Organic geochemistry of DSDP Site 467

Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17*(H), 18*(H), 21beta(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.

Mesozooplankton biomass data from Disko Bay, West Greenland, 2008

The study site was located in the Disko Bay off Qeqertarsuaq, western Greenland. Due to land-connected sea ice coverage during winter, 2 sampling sites were combined. At the first site in winter (21 February to 23 March 2008), sampling was conducted through a hole in the ice at ca. 65 to 160 m depth approximately 0.5 nautical mile (n mile) south of Qeqertarsuaq (69° 14' N, 53° 29' W). In spring and summer (9 April to 18 July), sampling was done at a monitoring station 1 n mile south from Qeqertarsuaq (69° 14' N, 53° 23' W) at 300 m depth. Sampling was carried out between 10:00 and 17:00 h. During sampling from the ice, mesozooplankton was collected using a modified WP-2 net (45 µm) equipped with a closing mechanism (Hydrobios). Samples were collected in 3 depth strata (0-50, 50-100, and 100-150 m). During ship-based sampling, mesozooplankton was collected with a multinet (50 µm) equipped with a flow meter (Multinet, Hydrobios type midi), and 2 additional depth strata (150-200m and 200-250 m) were included. In addition to the seasonal study one diurnal investigation with sampling every 6 h was conducted from 29 April at 12:00 h to 30 April 30 at 12:00 h. Samples were immediately preserved in buffered formalin (5% final concentration) for later analyses. Biomass values of the different copepod species were calculated based on measurements of prosome length, and length/weight relationships. Two regressions for Calanus spp. were established for biomass calculations: one applicable prior to and during the phytoplankton bloom until 4 May, and another from 9 May onwards.

Mesozooplankton size data from Disko Bay, West Greenland, 2008

The study site was located in the Disko Bay off Qeqertarsuaq, western Greenland. Due to land-connected sea ice coverage during winter, 2 sampling sites were combined. At the first site in winter (21 February to 23 March 2008), sampling was conducted through a hole in the ice at ca. 65 to 160 m depth approximately 0.5 nautical mile (n mile) south of Qeqertarsuaq (69° 14' N, 53° 29' W). In spring and summer (9 April to 18 July), sampling was done at a monitoring station 1 n mile south from Qeqertarsuaq (69° 14' N, 53° 23' W) at 300 m depth. Sampling was carried out between 10:00 and 17:00 h. During sampling from the ice, mesozooplankton was collected using a modified WP-2 net (45 µm) equipped with a closing mechanism (Hydrobios). Samples were collected in 3 depth strata (0-50, 50-100, and 100-150 m). During ship-based sampling, mesozooplankton was collected with a multinet (50 µm) equipped with a flow meter (Multinet, Hydrobios type midi), and 2 additional depth strata (150-200m and 200-250 m) were included. In addition to the seasonal study one diurnal investigation with sampling every 6 h was conducted from 29 April at 12:00 h to 30 April 30 at 12:00 h. Samples were immediately preserved in buffered formalin (5% final concentration) for later analyses. Biomass values of the different copepod species were calculated based on measurements of prosome length, and length/weight relationships. Two regressions for Calanus spp. were established for biomass calculations: one applicable prior to and during the phytoplankton bloom until 4 May, and another from 9 May onwards.

Distribution of trace fossils and ichnofabric indices in ODP holes of Leg 119

Trace fossils and ichnofabric were examined from cores of Late Cretaceous to Quaternary age recovered from the Kerguelen Plateau, Indian Ocean. Nearly all of the strata are completely bioturbated, with ichnofabric index 6 most commonly recorded. Preserved discrete trace fossils include Chondrites, Planolites, Zoophycos, and Thalassinoides. A continuous Cretaceous/Tertiary boundary section preserved at ODP Site 738 occurs within a 15-cm-thick interval of laminated sediments. The lack of bioturbation indicates the disappearance of bioturbating organisms from the seafloor, possibly as a result of the same factors that caused the mass extinction or changes in other environmental conditions - most probably, bottom-water oxygen concentrations.

