Terrestrial organic matter in marine sediments of the Central Equatorial Atlantic

Terrestrial organic matter (OM) in pelagic sediments is discussed with regard to depositional processes and land-sea interactions in the modern and past glacial/interglacial Equatorial Atlantic. Special emphasis is placed on a critical evaluation of different analytical approaches (C/N, Rock-Eval Pyrolysis, stable carbon isotopes, palynology, organic petrology, and selected biomarkers) which are currently used for the qualitative and quantitative assessment of terrigenous organic carbon. If binary mixing equations are used to calculate terrestrial and marine proportions of organic carbon, we consider the definition of endmember values to be most critical since these values may be biased by a great number of independent controls. A combination of geochemical methods including optical studies (organic petrology and palynology) is therefore suggested to evaluate each individual proxy. Organic geochemical analyses performed on sediments from the modern and Late Quaternary Equatorial Atlantic evidence fluctuations in eolian supply of terrigenous OM related to changes in intensity of the trade winds. Quantification of this organic fraction leads to differing proportions depending on the approach applied, i.e. the organic carbon isotopic composition or maceral analyses. Modern distribution of terrigenous OM reveals a decrease in supply towards the basin contributing less than a fifth of the total OM in pelagic areas. Organic geochemical data indicate that sedimentation in the modern northeastern Brasil Basin is affected by lateral advection of reworked OM probably from southern source areas. Glacial/interglacial deposits from the pelagic Equatorial Atlantic (ODP Site 663), covering isotopic stages 12 and 11, reveal that deposition of terrigenous OM was higher under past glacial conditions, in correspondence to generally enhanced dust fluxes. Proportions of terrigenous OM, however, never exceed 50% of the total OM according to maceral analyses. Other estimates, recently proposed by Verardo and Ruddiman (1996), are considered to be too high probably for analytical reasons. Palynological records in the Equatorial Atlantic parallel dust records. Increased portions of grass pollen suggest the admixture of C4-plant material under modern and past glacial conditions. It is therefore assumed, as one possible interpetation, that C4-plant debris has an effect on sedimentary d13Corg and might explain differences between isotopic and microscopic quantitative estimates. Using the difference between these two records, we calculate that maximum supply of C4-material remains below 20% of the total OM for the deep modern and past glacial/interglacial Equatorial Atlantic.

Multicentennial resolution proxy records from splicings of MD96-2080 and MD02-2594, Agulhas Bank Splice (ABS)

[1] Planktonic d18O and Mg/Ca-derived sea surface temperature (SST) records from the Agulhas Corridor off South Africa display a progressive increase of SST during glacial periods of the last three climatic cycles. The SST increases of up to 4°C coincide with increased abundance of subtropical planktonic foraminiferal marker species which indicates a progressive warming due to an increased influence of subtropical waters at the core sites. Mg/Ca-derived SST maximizes during glacial maxima and glacial Terminations to values about 2.5°C above full-interglacial SST. The paired planktonic d18O and Mg/Ca-derived SST records yield glacial seawater d18O anomalies of up to 0.8 per mill, indicating measurably higher surface salinities during these periods. The SST pattern along our record is markedly different from a UK'37-derived SST record at a nearby core location in the Agulhas Corridor that displays SST maxima only during glacial Terminations. Possible explanations are lateral alkenone advection by the vigorous regional ocean currents or the development of SST contrasts during glacials in association with seasonal changes of Agulhas water transports and lateral shifts of the Agulhas retroflection. The different SST reconstructions derived from UK'37 and Mg/Ca pose a significant challenge to the interpretation of the proxy records and demonstrate that the reconstruction of the Agulhas Current and interocean salt leakage is not as straightforward as previously suggested.

