North Atlantic IODP Site 303-U1308 Middle Pleistocene Heinrich Events record

Heinrich events are well documented for the last glaciation, but little is known about their occurrence in older glacial periods of the Pleistocene. Here we report scanning XRF and bulk carbonate d18O results from Integrated Ocean Drilling Program Site U1308 (reoccupation of Deep Sea Drilling Project Site 609) that are used to develop proxy records of ice-rafted detritus (IRD) for the last ~1.4 Ma. Ca/Sr is used as an indicator of IRD layers that are rich in detrital carbonate (i.e., Heinrich layers), whereas Si/Sr reflects layers that are poor in biogenic carbonate and relatively rich in detrital silicate minerals. A pronounced change occurred in the composition and frequency of IRD at ~640 ka during marine isotope stage (MIS) 16, coinciding with the end of the middle Pleistocene transition. At this time, "Hudson Strait" Heinrich layers suddenly appeared in the sedimentary record of Site U1308, and the dominant period of the Si/Sr proxy shifted from 41 ka prior to 640 ka to 100 ka afterward. The onset of Heinrich layers during MIS 16 represents either the initiation of surging of the Laurentide Ice Sheet (LIS) off Hudson Strait or the first time icebergs produced by this process survived the transport to Site U1308. We speculate that ice volume (i.e., thickness) and duration surpassed a critical threshold during MIS 16 and activated the dynamical processes responsible for LIS instability in the region of Hudson Strait. We also observe a strong coupling between IRD proxies and benthic d13C variation at Site U1308 throughout the Pleistocene, supporting a link between iceberg discharge and weakening of thermohaline circulation in the North Atlantic.

Sedimentology on two core from the Bransfield Strait area

The raw material for these investigations are samples from marine (sub)surface sediments around the northern part of the Antarctic Peninsula. They had been sampled in the years 1981 to 1986 during several expeditions of the research vessels Meteor, Polarstern and Walther Herwig. 83 box core, gravity core and dredge samples from the area of the Bransfield Strait, the Powell Basin and the northern Weddell Sea have been examined for their grain-size distribution, their mineralogical and petrographical composition. Silt prevails and its clay proportions exceed 25% wt. in water depths greater than 2000 m. The granulometrical results reveal some typical sedimentation processes within the area of investigation. While turbiditic processes together with sediment input from melting icebergs control the sedimentation in the Weddell Sea, the South Orkney Island Plateau and the Powell Basin, the fine grained material from Bransfield Strait mainly relies on marine currents in the shelf area. In addition, the direct sediment input of coarse shelf sediments from the Bransfield Strait into the Powell Basin through submarine canyons could be proven. Variations in the grain-size composition with sediment depth are smalI. The mineral composition of the clay and fine silt fractions is quite uniform in all samples. There are (in decreasing order): illite, montmorillonite, chlorite, smectite, mixed-Iayers, as well as detrital quartz and feldspars. A petrographically based sediment stratigraphy can be established in using the considerable changes in the chlorite- and Ca-plagioclase portions in samples from Core 224. For this sedimentation area a mean sedimentation rate of 7 cm/1000 a is assumed. Remarkable changes in the portions of amorphous silica components - diatom skeletons and volcanic glass shards - appear all over the area of investigation. They contribute between 4-83 % to the clay and fine silt fraction. Several provinces according to the heavy mineral assemblages in the fine sand fraction can be distinguished: (i) a province remarkably influenced by minerals of volcanic origin south and north of the South Shetland Islands; (ii) a small strip with sediment dominated by plutonic material along the western coast of the Antarctic Peninsula and (iii) a sediment controlled by metamorphic minerals and rock fragments in the area of the Weddell Sea and Elephant Island. While taking the whole grain-size spectrum into account a more comprehensive interpretation can be given: the accessoric but distinct appearance of tourmaline, rutile and zircon in the heavy mineral assembly along the northwestern coast of the Antarctic Peninsula is in agreement with the occurrence of acid volcanic rock pieces in the coarse fraction of the ice load detritus in this region. In the vicinity of the South Shetland Islands chlorite appears in remarkable portions in the clay fraction in combination with leucoxene, sphene and olivine, and pumice as well as pyroclastic rocks in the medium and coarse grain fractions, respectively. Amphiboles and amphibole-schists are dominant on the South Orkney Island Plateau. In the sediments of the northwestern Weddell Sea the heavy mineral phases of red spinel, garnet, kyanite and sillimanite in connection with medium to highgrade metamorphic rocks especially granulitic gneisses, are more abundant. A good conformity between the ice rafted rock sampIes and the rocks in the island outcrops could be proven, especially in the vicinity of offshore islands nearby. On the continent enrichments of rock societies and groups appear in spacious outlines: acid effusive rocks in the west of the ice divide on the Antarctic Peninsula, clastic sedimentites at the tip of the Antarctic Peninsula and granoblastic gneisses in central and eastern Antarctica. Coarse grain detritus with more than 1 cm of diameter must have been rafted by icebergs. These rock fragments are classified as rock types, groups and societies. The spacial distribution of their statistically determined weight relations evidently shows the paths of the iceberg drift and in nexus with already known iceberg routes also point to the possible areas of provenance, provided that the density of sample locations and the number of rock pieces are sufficient.

