Chemical and isotope composition of carbonate nodules and host bottom sediments from Core DM9-666, Gulf of California

Results of mineralogical and isotopic analyzes of sulfur and carbon in carbonate nodules and host bottom sediments and results of 14C measurement in carbonate nodules are reported. It is proved that the carbonate nodules formed 11-22 thousand years ago in anaerobic diagenesis of bottom sediments rich in organic matter. Isotopic light metabolic carbon dioxide was a source of carbonate for nodules. It formed during microbial degradation of organic matter of bottom sediments.

Documentation, profile descriptions and analytical results of loes profiles from Bavaria, southern Germany

This study investigates the landscape evolution and soil development in the loess area near Regensburg between approximately 6000-2000 yr BP (radiocarbon years), Eastern Bavaria. The focus is on the question how man and climate influenced landscape evolution and what their relative significance was. The theoretical background concerning the factors that controlled prehistoric soil erosion in Middle Europe is summarized with respect to rainfall intensity and distribution, pedogenesis, Pleistocene relief, and prehistoric farming. Colluvial deposits , flood loams, and soils were studied at ten different and representative sites that served as archives of their respective palaeoenvironments. Geomorphological, sedimentological, and pedological methods were applied. According to the findings presented here, there was a high asynchronity of landscape evolution in the investigation area, which was due to prehistoric land-use patterns. Prehistoric land use and settlement caused highly difIerenciated phases of morphodynamic activity and stability in time and space. These are documented at the single catenas ofeach site. In general, Pleistocene relief was substantially lowered. At the same time smaller landforms such as dells and minor asymmetric valleys filled up and strongly transformed. However, there were short phases at many sites, forming short lived linear erosion features ('Runsen'), resulting from exceptional rainfalls. These forms are results of single events without showing regional trends. Generally, the onset of the sedimentation of colluvial deposits took place much earlier (usually 3500 yr BP (radiocarbon) and younger) than the formation of flood loams. Thus, the deposition of flood loams in the Kleine Laaber river valley started mainly as a consequence of iron age farming only at around 2500 yr BP (radiocarbon). A cascade system explains the different ages of colluvial deposits and flood loams: as a result of prehistoric land use, dells and other minor Pleistocene landforms were filled with colluvial sediments. After the filling of these primary sediment traps , eroded material was transported into flood plains, thus forming flood loams. But at the moment we cannot quantify the extent ofprehistoric soil erosion in the investigation area. The three factors that controlled the prehistoric Iandscapc evolution in the Ioess area near Regensburg are as follows: 1. The transformation from a natural to a prehistoric cultural landscape was the most important factor: A landscape with stable relief was changed into a highly morphodynamic one with soil erosion as the dominant process of this change. 2. The sediment traps of the pre-anthropogenic relief determined where the material originated from soil erosion was deposited: either sedimentation took place on the slopes or the filled sediment traps of the slopes rendered flood loam formation possible. Climatic influence of any importance can only be documented as the result of land use in connection with singular and/or statistic events of heavy rainfalls. Without human impact, no significant change in the Holocene landscape would have been possible.

Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.

Age-depth relation, radiocarbon ages and tephra geochemistry of core 5022-2CP from Laguna Potrok Aike, southern Patagonia

The 106 m long composite profile from site 2 of ICDP expedition 5022 (PASADO) at Laguna Potrok Aike documents a distinct change in sedimentation patterns from pelagic sediments at the top to dominating mass movement deposits at its base. The main lithological units correspond to the Holocene, to the Lateglacial and to the last glacial period and can be interpreted as the result of distinct environmental variations. Overflow conditions might have been achieved during the last glacial period, while signs of desiccation are absent in the studied sediment record. Altogether, 58 radiocarbon dates were used to establish a consistent age-depth model by applying the mixed-effect regression procedure which results in a basal age of 51.2 cal. ka BP. Radiocarbon dates show a considerable increase in scatter with depth which is related to the high amount of reworking. Validation of the obtained chronology was achieved with geomagnetic relative paleointensity data and tephra correlation.

