Analyses of ferromanganese micronodules from the central Arctic Ocean

In order to determine geochemical compositions of Late Cenozoic Arctic seawater, oxide fractions were chemically separated from 15 samples of hand-picked ferromanganese micronodules (50-300 mu m). The success of the chemical separation is indicated by the fact that >97% of the Sr in the oxide fraction is seawater-derived. Rare-earth element (REE) abundances of the Arctic micronodule oxide fractions are much lower than those of bulk Fe-Mn nodules from other ocean basins of the world (e.g., 33 vs. 145 ppm Nd), but the Arctic oxides are enriched in Ce relative to Nd (Ce-N/Nd-N=2.2+/-0.5) and have convex-upward, shale-normalized REE patterns (Nd-N/Gd-N=0.61+/-0.06, Gd-N/Yb-N = 1.5+/-0.2, Nd-N/Yb-N = 0.9+/-0.2), typical of other hydrogenous and diagenetic marine Fe-Mn-oxides. Bulk sediment samples from the central Arctic Ocean have REE abundances and patterns that are characteristic of those of post-Archean shale. Non-detrital fractions (calcite + oxide coatings) of Recent Arctic foraminifera have REE abundances and patterns similar to those of Recent foraminifera from the Atlantic Ocean. Electron microprobe analyses (n=178) of transition elements in 29 Arctic Fe-Mn micronodules from five different stratigraphic intervals of Late Cenozoic sediment indicate that oxide accretion occurred as a result of hydrogenetic and diagenetic processes close to the sediment-seawater interface. Transition element ratios suggest that no oxide accretion occurred during transitions from oxic to suboxic diagenetic conditions. Only K is correlated with Si and Al, and ratios of these elements suggest that they are associated with illite or phillipsite. Ca and Mg are correlated with Mn, which indicates variable substitution of these elements from seawater into the manganate phase. The geochemical characteristics of Arctic Fe-Mn micronodules indicate that the REEs of the oxide fractions were ultimately derived from seawater. However, because of minute contributions of Sr from siliciclastic detritus during diagenesis or during the chemical leaching procedure, Sr isotope compositions of the oxide fractions cannot be used to trace temporal changes in the Sr-87/Sr-86 ratio of Arctic seawater or to improve the chronostratigraphy.

Particle fluxes and in-situ particle properties measured with sediment traps and a moored camera system from 2008 - 2010 in region off Cape Blanc / NW-Africa

We compared particle data from a moored video camera system with sediment trap derived fluxes at ~1100 m depth in the highly dynamic coastal upwelling system off Cape Blanc, Mauritania. Between spring 2008 and winter 2010 the trap collected settling particles in 9-day intervals, while the camera recorded in-situ particle abundance and size-distribution every third day. Particle fluxes were highly variable (40-1200 mg m**-2 d**-1) and followed distinct seasonal patterns with peaks during spring, summer and fall. The particle flux patterns from the sediment traps correlated to the total particle volume captured by the video camera, which ranged from1 to 22 mm**3 l**-1. The measured increase in total particle volume during periods of high mass flux appeared to be better related to increases in the particle concentrations, rather than to increased average particle size. We observed events that had similar particle fluxes, but showed clear differences in particle abundance and size-distribution, and vice versa. Such observations can only be explained by shifts in the composition of the settling material, with changes both in particle density and chemical composition. For example, the input of wind-blown dust from the Sahara during September 2009 led to the formation of high numbers of comparably small particles in the water column. This suggests that, besides seasonal changes, the composition of marine particles in one region underlies episodical changes. The time between the appearance of high dust concentrations in the atmosphere and the increase lithogenic flux in the 1100 m deep trap suggested an average settling rate of 200 m d**-1, indicating a close and fast coupling between dust input and sedimentation of the material.

Tab. 1: Mass changes and balances 1982/83 for stakes on the Inland Ice at Päkitsup ilordlia north-east of Jakobshavn

In connection with hydropower investigations in West Greenland mass balance measurements have been carried out 1982/83 on the Inland lce at Päkitsup ilordlia north-east of Jakobshavn. The mass balance was measured at seven stakes drilled into the ice at altitudinal intervals of 200 metres from 300 m to 1500 m a.s.l. The measurements show that mass balance conditions in the Jakobshavn area must have been abnormally positive for the 1982/83 hydrological year.