Uranium contents and isotope ratios of uranium and strontium in sediments, leachates and pore fluids from ODP Hole 162-984A

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by a-recoil injection of 234Th. The fraction of 238U decays that result in a-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 0.0000004 to 0.000002 1/yr. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 1000 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ~ 0.1 1/age for ages spanning 1000 to 500,000,000 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.

Sedimentation in the vicinity of Leg 92 Drill Sites: Studies of site survey cores

Surveys of the areas surrounding the sites drilled on the Leg 92 19°S transect showed that sedimentation at all except the oldest site is dominated by calcium carbonate deposition. The sediments in the area of the oldest site, west of the Austral Fracture Zone, are being deposited beneath the calcium carbonate compensation depth and are dominated by terrigenous and metal-rich hydrogenous and hydrothermal sediments. The noncarbonate sediments in all of the areas east of the Austral Fracture Zone are dominated by hydrothermal sediment similar in composition to that presently being deposited at the East Pacific Rise. Although no biogenic microfossils were present in smear slides of the sediment, geochemical partitioning suggests that a remnant signal of siliceous biogenic deposition may be preserved, especially in gravity core (GC) 8, which was collected from a high heat flow zone near Site 600. The siliceous sediment may also result from the deposition of amorphous hydrothermal silica from the higher concentrations of pore water SiO2 characteristic of the upwelling waters. Sedimentation on the broad plateaus that characterize each area is quite uniform and suggests that sites on these plateaus will be broadly representative of pelagic sedimentation in the area.