Sedimentology and geochemistry of core GIK23258-2 in the Barents Sea

At the western continental margin of the Barents Sea, 75°N, hemipelagic sediments provide a record of Holocene climate change with a time resolution of 10-70 years. Planktic foraminifera counts reveal a very early Holocene thermal optimum 10.7-7.7 kyr BP, with summer sea surface temperatures (SST) of 8°C and a much enhanced West Spitsbergen Current. There was a short cooling between 8.8 and 8.2 kyr BP. In the middle and late Holocene summer, SST dropped to 2.5°-5.0°C, indicative of reduced Atlantic heat advection, except for two short warmings near 2.2 and 1.6 kyr BP. Distinct quasi-periodic spikes of coarse sediment fraction (with large portions of lithic grains, benthic and planktic foraminifera) record cascades of cold, dense winter water down the continental slope as a result of enhanced seasonal sea ice formation and storminess on the Barents shelf over the entire Holocene. The spikes primarily cluster near recurrence intervals of 400-650 and 1000-1350 years, when traced over the entire Holocene, but follow significant 885-/840- and 505-/605-year periodicities in the early Holocene. These non-stationary periodicities mimic the Greenland-[Formula: See Text]Be variability, which is a tracer of solar forcing. Further significant Holocene periodicities of 230, (145) and 93 years come close to the deVries and Gleissberg solar cycles.

Dissolved Si isotope composition measured in water samples during METEOR cruises M77/3 and M77/4

Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (d30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50'W and 82°00'W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions d30Si(OH)4 (+2.2 per mil to +4.4 per mil) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 µmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 µmol/kg are characterized by a large range in d30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the d30Si(OH)4 signature in the subsurface water column. Deep water masses (>2000 m) in the study area show a mean d30Si(OH)4 of +1.2±0.2 per mil, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher d30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between d30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of d30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a consequence of the mixing of several end member water masses with distinct Si isotope signatures including Lower Circumpolar Deep Water (LCDW) and North Pacific Deep Water (NPDW).

Analytical results from sediment core MD03-2698

It is well established that orbital scale sea-level changes generated larger transport of sediments into the deep-sea during the last glacial maximum than the Holocene. However, the response of sedimentary processes to abrupt millennial-scale climate variability is rather unknown. Frequency of distal turbidites and amounts of advected detrital carbonate are estimated off the Lisbon-Setúbal canyons, within a chronostratigraphy based on radiometric ages, oxygen isotopes and paleomagnetic key global anomalies. We found that: 1) Higher frequency of turbidites concurred with Northern Hemisphere coldest temperatures (Greenland Stadials [GS], including Heinrich [H] events). But more than that, an escalating frequency of turbidites starts with the onset of global sea-level rising (and warming in Antarctica) and culminates during H events, at the time when rising is still in its early-mid stage, and the Atlantic Meridional Overturning Circulation (AMOC) is re-starting. This short time span coincides with maximum gradients of ocean surface and bottom temperatures between GS and Antarctic warmings (Antarctic Isotope Maximum; AIM 17, 14, 12, 8, 4, 2) and rapid sea-level rises. 2) Trigger of turbidity currents is not the only sedimentary process responding to millennial variability; land-detrital carbonate (with a very negative bulk d18O signature) enters the deep-sea by density-driven slope lateral advection, accordingly during GS. 3) Possible mechanisms to create slope instability on the Portuguese continental margin are sea-level variations as small as 20 m, and slope friction by rapid deep and intermediate re-accommodation of water masses circulation. 4) Common forcing mechanisms appear to drive slope instability at both millennial and orbital scales.

(Table 2) Composition of the deapest pore fluids from ODP Holes 168-1030B and 168-1031A

On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by

Seawater carbonate chemistry and swimming behaviors of the raphidophyte Heterosigma akashiwo in a laboratory experiment