Chemical and isotopic compositions and age of carbonates from the Lost City hydrothermal field, Mid-Atlantic Ridge

Two genetically different types of authigenic carbonate mounds are studied: (1) from an active hydrothermal field related to serpentinite protrusions in a zone of intersection of a transform fracture zone with the Mid-Atlantic Ridge, (2) from an active field of methane seepings in the Dnieper canyon of the Black sea. General geochemical conditions, under which authigenic carbonate formation occurs within these two fields, were found. They include: presence of reduced H2S, H2, and CH4 gases at absence of free oxygen; high alkalinity of waters participating in carbonate formation; similarity of textural and structural features of authigenic aragonite, which represents the initial carbonate mineral of the mounds; paragenesis of aragonite with sulfide minerals; close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested. It implies their microbial sulfate reduction over hydrogen from fluid in the subsurface mixing zone of hydrothermal solution and adjacent seawater.

Pollen record and age determination of sediment core Fersina 2

Pollen analysis of samples taken from the core of the water well Fersina 2 (Adige Valley, Prov. Trento, NE Italy) did not reveal any indication of an interglacial or Holocene age of the uppermost 190 m in the sediment sequence deposited in the over-deepened Adige River Valley. The sediment sequence dates entirely from late-glacial times. Four radiocarbon ages of pieces of wood indicate that about 165 m of the upper part of the profile are of Younger Dryas age. The lower part of the sequence dates from the Allerød or Bølling/Allerød and a preceding cold phase, probably the Oldest Dryas. Accordingly the deposition of the sequence took about 2500 or 3500 years and was completed long before the onset of the Neolithic. Our results are in excellent agreement with findings in other formerly glaciated alpine valleys (e.g. the Traun, Salzach and Enns valleys in the Northern Alps). The final depth of the Fersina 2 well is 190 m. It is very likely that the sediment sequence found below this level in the nearby 423 m deep Fersina 1 well was also deposited after the deglaciation of the Adige Valley at the end of the last glacial period.

Mid-Miocene planktonic foraminifera of the Kerguelen Plateau, Antarctica

Miocene deep-sea sediments from ODP Site 744 (Kerguelen Plateau, southern Indian Ocean) contain abundant and diverse planktonic foraminiferal assemblages. Their analysis led to the identification of the interval between 17.0 and 14.2 Ma as a time of mid-Miocene warmth, which is investigated here in detail. This investigation includes reconstruction of trends in foraminiferal faunal composition and diversity through time, as well as in morphology and coiling direction within Globorotalia praescitula and Globorotalia zealandica plexi. These two large-globorotaliid plexi constitute the most characteristic component of the mid-Miocene foraminiferal faunas at ODP Site 744. Selected benthic (Cibicidoides sp.) and planktonic foraminifera were also analyzed for delta18O and delta13C ratios. Distinctive planktonic assemblages were the basis for identification of three foraminiferal biofacies between 17.0 and 14.2 Ma. The most prominent faunal changes took place between Biofacies 2 and 3 (15.5-15.0 Ma). Six of 11 macroperforate planktonic foraminifera from the >150-µm size fraction occur principally within Biofacies 3. Three other taxa are present throughout the interval analyzed. Moreover, both aforementioned globorotaliid plexi exhibit an increase in morphological diversity between Biofacies 2 and 3. Within the same interval, the G. zealandica plexus shows a switch from random coiling (50% sinistral) to clearly sinistral-dominated coiling. The faunal changes recognized are interpreted as the result of foraminiferal immigrations (increase in faunal diversity) and evolutionary trends (increase in morphological variability and change in coiling mode among the globorotaliid plexi). The stable isotopic results allow paleoenvironmental interpretation of these faunal changes. According to the delta18O values, no significant change in sea-surface temperature occurred between 17.0 and 14.2 Ma. However, the same data suggest an increase in ecological distance between various niches, which is expressed by a rising delta18O gradient recorded between various planktonic taxa upward within the section. This trend suggests niche-space availability as a likely factor responsible for the faunal changes recognized. Changes in the shape and depth of the thermocline, as well as in seasonality and eutrophication are considered as possible causes. Among these an increase in seasonality appears to have been responsible for the increase in species and morphological diversities between 15.5 and 15.0 Ma. The proposed scenario suggests that changes in seasonality may be an important factor driving faunal migrations and evolution. Variable seasonality may also affect the oxygen isotopic record of planktonic foraminiferal taxa.

