Geochemical analyses from the Caravaca K/T boundary section, Spain

Thirty-six different geochemical and foraminiferal analyses were conducted on samples collected at closely spaced intervals across the Cretaceous/Tertiary (K/T) boundary exposed at Caravaca, Spain. A rapid reduction in the gradient between d13C values in fine fraction carbonate and benthic foraminiferal calcite and a decrease in the abundance of phosphorus (a proxy for organic carbon) and calcium were recorded in sediments 0-0.5 cm above the K/T boundary. These trends imply that an abrupt mass mortality occurred among pelagic organisms, leading to a significant reduction in the flux of organic carbon to the seafloor. In addition, variations in sulfur isotope ratios, the hydrocarbon-generating potential of kerogen (measured as the hydrogen index), and foraminiferal indices of dissolved oxygen level all imply that a rapid decrease in dissolved oxygen was coincident with the d13C event. Evidence of the low oxygen event has also been recognized in Japan and New Zealand, suggesting that intermediate water oxygen minima were widely developed during earliest Danian time. A threefold increase in the kaolinite/illite ratio and a 1.2 per mill decrease in d18O (carbonate fine fraction) were recorded in the basal 0.1-2 cm of Danian age sediments. These trends suggest that atmospheric warming and an increase in surface water temperature occurred 0-3 kyr after the d13C event. Recovery in the difference between d13C values in the carbonate fine fraction and in benthic foraminiferal calcite as well as increases in phosphorus and calcium contents occur at the base of planktonic foraminiferal Zone Pla, implying that an increase in primary productivity commenced some 13 kyr after the K/T boundary.

Geochemical analysis of surface sediments from the ocean floor and from sea ice in the northern Atlantic and Arctic Oceans

Barium in marine terrigenous surface sediments of the European Nordic Seas is analysed to evaluate its potential as palaeoproductivity proxy. Biogenic Ba is calculated from Ba and Al data using a conventional approach. For the determination of appropriate detrital Ba/Al ratios a compilation of Ba and Al analyses in rocks and soils of the catchments surrounding the Nordic Seas is presented. The resulting average detrital Ba/Al ratio of 0.0070 is similar to global crustal average values. In the southern Nordic Seas the high input of basaltic material with a low Ba/Al ratio is evident from high values of magnetic susceptibility and low Al/Ti ratios. Most of the Ba in the marine surface sediments is of terrigenous and not of biogenic origin. Variability in the lithogenic composition has been considered by the application of regionally varying Ba/Al ratios. The biogenic Ba values are comparable with those observed in the central Arctic Ocean, they are lower than in other oceanic regions. Biogenic Ba values are correlated with other productivity proxies and with oceanographic data for a validation of the applicability in paleoceanography. In the Iceland Sea and partly in the marginal sea-ice zone of the Greenland Sea elevated values of biogenic Ba indicate seasonal phytoplankton blooms. In both areas paleoproductivities may be reconstructed based on Ba and Al data of sediment cores.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Geochemical measurements of the Tasmanian Gateway from ODP Hole 189-1172A

Tectonic changes that produced a deep Tasmanian Gateway between Australia and Antarctica are widely invoked as the major mechanism for Antarctic cryosphere growth and Antarctic Circumpolar Current (ACC) development during the Eocene/Oligocene (E/O) transition (34-33 Ma). Ocean Drilling Program (ODP) Leg 189 recovered near-continuous marine sedimentary records across the E/O transition interval at four sites around Tasmania. These records are largely barren of calcareous microfossils but contain a rich record of siliceous- and organic-walled marine microfossils. In this study we integrate micropaleontological, sedimentological, geochemical, and paleomagnetic data from Site 1172 (East Tasman Plateau) to identify four distinct phases (A-D) in the E/O Tasmanian Gateway deepening that are correlative among ODP Leg 189 sites. Phase A, prior to 35.5 Ma: minor initial deepening characterized by a shallow marine prodeltaic setting with initial condensation episodes. Phase B, 35.5-33.5 Ma: increased deepening marked by the onset of major glauconitic deposition and inception of energetic bottom-water currents. Phase C, 33.5-30.2 Ma: further deepening to bathyal depths, with episodic erosion by increasingly energetic bottom-water currents. Phase D, <30.2 Ma: establishment of stable, open-ocean, warm-temperate, oligotrophic settings characterized by siliceous-carbonate ooze deposition. Our combined evidence indicates that this early Oligocene Tasmanian Gateway deepening initially produced an eastward flow of relatively warm surface waters from the Australo-Antarctic Gulf into the southwestern Pacific Ocean. This "proto-Leeuwin" current fundamentally differs from previous regional reconstructions of eastward flowing cool water (e.g., a "proto-ACC") during the early Oligocene and thereby represents an important new constraint for reconstructing regional- to global-scale dynamics for this major global change event.