Late Cretaceous-Cenozoic magnetostratigraphic and biostratigraphic correlation of DSDP Hole 73-519 in the South Atlantic

DSDP Leg 73 sediment cores allow direct calibrations of magnetostratigraphy and biostratigraphy for much of the latest Cretaceous to Cenozoic in the mid-latitude South Atlantic Ocean. A complete record of the Cenozoic was not obtained, however, because strong dissolution, poor core recovery and intense core disturbance have masked the biostratigraphy or magnetostratigraphy over some intervals of all recovered sections. DSDP Leg 73 results show the following correlations: Early/middle Miocene in Chron 16 Oligocene/Miocene within Subchron C6CN Eocene/Oligocene within Subchron C13R Middle/late Eocene top of Chron C17 Early/late Paleocene top of Subchron C27N Cretaceous/Tertiary within Subchron C29R

Chemistry of secondary minerals from the deep sheeted dike complex of ODP Holes 137-504B and 140-504B

Dolerites sampled from the lower sheeted dikes from Hole 504B during Ocean Drilling Program Legs 137 and 140, between 1562.4 and 2000.4 mbsf, were examined to document the mineralogy, petrography, and mineral parageneses associated with secondary alteration, to constrain the thermal history and composition of hydrothermal fluids. The main methods used were mineral chemical analyses by electron microprobe, X-ray diffraction, and cathodoluminescence microscopy. Temperatures of alteration were estimated on the basis of single and/or coexisting mineral chemistry. Permeability is important in controlling the type and extent of alteration in the studied dike section. At the meter-scale, intervals of weakly altered dolerites containing fresh olivine are interpreted as having experienced restricted exposure to hydrothermal fluids. At the centimeter- or millimeter-scale, alteration patches and extensively altered halos adjacent to veins reflect the permeability related to intergranular primary porosity and cracks. Most of the sheeted dike alteration in this case resulted from non-focused, pervasive fluid-rock interaction. This study confirms and extends the previous model for hydrothermal alteration at Hole 504B: hydrothermal alteration at the ridge axis followed by seawater recharge and off-axis alteration. The major new discoveries, all related to higher temperatures of alteration, are: (1) the presence of hydrothermal plagioclase (An80-95), (2) the presence of deuteric and/or hydrothermal diopside, and (3) the general increasing proportion of amphiboles, and particularly magnesio-hornblende with depth. We propose that the dolerites at Hole 504B were altered in five stages. Stage 1 occurred at high temperatures (less than 500° to 700°C) and involved late-magmatic formation of Na- and Ti-rich diopside, the hydrothermal formation of Na, Ti-poor diopside and the hydrothermal formation of an assemblage of An-rich plagioclase + hornblende. Stage 2 occurred at lower temperatures (250°-320°C) and is characterized by the appearance of actinolite, chlorite, chlorite-smectite, and/or talc (in low permeability zones) and albite. During Stage 3, quartz and epidote precipitated from evolved hydrothermal fluids at temperatures between 310° and 320°C. Anhydrite appeared during Stage 4 and likely precipitated directly from heated seawater. Stage 5 occurred off-axis at low temperatures (250°C) with laumontite and prehnite from evolved fluids.

Elemental and isotopic compositions of metalliferous and pelagic sediments from the Galapagos mounds area, data of DSDP Leg 70

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at a subsurface depth of ~2-20 m; Mn-oxide material is limited to the upper 2 m of these mounds. The nontronite forms intervals of up to a few metres thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. The metalliferous phases represent essentially authigenic precipitates, apparently formed in the presence of upwelling basement-derived hydrothermal solutions which dissolved pre-existent pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major-element composition between nontronitic material from varying locations within the mounds; and (2) adjacent granules from a given sample have very similar compositions and are internally homogeneous. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of solution Eh and composition during nontronite formation. The Pb-isotopic composition of the nontronite and Mn-oxide sediments indicates that they were formed from solutions which contained variable proportions of basaltic Pb, introduced into pore waters by basement-derived solutions, and of normal-seawater Pb. However, the Sr-isotopic composition of these sediments is essentially indistinguishable from the value for modern seawater. On the basis of 18O/16O ratios, formation temperatures of ~20-30°C have been estimated for the nontronites. By comparison, temperatures of up to 11.5°C at 9 m depth have been directly measured within the mounds and heat flow data suggest present basement-sediment interface temperatures of 15-25°C.

