Barium concentrations und stable isotope ratios of late Paleocene deep-sea sediments

Deep-sea sediment Ba* (Ba/Al2O3(sample) * 15% - Ba(aluminosilicate) records show increasing values synchronous with the evolution of the late Paleocene global d13C maximum, reflecting an increase in marine surface primary production and biogenic barite formation at this time. At two oligotrophic locations, Deep Sea Drilling Project (DSDP) Sites 384 and 527 in the North and South Atlantic, respectively, Ba* increases from 160-360 ppm in the early Paleocene to 1100-3000 ppm during the d13C maximum. At equatorial DSDP Site 577, positioned within or near the high-productivity zone, Ba* increases from ~15,500 ppm in the early Paleocene to ~25,400 ppm in conjunction with late Paleocene maximum d13C values. Linear fitted correlation plots of sediment Ba* content versus surface water d13C in all three regions support barite originating in the euphotic zone. The early to late Paleocene relative increase in Ba* illustrates how burial rates of Corg (relative to Al2O3) accelerated by a factor of ~1.8 and ~6.0 in the eutrophic and oligotrophic areas, respectively. A tentative estimate, weighing our result for the entire ocean, suggests that accumulation rates of organic carbon increased by a factor of 2 during the late Paleocene d13C maximum.

Geochemistry, SiO2 minerals and isotopes at DSDP Hole 72-516F

Cherts recovered during DSDP Leg 72 from Rio Grande Rise sediments (Site 516) consist of both cristobalite and quartz, and contain ghosts of foraminifers and (more rare) radiolarians. Porcelanite made of disordered cristobalite is found in most old enclosing sediments. Local dissolution of siliceous microfossils during diagenesis is the most likely source of the silica required for the chert formation. As sediment age increases, the proportion of biogenic silica decreases and authigenic silica increases.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Stable oxygen isotope ratios of pore waters from ODP Leg 166 sites

This study investigates the d18O of pore waters from Sites 1003 through 1007, drilled along the western margin of the Great Bahama Bank during Leg 166 of the Ocean Drilling Program. These pore waters generally show a positive correlation between d18O and the concentration of chloride. The exception to this trend is Site 1006, where the pore waters exhibit nonlinear behavior with respect to chloride. The correlation between the concentration of Cl- and d18O at most of the sites appears to be a coincidence because although the increase in Cl- is a result of diffusion from an underlying source, the increases in d18O result from the recrystallization of metastable carbonates in the presence of a geothermal gradient. The difference in behavior in the d18O of the pore water at Site 1006 is probably a result of the relative reduced rate of carbonate recrystallization at this site. The d18O of the pore waters in the upper portion of the cores shows a pattern similar to the concentration of chloride in that there is an interval of 30-50 m in which neither the d18O nor the concentration of Cl- changes. This interval is consistent with either an interval of very rapid deposition of sediment or the advection of fluid through the platform. Both the d18O and the concentration of Cl- increase toward the platform, suggesting an input of saline and isotopically heavy water from the platform surface.

Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.

Major nannofossils, carbon and oxygen isotopes and carbon composition of ODP leg 194 site survey gravity cores

Biostratigraphic, sedimentologic, and geochemical analyses of hemipelagic periplatform sediments from shallow gravity cores taken during the Ocean Drilling Program Leg 194 site survey reveal that, despite the strong currents and almost infilled intraplatform bathymetric depressions, recent sedimentation at the location of the Leg 194 drill sites recorded glacial-interglacial cycles. Sediment analyses included determination of sediment type, carbonate content, bulk stable oxygen isotope composition, and calcareous nannofossil zones. Glacial periods, identified by elevated bulk d18O, are characterized by darker sediment color, coarser grain size, and lower carbonate content, whereas interglacial periods yield lighter-colored, finer, and carbonate-rich sediments. These data from the shallowmost few meters of Marion Plateau sediments complement the subsurface information of Leg 194 holes, in which the top few meters have not been analyzed in such a high-resolution fashion. In addition, these gravity cores are more likely to have recovered the sediments closest to the sediment/water interface as compared to the hydraulic piston cores collected during Leg 194.