Mineralogy of ODP Site 105-645

Cores from the upper 70 meters below seafloor (mbsf) (upper Pleistocene) at Ocean Drilling Program (ODP) Site 645 in Baffin Bay show dramatic meter-scale changes in color and mineralogy. Below this interval, mineralogical changes are more gradual to the top of the Miocene at about 550 mbsf. The Pliocene-Pleistocene section can be divided into five facies: Facies 1 - massive, poorly sorted, gravel-bearing muds; Facies 2 - gray silty clays and silty muds; Facies 3 - laminated detricarbonate silty muds; Facies 4 - silty sand and sandy silt; and Facies 5 - poorly sorted muddy sands and silty muds. Facies 4 and 5 are restricted to the Pliocene section below depths of about 275 mbsf. The mineralogical/color cycles in the upper 70 mbsf are the result of alternations between Facies 2 and three lithotypes of Facies 1: lithotype A - tan-colored, carbonate-rich, gravel-bearing mud; lithotype B - weak, red-colored, gravel-bearing mud rich in sedimentary rock fragments; and lithotype C - gray, gravel-bearing mud. A fourth lithotype, D, is restricted to depths of 168-275 mbsf and is dark gray, carbonate-poor, gravel-bearing mud. We believe that all lithotypes of Facies 1 and the sand and gravel fractions of Facies 2 and 3 were deposited by ice rafting. Depositional processes for Facies 4 and 5 probably include ice rafting and bottom- and turbidity-current transport. Data from petrographic analyses of light and heavy sand-sized grains and X-ray analyses of silt- and clay-size fractions suggest that tan-colored sediments (lithotype A of Facies 1; Facies 3) were derived mainly from Paleozoic carbonates of Ellesmere, Devon, and northern Baffin islands. Weak red sediments (lithotype B) contain significant red sedimentary clasts, reworked quartzarenite grains and clasts, and rounded colorless garnets, all derived from Proterozoic sequences of the Borden and Thule basins, and from minor Mesozoic red beds. Other sediments in the upper 335 mbsf at Site 645 contain detritus from a heterogeneous mixture of sources, including Precambrian shield terranes around Baffin Bay. Sediments from 335 to 550 mbsf (Facies 5) are rich in friable sedimentary clasts and detrital micas and contain glauconite and, in a few samples, reworked diatoms. These components suggest derivation from poorly consolidated Mesozoic-Tertiary sediments in coastal outcrops and beneath the modern shelves of northeastern Baffin Island and western Greenland. For the upper Pleistocene section (about 0-100 mbsf), marked mineralogical cyclicity is attributed to fluctuating glacial margins, calving rates, and iceberg melting rates, particularly around the northern end of Baffin Bay. Tan-colored, carbonate-rich units were derived at times of maximum advance of glaciers on Ellesmere and Devon islands, during relatively warm intervals induced by incursion of warm Atlantic surface water into the bay. At the beginning of these warmer episodes, most icebergs were contributed by glaciers near sea level around the Arctic channels, which resulted in deposition of weak red, ice-rafted units rich in Proterozoic sedimentary clasts.

Mineralogical-sedimentological and chemical investigation of sediments from Cross Bank off Florida

The sediments of a core of.1.55 m length taken on the windward side of the Cross Bank, Florida Bay, are clearly subdivided into two portions, as shown by grain size analysis: silt-sized particles predominate in the relatively homogeneous lower two thirds of the core. This is succeeded abruptly by a thin layer of sand, containing fragments of Halimeda. They indicate a catastrophic event in the Florida Bay region, because Halimeda does not grow within Florida Bay. Above this layer, the amount of sand decreases at first and then continuously increases right to the present sediment-water-interface. The median and skewness increase simultaneously with the increase in the sand and granule portion. We assume that the changing grain size distribution was determined chiefly by the density of the marine flora: during the deposition of the lower two thirds of the core a dense grass cover acted as a sediment catcher for the fine-grained detritus washed out of the shallow basins of the Florida Bay, and simultaneously prohibited renewed reworking. Similar processes go on today on the surface of most mud banks of Florida Bay. The catastrophic event indicated by the sand layer probably changed the morphology of the bank to such an extent that the sampling point was shifted more to the windward side of the bank. This side is characterized by less dense plant growth. Therefore, less detritus could be caught and the material deposited could be reworked. The pronounced increase in skewness in the upper third of the core certainly indicates a strong washing out of the smaller-sized particles. The sediments are predominantly made up of carbonates, averagely 88.14 percent. The average CaCO3-content is 83.87 percent and the average MgCO3-content amounts to 4.27 percent. The chief carbonate mineral is aragonite making up 60.1 percent of the carbonate portion in the average, followed by high-magnesian calcite (33.8 percent) and calcite (6.1 percent). With increasing grain size the aragonite clearly increases at the cost of high-magnesian calcite in the upper third of the core. Chemically, this is shown by an increase of the CaCO3 : MgCO3-ratio. This increase is mainly caused by the more common occurrence of aragonitic fragments of mollusks in the coarse grain fractions. The bulk of the carbonates is made up of mollusks, foraminifera, ostracods, and - to a much lesser extent - of corals, worm-tubes, coccolithophorids, and calcareous algae, as shown by microscopic investigations. The total amount of the carbonate in the sediments is biogenic detritus with the possible exception of a very small amount of aragonite needles in the clay and fine silt fraction. The individual carbonate components of the gravel and sand fraction can be relatively easy identified as members of a particular animal or plant group. This becomes very difficult in the silt and clay fraction. Brownish aggregates are very common in the coarse and medium silt fraction. It was not always possible to clarify their origin (biogenic detritus, faecal pellets or carbonate particles cemented by carbonates or organic slime, etc.). Organic matter (plant fragments, rootlets), quartz, opal (siliceous sponge needles), and feldspar also occur in the sediments, besides carbonates. The lowermost part of the core has an age of 1365 +/- 90 years, as shown by 14C analysis.