Paleomagnetic and biostratigraphic properties and datums of ODP Leg 173 and Leg 149 sites

We have conducted an integrated paleomagnetic and biostratigraphic study on the Cenozoic sedimentary sequences of the southern Iberia Abyssal Plain margin, focusing on Ocean Drilling Program (ODP) Sites 897, 898, 900, 1067, 1068, and 1069. Reliable magnetostratigraphy from these six sites is presented in this paper. Sedimentary sections from Holes 897C, 898A, 900A, 1067A, 1068A, and 1069A have recorded a pattern of magnetic polarity reversals that correlates well with the known magnetic polarity timescale for the past 56 m.y. The polarity patterns from the Pliocene-Pleistocene turbidite sequence at the Leg 149 sites show that a reliable magnetostratigraphy can be established from the early Pliocene to Holocene, including the Gilbert/Gauss boundary (3.58 m.y.) through the Matuyama/Brunhes boundary (0.78 m.y.). On the basis of distinct intervals of magnetic reversal zones and biostratigraphic datums, five magnetozones (C21n-C25n) can be recognized at the three Leg 173 sites that range from middle Eocene to late Paleocene in age. The magnetostratigraphy of the Iberia sections allows the determination of sedimentation rates and better constraints on the timing of deformation. Combining the age and average inclination information available from the magnetostratigraphy, we also present paleolatitudes vs. time for the Iberia drill sites.

(Table 1) Isotopic and geochemical parameters of gas phase from underground fluids of the Baikal rift and its framing

Results of studying isotopic composition of helium in underground fluids of the Baikal-Mongolian region during the last quarter of XX century are summarized. Determinations of 3He/4He ratio in 139 samples of gas phase from fluids, collected at 104 points of the Baikal rift zone and adjacent structures are given. 3He/4He values lie within the range from 1x10**-8 (typical for crustal radiogenic helium) to 1.1x10**-5 (close to typical MORB reservoir). Repeated sampling in some points during more than 20 years showed stability of helium isotopic composition in time in each of them at any level of 3He/4He values. There is no systematic differences of 3He/4He in samples from surface water sources and deeper intervals of boreholes in the same areas. Universal relationship between isotopic composition of helium and general composition of gas phase is absent either, but the minimum 3He/4He values occurred in methane gas of hydrocarbon deposits, whereas in nitrogen and carbon dioxide gases of helium composition varied (in the latter maximum 3He/4He values have been measured). According to N2/Ar_atm ratio nitrogen gases are atmospheric. In carbonic gas fN2/fNe ratio indicates presence of excessive (non-atmogenic) nitrogen, but the attitude CO2/3He differs from one in MORB. Comparison of helium isotopic composition with its concentration and composition of the main components of gas phase from fluids shows that it is formed under influence of fractionation of components with different solubility in the gas-water system and generation/consumption of reactive gases in the crust. Structural and tectonic elements of the region differ from the spectrum of 3He/4He values. At the pre-Riphean Siberian Platform the mean 3He/4He = (3.6+/-0.9)x10**- 8 is very close to radiogenic one. In the Paleozoic crust of Khangay 3He/4He = (16.3+/-4.6)x10**-8, and the most probable estimate is (12.3+/-2.9)x10**-8. In structures of the eastern flank of the Baikal rift zone (Khentei, Dauria) affected by the Mz-Kz activization 3He/4He values range from 4.4x10**-8 to 2.14x10**-6 (average 0.94x10**-6). Distribution of 3He/4He values across the strike of the Baikal rift zone indicates advective heat transfer from the mantle not only in the rift zone, but also much further to the east. In fluids of the Baikal rift zone range of 3He/4He values is the widest: from 4x10**-8 to 1.1x10**-5. Their variations along the strike of the rift zone are clearly patterned, namely, decrease of 3He/4He values in both directions from the Tunka depression. Accompanied by decrease in density of conductive heat flow and in size of rift basins, this trend indicates decrease in intensity of advective heat transfer from the mantle to peripheral segments of the rift zone. Comparing this trend with data on other continental rift zones and mid-ocean ridges leads to the conclusion about fundamental differences in mechanisms of interaction between the crust and the mantle in these environments.