Stable carbon and oxygen isotopes of foraminifera fand carbon content of ODP Leg 107 holes

High-resolution bio- and chemostratigraphy of an earliest Pliocene section from ODP Site 652 indicates that postflood paleoceanographic conditions in the Tyrrhenian Sea can be sub-divided into two discrete intervals. The first is manifested by an acme of Sphaeroidinellopsis spp., increasing carbonate contents, and a progressive decrease upsection in both the d13C and dl8O values of the planktonic foraminifera. The lower part of the acme interval contains unusual surface-to-bottom water isotope gradients suggesting a stratification of two water masses. Normal gradients in the upper part of the acme interval suggest a well-mixed water body. Between the end of the acme interval and the MP11/MP12 boundary, denoted by the first occurrence (F.O.) of Globorotalia margaritae, a migrational first appearance, there was a catastrophic collapse of the gradient marking an onset of the second post-flood interval. The disintegration of habitable conditions is suggested by a sharp decrease in carbonate content and the disappearance of the benthonic assemblage, which is subsequently replaced predominantly by Uvigerinapygmea, indicative of cold, low-oxygenated bottom waters. The introduction of benthonic species denoting well-oxygenated bottom conditions occurs within the lower MP12 zone. Superimposed on these overall trends are shorter term, warm-cold cycles, which are interpreted as orbitally induced, climatic fluctuations. Correlative studies of the less complete earliest Pliocene sections from ODP Holes 653B and 654A confirm these interpretations. A scenario derived from an integration of all the stratigraphic data indicates that normal paleoceanographic conditions were operating in the Tyrrhenian Sea only approximately 250,000 yr after the cessation of Messinian evaporative conditions at the Miocene/Pliocene boundary. The post-flood interval is marked by an initial period of gradual infilling, the Sphaeroidinellopsis spp. acme interval, followed by a disintegration of oceanographic conditions and a second recovery period. A sudden influx of cold, deep Atlantic waters into the Tyrrhenian Sea, resulting from a major tectonic break in the Gibraltar sill, may have caused this catastrophic reversal in the orderly recovery of normal paleoceanographic conditions in the post-flood period.

Comparison of accumulation rates and stable isotope ratios

Since 1979/80, glaciological studies have been carried out at Ekströmisen, Antarctica, including accumulation-stake measurements, snow-pit and shallow-firn-core studies. Snowstratigraphy, chemical properties and stable-isotope ratios (d18O) were investigated. This study focuses on three cores taken between 1982 and 1998. The 1998 core was dated using dielectric profiling, d18O profiles and stake measurements. Accumulation rates showhigh interannual and spatial variability due to the extreme wind influence. No significant trend was found for the last 50 years; during the first half of the 20th century, accumulation decreased. The high spatial and interannual variability, however, means that trends must be interpreted with care. In spite of the highly irregular accumulation distribution, stable-isotope ratios show little spatial variability. The mean annual d18O values of cores B04 and FB0198 agree fairly well for the time period 1955-82 covered by both cores. d18O values have increased during most of the 20th century; since the late 1980s a decrease is observed. This change is not related to air temperature, since mean annual air temperatures at Neumayer show no significant trend over the last two decades.

Water chemistry of lakes from the Antarctic

This paper reviews Japanese limnological studies mainly in the McMurdo and Syowa oases, with special emphasis on the nutrient distribution. Generally, the chemical composition of the major ionic components in the coastal lakes and ponds is similar to that in seawater, while that in inland Dry Valley lakes and ponds of the McMurdo Oasis is abundant in calcium, magnesium and sulfate ions. The former can be explained by the direct influences of sea salts, while the latter is mainly attributable to the accumulation of atmospheric salts. Most saline lakes are meromictic. Dissolved oxygen concentrations in the upper layers are saturated or supersaturated, but the bottom layers are anoxic and often hydrogen sulfide occurs. The concentrations of nutrients vary largely not only among the lakes but also with depth. Silicate-Si, which is generally abundant in all freshwater and saline lakes, may be due to erosions of soils and rocks. Nitrite-N concentrations in both freshwater and saline lakes are generally low. Nitrate-N concentrations in the oxic layers of the inland saline lakes in the McMurdo Oasis arc often high, but not high in the coastal saline lakes of the Syowa and Vestfold oases. The abundance of phosphate-P and ammonium-N in the bottom stagnant layers of saline lakes can be explained by the accumulation of microbially released nutrients due to the decomposition of organic substances. Nutrients are supplied mainly from meltstreams in the catchment areas, and are proved to play an important role in primary production.