Geochemistry of recent sediments of the East African continental margin, Arabian Sea

Chemical analyses have been carried out on 40 samples from the sediment surface and 210 samples from cores that were taken from the edge of the African continental block at the Arabian Sea (coasts of Somalia and Kenya, from Cape Guardafui to Mombasa) on the occasion of the Indian Ocean Expedition of the German research vessel "Meteor" during the years 1964/65. The carbonate content shows its maximum on the northern part of the continental shelf of Africa, where fossil reef debris furnish the detritic portion of carbonate. In the southern part of the continental shelf of Africa the portion of carbonate is low, as it is heavily diluted by the non-carbonatic detritus. It is also in the deep-sea that a lower carbonate content is encountered below the calcite compensation depth. Trace elements in the carbonates: On the shelf and in its vicinity Sr and Mg are enriched. The enrichment has been brought about by the portion of reef debris, as this latter contains aragonite (enrichment of Sr) as well as high-magnesium calcite. The greatest part of the slope contains carbonates that are poor in trace elements and mainly made up of foraminifera (and of coccoliths). Below the carbonate compensation depth another enrichment of Mg takes place in the carbonates, which is probably due to a selective dissolution of calcite in comparison to dolomite. The iron and manganese contents of the carbonates are high (iron higher in coast proximity, manganese higher in the depth), but not genuine, as they come about in the course of the extraction of the carbonates as a result of the dissolution of authigenic Mn-Fe-minerals. Non-carbonatic portion of the sediments: In coast proximity an enrichment of quartz comes about. Within the quartz-rich zone it is the elements V, Cr, Fe, Ti, and B that have been enriched in the non-carbonatic components. This enrichment must be attributed to an elevated content of heavy minerals. In the case of Ti and Fe the preliminary enrichment brought about by processes of lateritisation on the continent plays a certain role. Toward the deep-sea an enrichment of the elements Mn Ni, Cu, and Zn takes place; these enrichments must be explained by authigenic Mn-Fe-minerals. Within the Mn-rich zone a belt running parallel to the coast stands out that shows an increased Mn-enrichment. However, this increase in enrichment does not apply to the elements Ni, Cu, and Zn. It is probable that this latter increased enrichment comes about as a result of the migration of manganese to the sediment surface. (Within the sediments there prevail reductive conditions, in the presence of which Mn is capable of migration, whereas at the sediment surface its precipitation comes about under oxidizing conditions). The quantity of organic matter mainly is dependent on grain size and on the rate of sedimentation. On the shelf an impoverishment of organic matter is to be encountered, as the sediments are coarse-grained. In the depth the impoverishment must be explained on the strength of a small rate of sedimentation. Between those two ranges organic substance is enriched. P and N show an enrichment in comparison to Corg with this applying all the more the smaller the absolute quantity of Corg is. In this particular case one has to do with an enrichment coming about during the diagenetic processes of organic matter. A comparison with the sediments from the Indian and Pakistani continental border in Arabian Sea shows as follows: on the African continental border the coarse detrital material has been transported farther out to deep-sea, which has something to do with the greater inclination of the surface of sedimentation. Carbonate is found in greater abundance on the African side. Its chemical composition is influenced by reef-debris which is missing by Indian-Pakistani side. The content of organic matter is lower on the African side. Contrary to that, the enrichments of N and P compared to organic matter are of an equal order of magnitude on both sides of the Arabian Sea.