Stable carbon and oxygen isotope compositions of Eocene benthic foraminifera from ODP Site 207-1258

'Hyperthermals' are intervals of rapid, pronounced global warming known from six episodes within the Palaeocene and Eocene epochs (~65-34 million years (Myr) ago) (Zachos et al., 2005, doi:10.1126/science.1109004; 2008, doi:10.1038/nature06588; Roehl et al., 2007, doi:10.1029/2007GC001784; Thomas et al., 2000; Cramer et al., 2003, doi:10.1029/2003PA000909; Lourens et al., 2005, doi:10.1038/nature03814; Petrizzo, 2005, doi:10.2973/odp.proc.sr.198.102.2005; Sexton et al., 2006, doi:10.1029/2005PA001253; Westerhold et al., 2007, doi:10.1029/2006PA001322; Edgar et al., 2007, doi:10.1038/nature06053; Nicolo et al., 2007, doi:10.1130/G23648A.1; Quillévéré et al., 2008, doi:10.1016/j.epsl.2007.10.040; Stap et al., 2010, doi:10.1130/G30777.1). The most extreme hyperthermal was the 170 thousand year (kyr) interval (Roehl et al., 2007) of 5-7 °C global warming (Zachos et al., 2008) during the Palaeocene-Eocene Thermal Maximum (PETM, 56 Myr ago). The PETM is widely attributed to massive release of greenhouse gases from buried sedimentary carbon reservoirs (Zachos et al., 2005; 2008; Lourenbs et al., 2005; Nicolo et al., 2007; Dickens et al., 1995, doi:10.1029/95PA02087; Dickens, 2000; 2003, doi:10.1016/S0012-821X(03)00325-X; Panchuk et al., 2008, doi:10.1130/G24474A.1) and other, comparatively modest, hyperthermals have also been linked to the release of sedimentary carbon (Zachos et al., 2008, Lourens et al., 2005; Nicolo et al., 2007; Dickens, 2003; Panchuk et al., 2003). Here we show, using new 2.4-Myr-long Eocene deep ocean records, that the comparatively modest hyperthermals are much more numerous than previously documented, paced by the eccentricity of Earth's orbit and have shorter durations (~40 kyr) and more rapid recovery phases than the PETM. These findings point to the operation of fundamentally different forcing and feedback mechanisms than for the PETM, involving redistribution of carbon among Earth's readily exchangeable surface reservoirs rather than carbon exhumation from, and subsequent burial back into, the sedimentary reservoir. Specifically, we interpret our records to indicate repeated, large-scale releases of dissolved organic carbon (at least 1,600 gigatonnes) from the ocean by ventilation (strengthened oxidation) of the ocean interior. The rapid recovery of the carbon cycle following each Eocene hyperthermal strongly suggests that carbon was resequestered by the ocean, rather than the much slower process of silicate rock weathering proposed for the PETM (Zachos et al., 2005; 2003). Our findings suggest that these pronounced climate warming events were driven not by repeated releases of carbon from buried sedimentary sources (Zachos et al., 2008, Lourens et al., 2005; Nicolo et al., 2007; Dickens, 2003; Panchuk et al., 2003) but, rather, by patterns of surficial carbon redistribution familiar from younger intervals of Earth history.

(Table S1) Age determination of ODP Site 202-1240

Interannual-decadal variability in the equatorial Pacific El Niño-Southern Oscillation (ENSO) induces climate changes at global scale, but its potential influence during past global climate change is not yet well constrained. New high-resolution eastern equatorial Pacific proxy records of thermocline conditions present new evidence of strong orbital control in ENSO-like variability over the last 275,000 years. Recurrent intervals of saltier thermocline waters are associated with the dominance of La Niña-like conditions during glacial terminations, coinciding with periods of low precession and high obliquity. The parallel dominance of d13C-depleted waters supports the advection of Antarctic origin waters toward the tropical thermocline. This "oceanic tunneling" is proposed to have reinforced orbitally induced changes in ENSO-like variability, composing a complex high- and low-latitude feedback during glacial terminations.