Deep water formation in the North Pacific and deglacial CO2 rise

Deep water formation in the North Atlantic and Southern Ocean is widely thought to influence deglacial CO2 rise and climate change; here we suggest that deep water formation in the North Pacific may also play an important role. We present paired radiocarbon and boron isotope data from foraminifera from sediment core MD02-2489 at 3640 m in the North East Pacific. These show a pronounced excursion during Heinrich Stadial 1, with benthic-planktic radiocarbon offsets dropping to ~350 years, accompanied by a decrease in benthic d11B. We suggest this is driven by the onset of deep convection in the North Pacific, which mixes young shallow waters to depth, old deep waters to the surface, and low-pH water from intermediate depths into the deep ocean. This deep water formation event was likely driven by an increase in surface salinity, due to subdued atmospheric/monsoonal freshwater flux during Heinrich Stadial 1. The ability of North Pacific Deep Water (NPDW) formation to explain the excursions seen in our data is demonstrated in a series of experiments with an intermediate complexity Earth system model. These experiments also show that breakdown of stratification in the North Pacific leads to a rapid ~30 ppm increase in atmospheric CO2, along with decreases in atmospheric d13C and D14C, consistent with observations of the early deglaciation. Our inference of deep water formation is based mainly on results from a single sediment core, and our boron isotope data are unavoidably sparse in the key HS1 interval, so this hypothesis merits further testing. However we note that there is independent support for breakdown of stratification in shallower waters during this period, including a minimum in d15N, younging in intermediate water 14C, and regional warming. We also re-evaluate deglacial changes in North Pacific productivity and carbonate preservation in light of our new data, and suggest that the regional pulse of export production observed during the Bølling-Allerød is promoted by relatively stratified conditions, with increased light availability and a shallow, potent nutricline. Overall, our work highlights the potential of NPDW formation to play a significant and hitherto unrealized role in deglacial climate change and CO2 rise.

Carbon chemistry of oceanic crust

Carbonate mineral precipitation in the upper oceanic crust during low-temperature, off-axis, hydrothermal circulation is investigated using new estimates of the bulk CO2 content of seven DSDP/ODP drill cores. In combination with previously published data these new data show: (i) the CO2 content of the upper ~ 300 m of the crust is substantially higher in Cretaceous than in Cenozoic crust and (ii) for any age of crust, there is substantially more CO2 in Atlantic (slow-spreading) than Pacific (intermediate- to fast-spreading) crust. Modelling the Sr-isotopic composition of the carbonates suggests that > 80% of carbonate mineral formation occurs within < 20 Myr of crust formation. This means that the higher CO2 content of Cretaceous crust reflects a secular change in the rate of CO2 uptake by the crust. Oxygen isotope derived estimates of carbonate mineral precipitation temperatures show that the average and minimum temperature of carbonate precipitation was ~10 °C higher temperatures in the Cretaceous than in the Cenozoic. This difference is consistent with previous estimates of secular change in bottom seawater temperature. Higher fluid temperature within the crust will have increased reaction rates potentially liberating more basaltic Ca and hence enhancing carbonate mineral precipitation. Additionally, if crustal fluid pH is controlled by fluid-rock reaction, the higher Ca content of the Cretaceous ocean will also have enhanced carbonate mineral precipitation. New estimates of the rate of CO2 uptake by the upper ocean crust during the Cenozoic are much lower than previous estimates.

Oxygen, carbon and strontium isotope data for DSDP Hole 35-323

A downhole decrease in 18O, Mg(2+) and K+, an increase in Ca(2+) and a low 87Sr/86Sr ratio of 0.7067 in the pore fluids of DSDP site 323 were caused principally by the alteration of volcanic material. These chemical and isotopic patterns were produced by the alteration, in order of decreasing importance of: a 60-m thick basal layer of volcanic ash; the underlying basalts; and igneous components in the 640-m thick upper sequence composed largely of terrigenous material. A significant portion of the alteration of the ash in the basal sequence must have occurred before the deposition of the upper sediments, perhaps under the influence of advecting solutions. The rest of the alteration occurred during the deposition of the thick upper sediments. Mass balance considerations and the low d18O values of most of the alteration products suggest that much of the later alteration occurred progressively over the last 13 Myr. The principal alteration products were smectite, potassium feldspar, clinoptilolite and calcite.