Petrology and carbon and oxygen stable isotopic composition of macrofossils and sediments from the Blake-Bahama Formation, DSDP Hole 93-603B

Strata that record the evolutionary history of the North American continental margin in a region that serves as the basin margin interface between allochthonous sedimentation from the continent and pelagic sedimentation from the oceanic realm were recovered at Deep Sea Drilling Project Site 603, on the lower continental rise. The lowermost unit recovered at this site is composed of upper Berriasian-Aptian interbedded laminated limestone and bioturbated limestone with sandstone to claystone turbidites. This unit can be correlated with the Blake-Bahama Formation in the western North Atlantic. Studies of the laminated and bioturbated limestones were used to determine the depositional environment. Geochemical and petrographic studies suggest that the laminated limestones were deposited from the suspended particulate loads of the nepheloid layer associated with weak bottom-current activity as well as moderate to poorly oxygenated bottom-water conditions. Fragments of macrofossils are also found in the Blake-Bahama Formation drilled at Site 603. Twelve specimens and their host sediment were analyzed for their carbon and oxygen isotopic composition. The macrofossil samples chosen for analysis consist of nine samples of Inoceramus, two ammonite aptychi, and one belemnite sample. Depletion in 18O is observed in recrystallized specimens. The ammonite aptychi have been diagenetically altered and/or exhibit evidence of isotopic fractionation by the organism. Oxygen isotope paleotemperatures obtained from five well-preserved specimens - four of Inoceramus and one of a belemnite - suggest that bottom-water temperatures in the North Atlantic Basin during the Early Cretaceous were very warm, at least 11°C.

Physical properties of four profiles from the Triassic in Germany

The Norian Steinmergel-Keuper (SMK) represents a low-latitude cyclically-bedded playa system of the Mid-German Basin. We investigated a drilling site (core Morsleben) and sections from marginal positions. Dolomite/red mudstone beds form rhythmic alternations that were associated with varying monsoon activity. Hence, low K/Al ratios of dolomite beds suggest increased chemical weathering of the crystalline hinterland and therefore increased monsoonal rainfall. High K/Al ratios in red mudstone beds reflect increased physical weathering of the hinterlands during dryer periods. Dolomite layers reflect the lake stage (maximum monsoon) while red mudstones indicate the dry phase (minimum monsoon) of the playa cycle. We distinguished five major types of cyclic facies alternations, representing specific facies zones in the playa system. We have implemented spectrophotometry as a tool for high-resolution cyclostratigraphy. The dense sampling increment (up to 1 cm) allows for the recognition of all orbital frequencies. Sediment colour profiles reveal striking hierarchical cycles from semi-precession (SP, 99 kyr) over precession (P, 19.8 kyr) and obliquity (O, 36 kyr) to eccentricity (E1-2 109 kyr; E3, 413 kyr). A significant about 2 Myr-signal is attributed to the longer-term eccentricity E4. One monsoonal (precession) cycle includes two carbonate precipitation events. We propose that stratified mudstone and red mudstone are associated with maximum and minimum monsoon during the transition of the solstices in perihelion and aphelion, respectively. The two carbonate precipitation events were most likely created when equinoxes were in perihelion and aphelion, respectively. A sedimentary semi-precession response cycle is a novel finding for the Norian strata. The obliquity signal is attributed to incoming atmospheric moisture from the northeast of the SMK basin. The E4 cycle controls lake-level changes over long times. Apparently, E4 is responsible whether or not a threshold value is crossed. Bundles of 109 kyr and 413 kyr in red mudstones suggest a dry system with reduced monsoonal activity. In contrast, humid periods reveal thick layers of dolomite beds, indicating that during those intervals the monsoonal activity was strong enough to prevent the playa system from drying out completely.

Mineral composition and experimental results from XRD analyses of sediments from ODP Leg 190 sites

X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

Geochemistry of serpentine muds of ODP Leg 125 holes

The <63-µm fractions of serpentinite muds from two seamounts on the Mariana and Izu-Bonin forearcs were analyzed for mineral composition by X-ray diffraction and for chemical composition by X-ray fluorescence. The silt fraction of the muds consists predominantly of chrysotile, brucite, and ample amorphous constituents. Chlorite and smectite are less abundant components. Of special interest is the occurrence of iowaite, a brucite-like, Cl-bearing mineral with a layered structure. Iowaite was not found in the samples from the summit site of one of the seamounts drilled; however, it is scattered throughout the strata, composing the flanks of both seamounts investigated. No systematic change of the iowaite abundance with depth was observed. The distribution of iowaite is confined to the surface of the flanks of the seamount. Based on the distribution on the mineral and its chemical composition, we suggest that the iowaite formed by oxidation of some of the ferrous iron in brucite contained in the serpentine mud as it contacted abyssal seawater during protrusion onto the seafloor. The resulting positive charge imparted to the brucite was compensated by the uptake of seawater chloride. Consequently, the formation of iowaite is restricted to the seafloor where oxygen and chloride are available for these reactions. The availability of oxygen is considered the limiting factor. We conclude that iowaite formation cannot be a major cause for the low chlorinity of pore fluids inside the seamounts.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Diatom biostratigraphy, Argon ages and chronology of ODP Hole 183-1138A