Calculation of paleoproductivity during the Eocene-Oligocene transition of ODP Site 113-689

High-resolution records of carbon and oxygen isotopes and benthic foraminiferal accumulation rates for the Eocene-Oligocene section at Ocean Drilling Program Site 689 (Maud Rise, Weddell Sea; paleodepth about 1500 m) were used to infer variations in paleoproductivity in relation to changes in climate and ventilation of the deeper-water column. The benthic foraminiferal abundance and isotope records show short-term fluctuations at periodicities of 100 and 400 ka, implying orbitally driven climatic variations. Both records suggest that intermediate-depth water chemistry and primary productivity changed in response to climate. During the Eocene, productivity increased during cold periods and during cold-to-warm transitions, possibly as a result of increased upwelling of nutrient-rich waters. In the Oligocene, in contrast, productivity maxima occurred during intervals of low delta18O values (presumably warmer periods), when a proto-polar front moved to the south of the location of Site 689. This profound transition in climate-productivity patterns occurred around 37 Ma, coeval with rapid changes toward increasing variability of the oxygen and carbon isotope and benthic abundance records and toward larger-amplitude delta18O fluctuations. Therefore, we infer that, at this time, temperature fluctuations increased and a proto-polar front formed in conjunction with the first distinct pulsations in size of the Antarctic ice sheet. We speculate that this major change might have resulted from an initial opening of the Drake Passage at 37 Ma, at least for surface- and intermediate-water circulation.

Geochemistry of Baltic Sea sediments and porewaters

Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link between iron oxyhydroxide dissolution and release of P from Baltic Sea sediments, we show that preferential remineralization of P with respect to carbon (C) and nitrogen (N) during degradation of organic matter plays a key role in determining the surplus of bioavailable P in the water column. Preferential remineralization of P takes place both in the water column and upper sediments and its rate is shown to be redox-dependent, increasing as reducing conditions become more severe at greater water-depth in the deep basins. Existing Redfield-based biogeochemical models of the Baltic may therefore underestimate the imbalance between N and P availability for primary production, and hence the vulnerability of the Baltic to sustained eutrophication via the fixation of atmospheric N. However, burial of organic P is also shown to increase during multidecadal intervals of expanded hypoxia, due to higher net burial rates of organic matter around the margins of the deep basins. Such intervals may be characterized by basin-scale acceleration of all fluxes within the P cycle, including productivity, regeneration and burial, sustained by the relative accessibility of the water column P pool beneath a shallow halocline.

Physical properties of sediment core AND-2A

Whole-core measurements of Wet Bulk Density (WBD), compressional (P)-wave velocity (Vp), and Magnetic Susceptibility were measured at a sampling interval of 1 or 2 centimetres (cm) throughout the AND-2A drill core for initial core characterisation and on-site correlation with seismic modeling to predict target-reflector depth. Measurements were made using a GEOTEK (Multi-Sensor-Core-Logger MSCL). Density and velocity standards were measured together with core runs of 3-6 metres (m) (and occasionally up to 18 m) throughout the entire depth range to monitor data quality. Drift of the magnetic susceptibility sensor was also monitored and corrected where necessary. These physical properties show a large range of values, reflecting the different nature of the various lithologies including extremely high velocity and density values in individual clasts, and the effects of cementation on porosity. A downcore increase in WBD and Vp occurs in the upper 200 m, however, no systematic trend exists at greater depths although large fluctuations on a m-decimetre- (dm) scale occur. Magnetic susceptibility is generally low (<100 x 10-5 SI), however, four intervals of high (>600 x 10-5 SI) susceptibility occur at 560, 800, 980 and 1 080 mbsf, indicating a relatively greater contribution of volcanic-derived material to the core site in the lower half of the AND-2A core.

Core correlation data and revised composite depth scale of Exp302 (ACEX) cores

Expedition 302 of the Integrated Ocean Drilling Program (IODP), also known as the Arctic Coring Expedition (ACEX), successfully penetrated a sequence of Cenozoic sediments draping the crest of the Lomonosov Ridge in the central Arctic Ocean. The cumulative sedimentary record spans the last 57 m.y. and was recovered from three sites located within 15 km of each other. Merging the recovered cores onto a common depth scale that accurately reflects their stratigraphic placement below the seafloor is a fundamental step toward interpreting this unique sedimentary record. However, the lack of overlapping recovery in adjacent holes and intervals of high core disturbance complicated traditional methods of stratigraphic correlation. Here we present a revised composite depth scale for the ACEX sediments, generated in part by performing a regional stratigraphic correlation with sediments recovered from previous expeditions to the Lomonosov Ridge. The revised depth scale also reassesses the offsets for cores in the upper 55 meters below seafloor, where no overlapping recovery was acquired, and proposes modifications to these depths.