Mediterranean Sea, and it is accompanied by surface water cooling following an initially rapid warming phase. A second period of significant isotopic depletion is in isotope stage 6 at the 150 kyr insolation maximum. While not expressed as a sapropel due to cold SST, it is in accord with a strengthened monsoon in the southern catchment.

Stable carbon and oxygen isotope record of Cretaceous planktonic foraminifera from DSDP (Table 1)

The Cretaceous Heterohelix moremani (Cushman) was the only biserial planktonic foraminiferal species from its first appearance in the late Albian up to the Cenomanian/Turonian boundary. Within that time, it increased gradually in abundance relative to other planktonic foraminifera in five Circum-North Atlantic sections. It is generally rare in upper Albian sediments, common in most of the Cenomanian and very abundant in sediments representing the latest Cenomanian Oceanic Anoxic Event. Short-term variations on the overall abundance trend correlate with positive excursions in the bulk carbonate delta13C record. Maximum rain rates of H. moremani during OAE2 show that this species was an opportunist that did well in extreme conditions, but its overall distribution indicates that it is not necessarily a marker for very high palaeoproductivity environments. Stable oxygen and carbon isotope measurements on foraminiferal species indicate that H. moremani was a surface water dweller at least in part of its geographic range, but incorporated 13C out of equilibrium with ambient seawater. It is depleted in delta13C relative to other planktonic foraminifera, which is attributed to vital effects related to its opportunistic character.

Re-OS and Pb isotope ratios of sediments from Saanich Inlet, Western Canada

Re-Os and Pb-Pb isotopic analysis of reduced varved sediments cored in the deeper basin of Saanich Inlet (B.C.) are presented. From core top to 61 cm down-core, spanning approximately the last 100 yrs of sedimentation, 187Os/188Os ratio and Os concentration respectively increase from ~0.8 to ~0.9 and from 55 to 60 ppt, whereas Re concentration decreases from 3600 to 2600 ppt. Re correlates with Corg (R2=0.6) throughout the entire section, whereas Os follows Re and Corg trends deeper down-core, suggesting a decoupling of a Re- and Os-geochemistry during burial and/or very early diagenesis. No systematic compositional differences are observed between seasonal laminae. 204Pb-normalized lead isotope ratios increase from sediment surface down to 7 cm down-core, then decrease steadily to pre-industrial levels at ~50 cm down-core. This pattern illustrates the contamination from leaded gasoline until the recent past. The measured Pb isotopic ratios point primarily toward gasoline related atmospheric lead from the USA. The osmium isotopic values measured are significantly lower than those of modern seawater-Os. In comparison with other anoxic environments, the osmium content of Saanich Inlet sediments is low, and its Os isotopic composition suggests significant inputs from unradiogenic sources (detrital and/or dissolved). Ultramafic lithologies in the watershed of the Fraser River are suspected to contribute to sedimentary inputs as well as to the input of dissolved unradiogenic osmium in the water of Saanich Inlet. The presence of some unradiogenic Os from anthropogenic contamination cannot be discounted near the core top, but since deeper, pre-anthropogenic levels also yielded unradiogenic Os results, one is led to conclude that the overall low 187Os/188Os ratios result from natural geochemical processes. Thus, the bulk sediment of Saanich Inlet does not appear to record 187Os/188Os composition of the marine end-member of the only slightly below normal salinity, fjord water. The low seawater-derived Os content of the sediment, coupled with unradiogenic Os inputs from local sources, explains the overall low isotopic values observed. As a consequence, such near-shore anoxic sediments are unlikely to record changes in the past ocean Os isotopic composition.

Cenomanian benthic foraminifera of Demerara Rise

This study is based on Cenomanian sediments of Ocean Drilling Program (ODP) Sites 1258 and 1260 from Demerara Rise (Leg 207, western tropical Atlantic, off Suriname, ~1000 and ~500 m paleo-water depth, respectively). Studied sediments consist of laminated black shales with TOC values between 3 and 18% and include the Mid Cenomanian Event (MCE), a positive carbon isotope excursion predating the well-known Oceanic Anoxic Event 2 (OAE 2). Benthic foraminiferal assemblages of the continuously eutrophic environment at Demerara Rise are characterized by low diversities (<= 9 species per sample) and large fluctuations in abundances, indicating oxygen depletion and varying organic matter fluxes. Dominant species at both sites are Bolivina anambra, Gabonita levis, Gavelinella dakotensis, Neobulimina albertensis, Praebulimina prolixa, and Tappanina cf. laciniosa. Benthic foraminiferal assemblages across the MCE show a threefold pattern: (1) stable ecological conditions below the MCE interval indicated by relatively high oxygenation and fluctuating organic matter flux, (2) decreasing oxygenation and/or higher organic matter flux during the MCE with decreasing benthic foraminiferal numbers and diversities (Site 1258) and a dominance of opportunistic species (Site 1260), and (3) anoxic to slightly dysoxic bottom-water conditions above the MCE as indicated by very low diversities and abundances or even the absence of benthic foraminifera. Slightly dysoxic conditions prevailed until OAE 2 at Demerara Rise. A comparison with other Atlantic Ocean and Tethyan sections indicates that the MCE reflects a paleoceanographic turning point towards lower bottom-water oxygenation, at least in the proto-North Atlantic Ocean and in the Tethyan and Boreal Realms. This general trend towards lower oxygenation of bottom waters across the MCE is accompanied by ongoing climate warming in combination with rising sea-level and the development of vast shallow epicontinental seas during the Middle and Late Cenomanian. These changes are proposed to have favoured the formation of warm and saline waters that may have contributed to intermediate- and deep-water masses at least in the restricted proto-North Atlantic and Tethyan Ocean basins, poor oxygenation of the Late Cenomanian sediments, and the changes in benthic foraminiferal assemblages across the MCE.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.