Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Color data, carbon and oxygen isotopes, and offsets from BBCP Polecat Bench cores 2A and 2B

The Earth's climate abruptly warmed by 5-8 °C during the Palaeocene-Eocene thermal maximum (PETM), about 55.5 million years ago**1,2. This warming was associated with a massive addition of carbon to the ocean-atmosphere system, but estimates of the Earth systemresponse to this perturbation are complicated by widely varying estimates of the duration of carbon release, which range from less than a year to tens of thousands of years. In addition the source of the carbon, and whether it was released as a single injection or in several pulses, remains the subject of debate**2-4. Here we present a new high-resolution carbon isotope record from terrestrial deposits in the Bighorn Basin (Wyoming, USA) spanning the PETM, and interpret the record using a carbon-cycle boxmodel of the ocean-atmosphere-biosphere system.Our record shows that the beginning of the PETMis characterized by not one but two distinct carbon release events, separated by a recovery to background values. To reproduce this pattern, our model requires two discrete pulses of carbon released directly to the atmosphere, at average rates exceeding 0.9 Pg C yr**-1, with the first pulse lasting fewer than 2,000 years.

Eocene sedimentary calcium carbonate contents and stable isotope composition of benthic foraminifera

'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.

Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

DISPRO datasets for validation of coastal hydrodynamic models

Appropriate field data are required to check the reliability of hydrodynamic models simulating the dispersion of soluble substances in the marine environment. This study deals with the collection of physical measurements and soluble tracer data intended specifically for this kind of validation. The intensity of currents as well as the complexity of topography and tides around the Cap de La Hague in the center of the English Channel makes it one of the most difficult areas to represent in terms of hydrodynamics and dispersion. Controlled releases of tritium - in the form of HTO - are carried out in this area by the AREVA-NC plant, providing an excellent soluble tracer. A total of 14 493 measurements were acquired to track dispersion in the hours and days following a release. These data, supplementing previously gathered data and physical measurements (bathymetry, water-surface levels, Eulerian and Lagrangian current studies) allow us to test dispersion models from the hour following release to periods of several years which are not accessible with dye experiments. The dispersion characteristics are described and methods are proposed for comparing models against measurements. An application is proposed for a 2 dimensions high-resolution numerical model. It shows how an extensive dataset can be used to build, calibrate and validate several aspects of the model in a highly dynamic and macrotidal area: tidal cycle timing, tidal amplitude, fixed-point current data, hodographs. This study presents results concerning the model's ability to reproduce residual Lagrangian currents, along with a comparison between simulation and high-frequency measurements of tracer dispersion. Physical and tracer data are available from the SISMER database of IFREMER (www.ifremer.fr/sismer/catal). This tool for validation of models in macro-tidal seas is intended to be an open and evolving resource, which could provide a benchmark for dispersion model validation.

Strontium and rubidium isotopes in serpentinites from ODP Site 195-1200

Subduction of the Pacific plate beneath the Mariana forearc releases fluids to the overlying mantle wedge that ascend, producing serpentinite "mud" that discharges on the ocean floor. As part of Leg 195 of the Ocean Drilling Program cores were obtained from drill-holes into the mud volcanoes. We report the isotopic composition of Sr in water squeezed from intervals of the cores, in the serpentinite mud, in leaches of the serpentinite mud, and in entrained small harzburgitic clasts. Except in the upper few meters below the seawater-mud interface, where pore water approaches seawater Sr concentration and isotopic ratio, Sr concentration and isotopic composition remain constant at 3-6 µmol/kg and ~0.7054. Because the elemental chemistry of the pore water is unlike seawater, this isotopic composition reflects fluids derived from the subducted slab, probably modified by reaction with mantle material during ascent. Higher Sr isotopic ratios, up to 0.7087, - but not with higher Sr concentrations in pore water - occur superimposed on an advection profile at 13-16 mbsf surrounding a thin layer of foraminiferal sand. Since the upward seepage velocity of slab fluids in the mud volcano vents is a few cm/yr, exchange of Sr between these carbonates and the rising fluids must have occurred within a maximum of a few hundred years, essentially instantaneously given the millions, or tens of millions, of years the mud volcanoes have been in existence. In contrast, the strontium isotopic compositions of leached serpentinite mud, and of small harzburgite clasts entrained in the mud, are always significantly greater than that of the pore water. In small harzburgite clasts the ratio reaches 0.7088, almost as high as the seawater value of 0.7092 and much higher than the value of typical mantle-derived strontium of ~0.704. The serpentinite muds and harzburgite clasts clearly equilibrated with seawater Sr when they were initially deposited at the surface of the seamount, but following burial they have not fully equilibrated with strontium in the pore water now discharging through the vents. These variations in the strontium isotopic composition of solids and pore waters are more consistent with episodic expulsion of fluids in the subduction zone than steady state flow. Whereas strontium in carbonates equilibrates isotopically within a few hundred years, strontium in buried harzburgite clasts does not equilibrate in the same time, assuming steady state rates of upward fluid flow. By inference, the harzburgite clasts and associated serpentinite mud must have been near the seafloor, unburied, for a yet undetermined but much longer period of time to have equilibrated from ~0.704 to 0.709 prior to subsequent burial. It may be possible to characterize at least the periodicity of fluid release in the mud volcano setting by investigating the zonation of strontium isotopic composition of hartzburgite clasts throughout the 60-meter deep composite cores.