Description and geochemical composition of tephra layers from ODP Hole 186-1150A and Site 186-1151

The sediments collected at Sites 1150 and 1151 during Leg 186 included many tephra layers and volcaniclastic detritus. In order to identify these tephras, the major oxide compositions of individual glass shards were determined by electron probe microanalyzer. The uppermost four tephras in sediments from Hole 1150A are correlated with the Towada-Hachinohe tephra (To-H; Tohoku district), Shikotsu Daiichi (1st) tephra (Spfa-1; Hokkaido district), Narugo-Yanagisawa tephra (Nr-Y; Tohoku district), and Aso-4 tephra (Kyushu district), respectively. The uppermost tephra in Hole 1151C is correlated with To-H tephra. To-H, Spfa-1, and Aso-4 tephras are also present in piston core KH94-3, LM-8, collected between Sites 1150 and 1151. Eruptive ages of To-H and Spfa-1 estimated from the oxygen isotopic Stages of core KH94-3, LM-8 are between 14.9-15.3 and 39.5-40.1 ka.

Mineralogy of silts from the Bengal Fan

Early Miocene to Quaternary sediments drilled from the Bengal Fan are divided into six zones by modal proportions of heavy minerals. The sediments were mostly derived from the Himalayas. Detritus from the Indian subcontinent is found sporadically in clay-rich sediments that were deposited during periods of slow sedimentation, when the deep-sea channel migrated away from the drilled sites. The oldest sediments, ranging from 17 to about 15 Ma, were derived mostly from the Precambrian and Paleozoic sedimentary rocks of the lower Himalayas. At about 15 Ma, metamorphic terrains were eroded in the source area. Further large-scale unroofing of metamorphic rocks occurred around 11 Ma. After 10 Ma, the major constituents in the drainage basin or the drainage pattern changed a few times. Between 3.5 and 0.5 Ma, a large peridotite body was unroofed by uplift and successive erosion of the central Himalayas. At this time, the single large river that had supplied detritus to the early Bengal Fan was divided into the Indus and Ganges rivers.

Fossil plant remains in DSDP Leg 80 holes

The lower part of the syn-rift Barremian-?Hauterivian section at Site 549 contains a large amount of acid-resistant land-derived organic matter that, as elsewhere in the Cretaceous sediments of the IPOD Leg 80 sites, is thermally immature. This plant debris was derived from a vegetation made up of many species of pteridophytes and gymnosperms. The palynofacies indicate that the sediments were deposited in shallow marginal and nonmarine environments and that the climate was probably warm temperate and fairly moist at the time. Source potential for gas is suggested at some horizons. Most of the younger Lower Cretaceous sediments at this and the other sites were deposited in more open marine conditions. Although they generally contain less organic matter, land plant remains continue to comprise a major part of the palynofacies. The Upper Cretaceous sediments were mainly deposited in well oxygenated conditions and are organically lean. However, stratigraphically restricted dark-colored shales at Sites 549 to 551 contain relatively large quantities of amorphous detritus of at least partly marine origin. These characteristics are suggestive of deposition during periods of restricted circulation and also of source potential for oil and gas if maturation levels had been higher.