A thick Neogene section was recovered in the upper ~300 m of Ocean Drilling Program Hole 1138A, drilled on the Central Kerguelen Plateau in the Indian sector of the Southern Ocean. Sediment lithologies consist primarily of mixed carbonate and biosiliceous clays and oozes, with several thin (1-3 cm) tephra horizons. The tephras are glass rich, well sorted, and dominantly trachytic to rhyolitic in composition. Volcaniclastic material in these horizons is interpreted to have originated from Heard Island, 180 km northwest of Site 1138, and was likely emplaced through both primary ash fall and turbiditic, submarine flows. A Neogene age-depth model for Hole 1138A is constructed primarily from 36 diatom biostratigraphic datums. Nannofossil and planktonic foraminifer biostratigraphy provides supporting age information. Additionally, four high-precision 40Ar-39Ar ages are derived from ash and tephra horizons, and these radiometric ages are in close agreement with the biostratigraphic ages. The integrated age-depth model reveals a reasonably complete lower Miocene to upper Pleistocene section in Hole 1138A, with the exception of a ~1-m.y. hiatus at the Miocene/Pliocene boundary. Another possible hiatus is also identified at the Oligocene/Miocene boundary. High Neogene sedimentation rates and the presence of both calcareous and siliceous microfossils, combined with datable tephra horizons, establish Site 1138 as a suitable target for future drilling legs with paleoceanographic objectives. This report also proposes two new diatom species, Fragilariopsis heardensis and Azpeitia harwoodii, from Pliocene strata of Hole 1138A.

(Table 1) Comparison of localities where Switzianthus (Anderson & Anderson) has been found with Dejerseya and Heidiphyllum occurrence

Fossil leaves of the Voltziales, an ancestral group of conifers, rank among the most common plant fossils in the Triassic of Gondwana. Even though the foliage taxon Heidiphyllum has been known for more than 150 years, our knowledge of the reproductive organs of these conifers still remains very incomplete. Seed cones assigned to Telemachus have become increasingly well understood in recent decades, but the pollen cones belonging to these Mesozoic conifers are rare. In this contribution we describe the first compression material of a voltzialean pollen cone from Upper Triassic strata of the Transantarctic Mountains. The cone can be assigned to Switzianthus Anderson & Anderson, a genus that was previously assumed to belong to an enigmatic group of pteridosperms from the Triassic Molteno Formation of South Africa. The similarities of cuticle and pollen morphology, together with co-occurrence at all known localities, indicate that Switzianthus most probably represents the pollen organ of the ubiquitous Heidiphyllum/Telemachus plant.

Reconstructed ice-sheet limit in the Kara and Barents Sea area at about 50,000 years ago (Markhida Line)

Glacial landforms in northern Russia, from the Timan Ridge in the west to the east of the Urals, have been mapped by aerial photographs and satellite images supported by field observations. An east-west trending belt of fresh hummock-and-lake glaciokarst landscapes has been traced to the north of 67°N. The southern boundary of these landscapes is called the Markhida Line, which is interpreted as a nearly synchronous limit of the last ice sheet that affected this region. The hummocky landscapes are subdivided into three types according to the stage of postglacial modification: Markhida, Harbei and Halmer. The Halmer landscape on the Uralian piedmont in the east is the freshest, whereas the westernmost Markhida landscape is more eroded. The west- east gradient in morphology is considered to be a result of the time-transgressive melting of stagnant glacier ice and of the underlying permafrost. The pattern of ice-pushed ridges and other directional features reflects a dominant ice flow direction from the Kara Sea shelf. Traces of ice movement from the central Barents Sea are only discernible in the Pechora River left bank area west of 50°E. In the Polar Urals the horseshoe-shaped end moraines at altitudes of up to 560 m a.s.l. reflect ice movement up-valley from the Kara Ice Sheet, indicating the absence of a contemporaneous ice dome in the mountains. The Markhida moraines, superimposed onto the Eemian strata, represent the maximum ice sheet extent in the western part of the Pechora Basin during the Weichselian. The Markhida Line truncates the huge arcs of the Laya-Adzva and Rogovaya ice-pushed ridges protruding to the south. The latter moraines therefore reflect an older ice advance, probably also of Weichselian age. Still farther south, fluvially dissected morainic plateaus without lakes are of pre-Eemian age, because they plunge northwards under marine Eemian sediments. Shorelines of the large ice-dammed Lake Komi, identified between 90 and 110 m a.s.l. in the areas south of the Markhida Line, are radiocarbon dated to be older than 45 ka. The shorelines, incised into the Laya-Adzva moraines, morphologically interfinger with the Markhida moraines, indicating that the last ice advance onto the Russian mainland reached the Markhida Line during the Middle or Early Weichselian, before 45 ka ago.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