World distribution of land cover changes, model in NetCDF format

The role of Pre- and Protohistoric anthropogenic land cover changes needs to be quantified i) to establish a baseline for comparison with current human impact on the environment and ii) to separate it from naturally occurring changes in our environment. Results are presented from the simple, adaptation-driven, spatially explicit Global Land Use and technological Evolution Simulator (GLUES) for pre-Bronze age demographic, technological and economic change. Using scaling parameters from the History Database of the Global Environment as well as GLUES-simulated population density and subsistence style, the land requirement for growing crops is estimated. The intrusion of cropland into potentially forested areas is translated into carbon loss due to deforestation with the dynamic global vegetation model VECODE. The land demand in important Prehistoric growth areas - converted from mostly forested areas - led to large-scale regional (country size) deforestation of up to 11% of the potential forest. In total, 29 Gt carbon were lost from global forests between 10 000 BC and 2000 BC and were replaced by crops; this value is consistent with other estimates of Prehistoric deforestation. The generation of realistic (agri-)cultural development trajectories at a regional resolution is a major strength of GLUES. Most of the pre-Bronze age deforestation is simulated in a broad farming belt from Central Europe via India to China. Regional carbon loss is, e.g., 5 Gt in Europe and the Mediterranean, 6 Gt on the Indian subcontinent, 18 Gt in East and Southeast Asia, or 2.3 Gt in subsaharan Africa.

Geologic-hydrologic setting and surface sedimentology in the Persian Gulf

1. Morphology and sedimentation The deepest parts of the Persian Gulf lie off the Iranian coast. Several swells separate the Persian Gulf into the Western Basin, the Central Basin and the Strait of Hormuz, which leads without noticeable morphological interruption onto the Biaban Shelf; the latter gradually drops off towards the continental slope, which itself has a strongly subdivided morphology. The sediment distribution in the Western Basin runs parallel to the basin's axis to a depth of 50 -60 m. This is caused by the shallow and uniform slope of the Iranian coast into the Western Basin, by clear exposure of the area to the Shamal-Winds and by tidal currents parallel to the basin's axis. Most other parameters also show isolines parallel to the coast line. Data from the sediment analyses show a net transport which extends out along the Central Swell: coarse fraction > 63 µ, total carbonate content, carbonate in fine fractions < 2 µ, 2-6 µ and 20-63 µ, calcite-aragonite ratios in the fine fractions 2-6 µ and 20-63 µ and quartz-dolomite ratios in fine fraction 2-6 µ. At least the uppermost 10-40 m of this sediment is late Holocene. This implies sedimentation rates of several meters per 1000 years. The slope from the Iranian coast into the Central Basin (max. depth 100 m) is generally steeper, with interspersed islands and flats. Both facts tend to disturb a sediment dustribition parallel to the basin's axis over extensive areas and may preclude any such trend from being detected by the methods and sample net used. The spatial distribution of the coarse fraction, however, seems to indicate sediment transport at greater water depths perpendicular to the basin's long axis and along the steepest gradients well into the Central Basin. The flats of the Central Basin have a sediment cover distinctly different from those of the deeper basin areas. Characteristic parameters are the extremely high percentages of coarse grained sediments, total content of carbonate CO2 over 40, low total organic carbon content, (however values are high if calculated on the basis of the < 63 µ fraction), low total N-content, and low C/N ratios. These characteristics probably result from the absence of any terrigenous material being brought in as well as from exposure to wave action. Finest terrigenous material is deposited in the innermost protected part of the Hormuz Bay. In the deep channel cut into the Biaban Shelf which carries the Persian Gulf out-flow water to the Indian Ocean, no fine grained sediment is deposited as shown by grain size data. 2. Geographic settings and sedimentation Flat lands border the Arabian coast of the Persian Gulf except for the Oman region. The high and steep Zagros Mountains form the Iranian coastline. Flat topography in combination with generally low precipitation precludes fluviatile sediment being added from the South. Inorganic and biogenic carbonates accumulating under low sedimentation rates are dominant on the shallow Arabic Shelf and the slopes into the Western and Central Basins. The fluviatile sediment brought in from the Iranian side, however decisively determine the composition of the Holocene sediment cover in the Persian Gulf and on the Biaban Shelf. Holocene sediments extend 20-30 km seaward into the Western Basin and about 25 km on to the Biaban Shelf. As mentioned before, sedimentation rates are of several meters/1000 years. The rocks exposed in the hinterland influence the sediments. According to our data the Redbeds of the Zagros Mountains determine the colour of the very fine grained sediments near the Iranian Coast of the Persian Gulf. To the West of Hormuz, addition of carbonate minerals is particularly high. Dolomite and protodolomite, deposited only in this area, as well as palygorskite, have proven to be excellent trace minerals. To the East of Hormuz, the supply of terrigenous carbonates is considerably lower. Clay minerals appear to bring in inorganically bound nitrogen thus lowering the C/N ratio in these sediments especially off river mouths. 3. Climate and sedimentation The Persian Gulf is located in a climatically arid region. This directly affects sedimentation through increased wind action and the infrequent but heavy rainfalls which cause flash floods. Such flash floods could be responsible for transporting sedheats into the Central Basin in a direction perpendicular to the Gulf's axis. Eolian influx is difficult to asses from our data; however, it probably is of minor importance from the Iranian side and may add, at the most, a few centimeters of fine sediment per 1000 years. 4. Hydrology and sedimentation High water temperatures favor inorganic carbonate precipitation in southern margin of the Gulf, and probably on the flats, as well as biogenic carbonate production in general. High evaporation plus low water inflow through rivers and precipitation cause a circulation pattern that is typical for epicontinental seas within the arid climate region. Surface water flows in from the adjoining ocean, in this case the Indian Ocean and sinks to the bottom of the Persian Gulf mainly in the northern part of the Western Basin, on the "Mesopotamischer Flachschelf" ard probably in the area of the "Arabischer Flachschelf". This sinking water continually rejuvenates the bottom out-flow water. The inflowing surface water from the Indian Ocean brings organic matter into the Persian Gulf, additional nutrients are added by the "fresh" upwelling waters of the Gulf of Oman. Both nutrients and organic matter diminish very rapidly as the water moves into the Persian Gulf. This depletion of nutrients and organic matter is the reasonfor generally low organic carbon contents of the Persian Gulf sediments. The Central Swell represents a distinct boundary, to the west of which the organic carbon content are lower than to the east when sediment samples of similar grain size distribution are compared. The outflow carries well oxygenated water over the bottom of the Persian Gulf and the resulting oxidation further decreases the content of organic matter. In the Masandam-Channel and in the Biaban-Shelf channel, the outflowing water prevents deposition of fine material and transports sediment particles well beyond the shelf margin. The outflowing water remains at a depth of 200-300 m depending on its density and releases ist suspending sediment load to the ocean floor, irrespectative of the bottom morphology. This is reflected in several parameters in which the sediments from beneath the outflow differ from nearby sediments not affected by the outflowing water. High carbonate content of total samples and of the individual size fraction as well as high aragonite and dolomite contents of individual size fractions characterize the sediment beneath the outflowing water. The tidal currents, which avt more or less parallel to the Gulf's axis, favor mixing of the water masses, they rework sediments at velocities reported here. This fact enlarges to a certain degree the extent of our interfaces which are based on only a few sample points (Persian Gulf and Biaban Shelf one sample per 620 km**2, continental slope one sample per 1000 km**2). The water on the continental slope shows and oxygen minimum at 200-1200 m which favors preservation of organically-bound carbon in the sediment. The low pH-values may even permit dissolution of carbonate minerals.