Calcium carbonate, biogenic opal, and organic carbon content and d15N ratios of sediments from the Bering Sea

Millennial-scale paleoceanographic changes in the Bering Sea during the last 71 kyrs were reconstructed using geochemical and isotope proxies (biogenic opal, CaCO3, and total organic carbon (TOC), nitrogen and carbon isotopes of sedimentary organic matters) and microfossil (radiolaria and foraminifera) data from two cores (PC23A and PC24A) which were collected from the northern continental slope area at intermediate water depths. Biogenic opal and TOC contents were generally high with high sedimentation rates during the last deglaciation. Laminated sediment depositions during the Early-Holocene (EH) and Bølling-Allerød (BA) were closely related with the increased primary productivity recorded by high biogenic opal and TOC contents and high d15N values. Enhanced surface-water productivity was attributed to increased nutrient supply from strengthened Bering Slope Current (BSC) and from increased amount of glacial melt-water, resulting in high C/N ratios and low d13C values, and high proportion of Rhizoplegma boreale during the last deglaciation. In contrast, low surface-water productivity during the last glacial period was due to depleted nutrient supply caused by strong stratification and to restricted phytoplankton bloom by extensive sea ice distribution under cold climates. Extensive formation of sea ice produces more oxygen-rich intermediate-water, leading to oxic bottom-water conditions due to active ventilation, which favored good preservation of oxic benthic foraminifera species. Remarkable CaCO3 peaks coeval with high biogenic opal and TOC contents in both cores during MIS 3 to MIS 4 are most likely correlated with Dansgaard-Oeschger (D-O) events. High d15N and d13Corg values during D-O interstadials support increased surface-water productivity resulting from nutrients supplied mainly by intensified BSC. During the EH, BA and D-O interstadials, dominant benthic foraminifera species indicate dysoxic bottom-water conditions as a result of increased surface-water productivity and weak ventilation of intermediate-water with mitigated sea ice development caused by strengthening of the Alaskan Stream. It is of note that the bottom-water conditions and formation of intermediate-water in the Bering Sea during the last glacial period are related to the variation of dissolved oxygen concentration of the bottom-water in the northeastern Pacific and to strong ventilation of intermediate-water in the northwestern Pacific. Thus, the millennial-scale paleoceanographic events in the Bering Sea during the D-O interstadials are closely associated with the intermediate-water ventilation, ultimately leading to weakening of North Pacific Intermediate Water.

Grain characteristics and XRD raw data of ODP Sites 162-981 and 162-984

Multisensor track data, including magnetic susceptibility, gamma-ray attenuation porosity evaluator (GRAPE) wet bulk density, and natural gamma emission, were collected on all cores recovered during Ocean Drilling Program Leg 162. Data from the upper Pliocene and lower Pleistocene of Sites 981 and 984 are here compared to results from analyses of a limited set of discrete samples, including benthic foraminiferal isotopic composition, grain size, carbonate content, abundance of foraminifers and lithic particles, and clay mineralogy. Natural gamma emission most closely monitors the input of felsic terrigenous material to these two sites. Magnetic susceptibility also tracks felsic terrigenous input at Site 981 but appears to reflect a separate, more mafic, terrigenous component at Site 984. The GRAPE record does not correlate well with any discretely measured variable at Sites 981 or 984.

Chronology and stable carbon isotopic ratios of sediments from the Western Pacific Warm Pool region

Instrumental data suggest that major shifts in tropical Pacific atmospheric dynamics and hydrology have occurred within the past century, potentially in response to anthropogenic warming. To better understand these trends, we use the hydrogen isotopic ratios of terrestrial higher plant leaf waxes (DDwax) in marine sediments from southwest Sulawesi, Indonesia, to compile a detailed reconstruction of central Indo-Pacific Warm Pool (IPWP) hydrologic variability spanning most of the last two millennia. Our paleodata are highly correlated with a monsoon reconstruction from Southeast Asia, indicating that intervals of strong East Asian summer monsoon (EASM) activity are associated with a weaker Indonesian monsoon (IM). Furthermore, the centennial-scale oscillations in our data follow known changes in Northern Hemisphere climate (e.g., the Little Ice Age and Medieval Warm Period) implying a dynamic link between Northern Hemisphere temperatures and IPWP hydrology. The inverse relationship between the EASM and IM suggests that migrations of the Intertropical Convergence Zone and associated changes in monsoon strength caused synoptic hydrologic shifts in the IPWP throughout most of the past two millennia.