We investigated the effects of pH on movement behaviors of the harmful algal bloom causing raphidophyte Heterosigma akashiwo. Motility parameters from >8000 swimming tracks of individual cells were quantified using 3D digital video analysis over a 6-h period in 3 pH treatments reflecting marine carbonate chemistry during the pre-industrial era, currently, and the year 2100. Movement behaviors were investigated in two different acclimation-to-target-pH conditions: instantaneous exposure and acclimation of cells for at least 11 generations. There was no negative impairment of cell motility when exposed to elevated PCO2 (i.e., low pH) conditions but there were significant behavioral responses. Irrespective of acclimation condition, lower pH significantly increased downward velocity and frequency of downward swimming cells (p < 0.001). Rapid exposure to lower pH resulted in 9% faster downward vertical velocity and up to 19% more cells swimming downwards (p < 0.001). Compared to pH-shock experiments, pre-acclimation of cells to target pH resulted in ~30% faster swimming speed and up to 46% faster downward velocities (all p < 0.001). The effect of year 2100 PCO2 levels on population diffusivity in pre-acclimated cultures was >2-fold greater than in pH-shock treatments (2.2 × 105 µm**2/s vs. 8.4 × 104 µm**2/s). Predictions from an advection-diffusion model, suggest that as PCO2 increased the fraction of the population aggregated at the surface declined, and moved deeper in the water column. Enhanced downward swimming of H. akashiwo at low pH suggests that these behavioral responses to elevated PCO2 could reduce the likelihood of dense surface slick formation of H. akashiwo through reductions in light exposure or growth independent surface aggregations. We hypothesize that the HAB alga's response to higher PCO2 may exploit the signaling function of high PCO2 as indicative of net heterotrophy in the system, thus indicative of high predation rates or depletion of nutrients.

Seawater carbonate chemistry and calcification in the Bahama Bank, 1964-1965

Carbon dioxide is lost from the ocean by calcium carbonate precipitation (-p), photosynthesis (-b) and gas evasion at the sea surface (-g). Among the most active sites are warm shallow seas. In this paper seasonal studies on the Great Bahama Bank relate these processes in an equation which takes into account the indirect effects of advection (a), evaporation (e), and eddy diffusion (d). Calcium carbonate precipitation is very seasonal and accounts for about half of the total losses. The delta sum CO2/deltaCa ratio is always about 1.87 on the bank. A high summer carbonate loss is inversely correlated with summer increases of chlorinity and temperature suggesting that CaCO3 is precipitated inorganically or biogenic production of CaCO3 is regulated by these parameters or both.

On the effects of circulation, sediment resuspension and biological incorporation by diatoms in an ocean model of aluminium, link to model data

The distribution of dissolved aluminium in the West Atlantic Ocean shows a mirror image with that of dissolved silicic acid, hinting at intricate interactions between the ocean cycling of Al and Si. The marine biogeochemistry of Al is of interest because of its potential impact on diatom opal remineralisation, hence Si availability. Furthermore, the dissolved Al concentration at the surface ocean has been used as a tracer for dust input, dust being the most important source of the bio-essential trace element iron to the ocean. Previously, the dissolved concentration of Al was simulated reasonably well with only a dust source, and scavenging by adsorption on settling biogenic debris as the only removal process. Here we explore the impacts of (i) a sediment source of Al in the Northern Hemisphere (especially north of ~ 40° N), (ii) the imposed velocity field, and (iii) biological incorporation of Al on the modelled Al distribution in the ocean. The sediment source clearly improves the model results, and using a different velocity field shows the importance of advection on the simulated Al distribution. Biological incorporation appears to be a potentially important removal process. However, conclusive independent data to constrain the Al / Si incorporation ratio by growing diatoms are missing. Therefore, this study does not provide a definitive answer to the question of the relative importance of Al removal by incorporation compared to removal by adsorptive scavenging.