Trace element profiles of the sea anemone Anemonia viridis living nearby a natural CO2 vent

Ocean acidification (OA) is not an isolated threat, but acts in concert with other impacts on ecosystems and species. Coastal marine invertebrates will have to face the synergistic interactions of OA with other global and local stressors. One local factor, common in coastal environments, is trace element contamination. CO2 vent sites are extensively studied in the context of OA and are often considered analogous to the oceans in the next few decades. The CO2 vent found at Levante Bay (Vulcano, NE Sicily, Italy) also releases high concentrations of trace elements to its surrounding seawater, and is therefore a unique site to examine the effects of long-term exposure of nearby organisms to high pCO2 and trace element enrichment in situ. The sea anemone Anemonia viridis is prevalent next to the Vulcano vent and does not show signs of trace element poisoning/stress. The aim of our study was to compare A. viridis trace element profiles and compartmentalization between high pCO2 and control environments. Rather than examining whole anemone tissue, we analyzed two different body compartments-the pedal disc and the tentacles, and also examined the distribution of trace elements in the tentacles between the animal and the symbiotic algae. We found dramatic changes in trace element tissue concentrations between the high pCO2/high trace element and control sites, with strong accumulation of iron, lead, copper and cobalt, but decreased concentrations of cadmium, zinc and arsenic proximate to the vent. The pedal disc contained substantially more trace elements than the anemone's tentacles, suggesting the pedal disc may serve as a detoxification/storage site for excess trace elements. Within the tentacles, the various trace elements displayed different partitioning patterns between animal tissue and algal symbionts. At both sites iron was found primarily in the algae, whereas cadmium, zinc and arsenic were primarily found in the animal tissue. Our data suggests that A. viridis regulates its internal trace element concentrations by compartmentalization and excretion and that these features contribute to its resilience and potential success at the trace element-rich high pCO2 vent.

Seawater carbonate chemistry and processes during experiments with Emiliania huxleyi (PML B93/11A)

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments. This is important in regulating marine carbon cycling and ocean-atmosphere CO2 exchange. The present rise in atmospheric CO2 levels causes significant changes in surface ocean pH and carbonate chemistry. Such changes have been shown to slow down calcification in corals and coralline macroalgae, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.