Foraminiferal study of ODP Hole 189-1171

Sequence boundary ages determined in shallow-water sediments obtained from ODP (Ocean Drilling Program) Leg 189 Site 1171 (South Tasman Rise) compare well with other stratigraphic records (New Jersey, United States, and northwestern Europe) and d18O increases from deep-sea records, indicating that significant (>10 m) eustatic changes occurred during the early to middle Eocene (51-42 Ma). Sequence boundaries were identified and dated using lithology, bio- and magnetostratigraphy, water-depth changes, CaCO3 content, and physical properties (e.g., photospectrometry). They are characterized by a sharp bioturbated surface, low CaCO3 content, and an abrupt increase in glauconite above the surface. Foraminiferal biofacies and planktonic/benthic foraminiferal ratios were used to estimate water-depth changes. Ages of six sequence boundaries (50.9, 49.2, 48.5-47.8, 47.1, 44.5, and 42.6 Ma) from Site 1171 correlate well to the timings of d18O increases and sequence boundaries identified from other Eocene studies. The synchronous nature of sequence boundary development from globally distal sites and d18O increases indicates a global control and that glacioeustasy was operating in this supposedly ice-free world. This is supported by previous modeling studies and atmospheric pCO2 estimates showing that the first time pCO2 levels decreased below a threshold that would support the development of an Antarctic ice sheet occurred at ca. 51 Ma. Estimates of sea-level amplitudes range from ~20 m for the early Eocene (51-49 Ma) and ~25 m to ~45 m for the middle Eocene (48-42 Ma) using constraints established for Oligocene d18O records.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Oxygen and carbon isotopes of planktic foraminifera and ageprofile datum description at DSDP Hole 69-504

A detailed oxygen isotope record (resolution: about 2500 years) has been obtained for the Pleistocene sediments at Hole 504. Preliminary measurements made deeper in the section suggest that at least the upper Pliocene section is also amenable to detailed stable isotope work. The record for the middle Pleistocene resembles that obtained previously from piston cores in the western equatorial Pacific, although the superior resolution of this high-accumulation-rate site reveals a greater amplitude of isotope variation than previously observed. The record for the lower Pleistocene reveals variation that is both greater in amplitude and higher in frequency than apparent from previously analyzed piston cores. The site provides the best material recovered to date for the study of the evolution of climatic variability during the past few million years.

Late Albian foraminiferal carbon and oxygen isotope data and biostratigraphic datums from ODP holes 171-1050C and 171-1052E

A late Albian-early Cenomanian record (~103.3 to 99.0 Ma), including organic-rich deposits and a d13C increase associated with oceanic anoxic event 1d (OAE 1d), is described from Ocean Drilling Program sites 1050 and 1052 in the subtropical Atlantic. Foraminifera are well preserved at these sites. Paleotemperatures estimated from benthic d18O values average ~14°C for middle bathyal Site 1050 and ~17°C for upper bathyal Site 1052, whereas surface temperatures are estimated to have ranged from 26°C to 31°C at both sites. Among planktonic foraminifera, there is a steady balance of speciation and extinction with no discrete time of major faunal turnover. OAE 1d is recognized on the basis of a 1.2 per mill d13C increase (~100.0-99.6 Ma), which is similar in age and magnitude to d13C excursions documented in the North Atlantic and western Tethys. Organic-rich "black shales" are present throughout the studied interval at both sites. However, deposition of individual black shale beds was not synchronous between sites, and most of the black shale was deposited before the OAE 1d d13C increase. A similar pattern is observed at the other sites where OAE 1d has been recognized indicating that the site(s) of excess organic carbon burial that could have caused the d13C increase has (have) yet to be found. Our findings add weight to the view that OAEs should be chemostratigraphically (d13C) rather than lithostratigraphically defined.