Stable isotope ratios on 3 sediment cores from Tagus prodelta off Lisbon

A high-resolution sedimentary sequence recovered from the Tagus prodelta has been studied with the objective to reconstruct multi-decadal to centennial-scale climate variability on the western Iberian Margin and to discuss the observations in a wider oceanographic and climatic context. Between ca. 100 BC and AD 400 the foraminiferal fauna and high abundance of Globorotalia inflata indicate advection of subtropical waters via the Azores Current and the winter-time warm Portugal Coastal Current. Between ca. AD 400 and 1350, encompassing the Medieval Climate Anomaly (MCA), enhanced upwelling is indicated by the planktonic foraminiferal fauna, in particular by the high abundance of upwelling indicator species Globigerina bulloides. Relatively light d18O values and high sea surface temperature (SST) (reconstructed from foraminiferal assemblages) point to upwelling of subtropical Eastern North Atlantic Central Water. Between ca. AD 1350 and 1750, i.e. most of the Little Ice Age, relatively heavy d18O values and low reconstructed SST, as well as high abundances of Neogloboquadrina incompta, indicate the advection of cold subpolar waters to the area and a southward deflection of the subpolar front in the North Atlantic, as well as changes in the mode of the North Atlantic Oscillation. In addition, the assemblage composition together with the other proxy data reveals less upwelling and stronger river input than during the MCA. Stronger Azores Current influence on the Iberian Margin and strong anthropogenic effect on the climate after AD 1750 is indicated by the foraminiferal fauna. The foraminiferal assemblage shows a significant change in surface water conditions at ca. AD 1900, including enhanced river runoff, a rapid increase in temperature and increased influence of the Azores Current. The Tagus record displays a high degree of similarity to other North Atlantic records, indicating that the site is influenced by atmospheric-oceanic processes operating throughout the North Atlantic, as well as by local changes.

Planktic foraminiferal abundance and faunal-derived sea surface temperature of eastern equatorial Pacific ODP Site 202-1240

Glacial cooling (~1-5°C) in the eastern equatorial Pacific (EEP) cold tongue is often attributed to increased equatorial upwelling, stronger advection from the Peru-Chile Current (PCC), and to the more remote subpolar southeastern Pacific water mass. However, evidence is scarce for identifying unambiguously which process plays a more important role in driving the large glacial cooling in the EEP. To address this question, here we adopt a faunal calibration approach using planktic foraminifers with a new compilation of coretop data from the eastern Pacific, and present new downcore variation data of fauna assemblage and estimated sea surface temperatures (SSTs) for the past 160 ka (Marine Isotope Stage (MIS) 6) from ODP Site 1240 in the EEP. With significant improvement achieved by adding more coretop data from the eastern boundary current, our downcore calibration results indicate that most of the glacial cooling episodes over the past 160 ka in the EEP are attributable to increased influence from the subpolar water mass from high latitudes of the southern Pacific. By applying this new calibration of the fauna SST transfer function to a latitudinal transect of eastern Pacific (EP) cores, we find that the subpolar water mass has been a major dynamic contributor to EEP cold tongue cooling since MIS 6.

(Table 2) 230Th, 230Th xs and 232Th concentrations in dissolved, particulate and total (dissolved+small particles) for all KEOPS stations, Marion Dufresne cruise MD145

In the context of the KErguelen Ocean and Plateau compared Study (KEOPS, 19 January-13 February 2005), particle dynamics were investigated using thorium isotope measurements over and off the Kerguelen plateau. Dissolved and particulate 230Th and 232Th samples were collected at nine stations. Dissolved excess 230Th concentrations (230Thxs) vary from 0.5 to 20.8 fg/kg and particulate 230Thxs concentrations from 0.1 to 10.0 fg/kg. Dissolved and particulate 232Th concentration ranges are 16.8-450.2 pg/kg and 3.8-502.8 pg/kg, respectively. The 230Thxs concentrations increase linearly with depth down to the bottom at most of the plateau stations and down to 1000 m at the off-plateau stations. This linear trend is observed down to the bottom (1550 m) at Kerfix, the open-ocean "upstream" station located west of the Kerguelen plateau. A simple reversible scavenging model applied to these data allowed the estimation of adsorption rate constant (k1~=0.2-0.8 per year), desorption rate constant (k-1~=1-8 per year) and partition coefficients (average K=0.16±0.07). Calculated particle settling velocities S deduced from this simple model are ca. 500 m/year at most of the plateau stations and 800 m/year at all the off-plateau stations. The plateau settling velocities are relatively low for such a productive site, compared to the surrounding HNLC areas. The difference might reflect the fact that lateral advection is neglected in this model. Taking this advection into account allows the reconstruction of the observed 230Thxs linear distributions, but only if faster settling velocities are considered. This implies that the 1D model strongly underestimates the settling velocity of the particles. In the deep layers, the occurrence of intense boundary scavenging along the escarpment due to bottom sediment re-suspension and interaction with a nepheloid layer, yielding a removal of ?50% of the Th stock along the northwestward transect, is suggested.