(Table 3) Stable isotope record of Cretaceous foraminifera from DSDP Hole 44-392A

Mid-Cretaceous (Barremian-Turonian) plankton preserved in deep-sea marl, organic-rich shale, and pelagic carbonate hold an important record of how the marine biosphere responded to short- and long-term changes in the ocean-climate system. Oceanic anoxic events (OAEs) were short-lived episodes of organic carbon burial that are distinguished by their widespread distribution as discrete beds of black shale and/or pronounced carbon isotopic excursions. OAE1a in the early Aptian (~120.5 Ma) and OAE2 at the Cenomanian/Turonian boundary (~93.5 Ma) were global in their distribution and associated with heightened marine productivity. OAE1b spans the Aptian/Albian boundary (~113-109 Ma) and represents a protracted interval of dysoxia with multiple discrete black shales across parts of Tethys (including Mexico), while OAE1d developed across eastern and western Tethys and in other locales during the latest Albian (~99.5 Ma). Mineralized plankton experienced accelerated rates of speciation and extinction at or near the major Cretaceous OAEs, and strontium isotopic evidence suggests a possible link to times of rapid oceanic plateau formation and/or increased rates of ridge crest volcanism. Elevated levels of trace metals in OAE1a and OAE2 strata suggest that marine productivity may have been facilitated by increased availability of dissolved iron. The association of plankton turnover and carbon isotopic excursions with each of the major OAEs, despite the variable geographic distribution of black shale accumulation, points to widespread changes in the ocean-climate system. Ocean crust production and hydrothermal activity increased in the late Aptian. Faster spreading rates [and/or increased ridge length] drove a long-term (Albian-early Turonian) rise in sea level and CO2-induced global warming. Changes in ocean circulation, water column stratification, and nutrient partitioning lead to a reorganization of plankton community structure and widespread carbonate (chalk) deposition during the Late Cretaceous. We conclude that there were important linkages between submarine volcanism, plankton evolution, and the cycling of carbon through the marine biosphere.

Abundance of mesozooplankton in the north-eastern Black Sea during SESRU02 cruise in September 2008

The SESRU_02_mesozooplankton dataset contains data collected in September 2008 at 15 stations located between 37°E and 39.5°E and between 42.4°N and 44.5°N in the north-eastern Black Sea. Samples were collected with a Juday net. Juday net: Vertical tows of a closing Juday net, with mouth area 0.1 m**2, mesh size 180 µm. Samples were taken from different layers. Towing speed: 1m/s. Samples were preserved by a 4% formaldehyde sea water buffered solution. Sampling volume was estimated by multiplying the mouth area with the wire length. Integrated samples were taken from the lower boundary of the oxic zone to the surface, stratified samples were taken according to CTD-profiles: samples were taken from the following depth strata: 1) the upper mixed layer (UML); 2) the layer of high temperature gradients (from the upper boundary of thermocline to the depth of 8 deg C temperature); 3) cold Intermediate layer (CIL) - the layer with the T< 8 deg C; 4) from the depth of sigma theta = 15.8 (oxycline) to the lower boundary of CIL; 5) from the depth of sigma theta = 16.2 to the depth of sigma theta = 15.8. Samples were analysed for zooplankton species and stage composition and abundance. The entire sample or an aliquot (1/2 to ¼) was analyzed under the binocular microscope. Mesozooplankton species and stages were identified and enumerated; meroplankton were identified and enumerated at higher taxonomic level. Taxonomic identification was done at Shirshov Institute of Oceanology using the relevant taxonomic literature (Rose, 1933, Brodsky, 1950 and Internet resources).