Geochemical composition of snow samples from Antarctica, Greenland and northeast Canada

In this paper, we present new detailed data on the trace metal content of more than 200 shallow polar snow samples collected at various depths in numerous locations mainly in Antarctica and Greenland. The samples were collected in ultraclean plexiglass or teflon tubes from the walls of hand dug pits, using stringent contamination free techniques controlled by severe blank tests. They were then analysed for Na, Mg, K, Ca, Fe, Al, Mn, Pb, Cd, Cu, Zn and Ag in clean room conditions by flameless atomic absorption, after a preconcentration step (by non boiling evaporation in teflon bulbs) which includes dissolving any solid particles by concentrated nitric and hydrofluoric acids. The overall precision on the measured concentrations is of the order of 10 % for all the metals except Pb (20 %) and Cd (35 %), using 95 % confidence limits. The data obtained are compared with those published previously in the literature. Part of these previous data are shown to be erroneously too high, probably because of con-tamination problems both during field collection and analysis.

(Table 2) Petrophysical, petrological, and geochemical characteristics of ODP Hole 163-990A sediments

Ocean Drilling Program Hole 990A penetrated 131 m of subaerially emplaced Paleocene flood basalts on the Southeast Greenland margin with a recovery of 74%. Shipboard P-wave velocity (Vp), density, and magnetic susceptibility were measured with 2- to 15-cm intervals on the core. Individual flow units were divided into four zones based on the observed petrophysical characteristics. From the top, these are Zone I (<7 m thick with a Vp of ~2.5 km/s), Zone II (3-5 m thick with a strongly increasing Vp from 2.5 to 5.5 km/s), Zone III (up to 20 m thick with a Vp of ~5.5-6.0 km/s), and Zone IV (<2 m thick with a strongly decreasing Vp from 6.0 to 2.5 km/s). Eighteen samples were selected from three of the fourteen penetrated basalt units for geochemical, petrological, and petrophysical studies focusing on the altered, low-velocity upper lava Zones I and II. Zone I is strongly altered to >50% clay minerals (smectite) and iron hydroxides, and the petrophysical properties are primarily determined by the clay properties. Zone II is intermediately altered with 5%-20% clay minerals, where the petrophysical properties are a function of both the degree of alteration and porosity variations. Shipboard and shore-based measurements of the same samples show that storage permanently lowers the elastic moduli of basalt from Zones I to III. This is related to the presence of even small quantities of swelling clays. The data show that alteration processes are important in determining the overall seismic properties of flood basalt constructions. The degree and depth of alteration is dependent on the primary lava flow emplacement structures and environment. Thus, the interplay of primary emplacement and secondary alteration structures determine the elastic properties of basalt piles. Rock property theories for sand-clay systems are further used to model the physical property variations in these altered crystalline rocks.