Glacial-interglacial record of ODP Site 181-1119 in the Canterbury Bright, Southwest Pacific Ocean

Ocean Drilling Program (ODP) Site 1119 is located at water depth 395 m near the subtropical front (STF; here represented by the Southland Front), just downslope from the shelf edge of eastern South Island, New Zealand. The upper 86.19 metres composite depth (mcd) of Site 1119 sediment was deposited at an average sedimentation rate of 34 cm/kyr during Marine Isotope Stages (MIS) 1-8 (0-252 ka), and is underlain across a ~25 kyr intra-MIS 8 unconformity by MIS 8.5-11 (277-367 ka) and older sediment deposited at ~14 cm/kyr. A time scale is assigned to Site 1119 using radiocarbon dates for the period back to ~39 ka, and, prior to then, by matching its climatic record with that of the Vostok ice core, which it closely resembles. Four palaeoceanographic proxy measures for surface water masses vary together with the sandy-muddy, glacial-interglacial (G/I) cyclicity at the site. Interglacial intervals are characterised by heavy delta13C, high colour reflectance (a proxy for carbonate content), low Q-ray (a proxy for clay content) and light delta18O; conversely, glacial intervals exhibit light delta13C, low reflectance, high Q-ray and heavy delta18O signatures. Early interglacial intervals are represented by silty clays with 10-105-cm-thick beds of sharp-based (Chondrites-burrowed), shelly, graded, fine sand. The sands are rich in foraminifera, and were deposited distant from the shoreline under the influence of longitudinal flow in relatively deep water. Glacial intervals comprise mostly micaceous silty clay, though with some thin (2-10 cm thick) sands present also at peak cold periods, and contain the cold-water scallop Zygochlamys delicatula. Interglacial sandy intervals are characterised by relatively low sedimentation rates of 5-32 cm/kyr; cold climate intervals MIS 10, 6 and 2 have successively higher sedimentation rates of 45, 69 and 140 cm/kyr. Counter-intuitively,and forced by the bathymetric control of a laterally-moving shoreline during G/I and I/G transitions, the 1119 core records a southeasterly (seaward) movement of the STF during early glacial periods, accompanied by the incursion of subtropical water (STW) above the site, and northwesterly (landward) movement during late glacial and interglacial times, resulting in a dominant influence then of subantarctic surface water (SAW). The history of passage of these different water masses at the site is clearly delineated by their characteristic delta13C values. The intervals of thin, graded sands-muds which occur within MIS 2-3, 6, 7.4 and 10 indicate the onset at times of peak cold of intermittent bottom currents caused by strengthened and expanded frontal flows along the STF, which at such times lay near Site 1119 in close proximity to seaward-encroaching subantarctic waters within the Bounty gyre. In common with other nearby Southern Hemisphere records, the cold period which represents the last glacial maximum lasted between ~23-18 ka at Site 1119, during which time the STF and Subantarctic Front (SAF) probably merged into a single intense frontal zone around the head of the adjacent Bounty Trough.

IODP Expedition 337, Shimokita Deep Coalbed Biosphere

Microbial life inhabits deeply buried marine sediments, but the extent of this vast ecosystem remains poorly constrained. Here we provide evidence for the existence of microbial communities in ~40° to 60°C sediment associated with lignite coal beds at ~1.5 to 2.5 km below the seafloor in the Pacific Ocean off Japan. Microbial methanogenesis was indicated by the isotopic compositions of methane and carbon dioxide, biomarkers, cultivation data, and gas compositions. Concentrations of indigenous microbial cells below 1.5 km ranged from <10 to ~10**4 cells cm**-3. Peak concentrations occurred in lignite layers, where communities differed markedly from shallower subseafloor communities and instead resembled organotrophic communities in forest soils. This suggests that terrigenous sediments retain indigenous community members tens of millions of years after burial in the seabed.