Zooplankton distribution and migration in low-oxygen modewater eddies

The eastern tropical North Atlantic (ETNA) features a mesopelagic oxygen minimum zone (OMZ) at approximately 300-600 m depth. Here, oxygen concentrations rarely fall below 40 µmol O2 kg-1, but are expected to decline under future projections of global warming. The recent discovery of mesoscale eddies that harbour a shallow suboxic (<5 µmol O2 kg-1) OMZ just below the mixed layer could serve to identify zooplankton groups that may be negatively or positively affected by on-going ocean deoxygenation. In spring 2014, a detailed survey of a suboxic anticyclonic modewater eddy (ACME) was carried out near the Cape Verde Ocean Observatory (CVOO), combining acoustic and optical profiling methods with stratified multinet hauls and hydrography. The multinet data revealed that the eddy was characterized by an approximately 1.5-fold increase in total area-integrated zooplankton abundance. At nighttime, when a large proportion of acoustic scatterers is ascending into the upper 150 m, a drastic reduction in mean volume backscattering (Sv, shipboard ADCP, 75kHz) within the shallow OMZ of the eddy was evident compared to the nighttime distribution outside the eddy. Acoustic scatterers were avoiding the depth range between about 85 to 120 m, where oxygen concentrations were lower than approximately 20 µmol O2 kg-1, indicating habitat compression to the oxygenated surface layer. This observation is confirmed by time-series observations of a moored ADCP (upward looking, 300kHz) during an ACME transit at the CVOO mooring in 2010. Nevertheless, part of the diurnal vertical migration (DVM) from the surface layer to the mesopelagic continued through the shallow OMZ. Based upon vertically stratified multinet hauls, Underwater Vision Profiler (UVP5) and ADCP data, four strategies have been identified to be followed by zooplankton in response to the eddy OMZ: i) shallow OMZ avoidance and compression at the surface (e.g. most calanoid copepods, euphausiids), ii) migration to the shallow OMZ core during daytime, but paying O2 debt at the surface at nighttime (e.g. siphonophores, Oncaea spp., eucalanoid copepods), iii) residing in the shallow OMZ day and night (e.g. ostracods, polychaetes), and iv) DVM through the shallow OMZ from deeper oxygenated depths to the surface and back. For strategy i), ii) and iv), compression of the habitable volume in the surface may increase prey-predator encounter rates, rendering zooplankton and micronekton more vulnerable to predation and potentially making the eddy surface a foraging hotspot for higher trophic levels. With respect to long-term effects of ocean deoxygenation, we expect avoidance of the mesopelagic OMZ to set in if oxygen levels decline below approximately 20 µmol O2 kg-1. This may result in a positive feedback on the OMZ oxygen consumption rates, since zooplankton and micronekton respiration within the OMZ as well as active flux of dissolved and particulate organic matter into the OMZ will decline.

(Supplementary Table 1) Proportions of methane (C1) to ethane (C2) and the stable isotope composition of methane (d13CCH4) of gas and oil collected by gas bubble sampler during cruise M 114 in the southern Gulf of Mexico

Hydrocarbon seepage is a widespread process at the continental margins of the Gulf of Mexico. We used a multidisciplinary approach, including multibeam mapping and visual seafloor observations with different underwater vehicles to study the extent and character of complex hydrocarbon seepage in the Bay of Campeche, southern Gulf of Mexico. Our observations showed that seafloor asphalt deposits previously only known from the Chapopote Knoll also occur at numerous other knolls and ridges in water depths from 1230 to 3150 m. In particular the deeper sites (Chapopopte and Mictlan knolls) were characterized by asphalt deposits accompanied by extrusion of liquid oil in form of whips or sheets, and in some places (Tsanyao Yang, Mictlan, and Chapopote knolls) by gas emission and the presence of gas hydrates in addition. Molecular and stable carbon isotopic compositions of gaseous hydrocarbons suggest their primarily thermogenic origin. Relatively fresh asphalt structures were settled by chemosynthetic communities including bacterial mats and vestimentiferan tube worms, whereas older flows appeared largely inert and devoid of corals and anemones at the deep sites. The gas hydrates at Tsanyao Yang and Mictlan Knolls were covered by a 5-to-10 cm-thick reaction zone composed of authigenic carbonates, detritus, and microbial mats, and were densely colonized by 1-2 m-long tube worms, bivalves, snails, and shrimps. This study increased knowledge on the occurrences and dimensions of asphalt fields and associated gas hydrates at the Campeche Knolls. The extent of all discovered seepage structure areas indicates that emission of complex hydrocarbons is a widespread, thus important feature of the southern Gulf of Mexico.