(Table 1) Organic and inorganic geochemical analysis of Late Jurassic to Early Cretaceous black shale sediments from the Norwegian-Greenland Seaway

The Late Jurassic to Early Cretaceous (Volgian-Ryazanian) was a period of a second-order sea-level low stand, and it provided excellent conditions for the formation of shallow marine black shales in the Norwegian-Greenland Seaway (NGS). IKU Petroleum Research drilling cores taken offshore along the Norwegian shelf were investigated with geochemical and microscopic approaches to (1) determine the composition of the organic matter, (2) characterize the depositional environments, and (3) discuss the mechanisms which may have controlled production, accumulation, and preservation of the organic matter. The black shale sequences show a wide range of organic carbon contents (0.5-7.0 wt %) and consist of thermally immature organic matter of type II to II/III kerogen. Rock-Eval pyrolysis revealed fair to very good petroleum source rock potential, suggesting a deposition in restricted shallow marine basins. Well-developed lamination and the formation of autochthonous pyrite framboids further indicate suboxic to anoxic bottom water conditions. In combination with very low sedimentation rates it seems likely that preservation was the principal control on organic matter accumulation. However, a decrease of organic carbon preservation and an increase of refractory organic matter from the Volgian to the Hauterivian are superimposed on short-term variations (probably reflecting Milankovitch cycles). Various parameters indicate that black shale formation in the NGS was gradually terminated by increased oxidative conditions in the course of a sea-level rise.

Bulk geochemical and Rock-Eval data of sediment core IKU-7430/10-U-01 (Table 1)

The late Volgian (early "Boreal" Berriasian) sapropels of the Hekkingen Formation of the central Barents Sea show total organic carbon (TOC) contents from 3 to 36 wt%. The relationship between TOC content and sedimentation rate (SR), and the high Mo/Al ratios indicate deposition under oxygen-free bottom-water conditions, and suggest that preservation under anoxic conditions has largely contributed to the high accumulation of organic carbon. Hydrogen index values obtained from Rock-Eval pyrolysis are exceptionally high, and the organic matter is characterized by well-preserved type II kerogen. However, the occurrence of spores, freshwater algae, coal fragments, and charred land-plant remains strongly suggests proximity to land. Short-term oscillations, probably reflecting Milankovitch-type cyclicity, are superimposed on the long-term trend of constantly changing depositional conditions during most of the late Volgian. Progressively smaller amounts of terrestrial organic matter and larger amounts of marine organic matter upwards in the core section may have been caused by a continuous sea-level rise.

Geochemical composition of minerals obtained from ODP Sites 180-1109, 180-1117 and 180-1118

During the last 8 m.y. the Papuan Peninsula region of Papua New Guinea has been affected by extension which opened the Woodlark Basin. The present-day spreading tip is located at the foot of the Moresby Seamount, a crustal block whose northern flank is an active low-angle normal fault related to this extension. During Ocean Drilling Program Leg 180 (7 June-11 August 1998), 11 sites (1108-1118) were drilled along a north-south-trending transect across the Woodlark Basin just ahead of the spreading tip. Four of these sites (1118, 1109, 1114, and 1117) reached the crystalline basement, which is composed of diabase and gabbro. Sites 1118 and 1109, located on the Woodlark Rise, belong to the hanging wall block, and Sites 1114 and 1117, located on the crest of the Moresby Seamount, belong to the footwall block and the fault zone itself. Most of the basalt, diabase, and gabbro that were recovered show a well-preserved magmatic texture. The diabase, which is the most abundant rock type, has a coarse-grained ophitic texture composed of poikilitic clinopyroxene including radiating, locally skeletal plagioclase laths with interstitial iron oxide grains. Secondary mineralogy consists of chlorite, zeolite, calcite, albite, and quartz. The gabbro shows a medium-grained granular texture. The magmatic mineralogy consists of euhedral laths of plagioclase and anhedral interstitial clinopyroxene. Secondary mineralogy consists of a magnesio to actinolitic hornblende, chlorite, clinozoisite, zeolite, quartz, and calcite. The retrograde metamorphic evolution of both gabbro and diabase occurred under low amphibolite to subgreenschist facies conditions associated mainly with brittle deformation and the development of a local low-temperature shear zone. This shows no evidence for high thermal gradient in the crust during the continental rifting.