Multiproxy sedimentation patterns of sediment cores from the continental margin off northeast Brazil

Tropical regions have been reported to play a key role in climate dynamics. To date, however, there are uncertainties in the timing and the amplitude of the response of tropical ecosystems to millennial-scale climate change. We present evidence of an asynchrony between terrestrial and marine signals of climate change during Heinrich events preserved in marine sediment cores from the Brazilian continental margin. The inferred time lag of about 1000 to 2000 years is much larger than the ecological response to recent climate change and appears to be related to the nature of hydrological changes.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Carbon cycling in the northern Humboldt Current off Chile

The structure of the zooplankton foodweb and their dominant carbon fluxes were studied in the upwelling system off northern Chile (Mejillones Bay; 23°S) between October 2000 and December 2002. High primary production (PP) rates (18 gC/m**2 d) were mostly due to the net-phytoplankton size fraction (>23 µm). High PP has been traditionally associated with the wind-driven upwelling fertilizing effect of equatorial subsurface waters, which favour development of a short food chain dominated by a few small clupeiform fish species. The objective of the present work was to study the trophic carbon flow through the first step of this 'classical chain' (from phytoplankton to primary consumers such as copepods and euphausiids) and the carbon flow towards the gelatinous web composed of both filter-feeding and carnivorous zooplankton. To accomplish this objective, feeding experiments with copepods, appendicularians, ctenophores, and chaetognaths were conducted using naturally occurring plankton prey assemblages. Throughout the study, the total carbon ingestion rates showed that the dominant appendicularian species and small copepods consumed an average of 7 and 5 µgC/ind d, respectively. In addition, copepods ingested particles mainly in the size range of nano- and microplankton, whereas appendicularians ingested in the range of pico- and nanoplankton. Small copepods and appendicularians removed a small fraction of total daily PP (range 6-11%). However, when the pico- + nanoplankton fractions were the major contributors to total PP (oligotrophic conditions), grazing by small copepods increased markedly to 86% of total PP. Under these more oligotrophic conditions, the euphausiids grazing increased as well, but only reached values lower than 5% of total PP. During this study, chaetognaths and ctenophores ingested an average of 1 and 14 copepods/ind d, respectively. In terms of biomass consumed, the potential impact of carnivorous gelatinous zooplankton on the small-size copepod community (preferred prey) was important (2-12% of biomass removed daily). However, their impact produced more significant results on copepod abundance (up to 33%), which suggests that carnivorous gelatinous zooplankton may even modulate (control) the abundance of some species as well as the size structure of the copepod community.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.

Barium in sediments off northwest Africa

High-resolution down-core analyses of the solid phase content of total barium (Batot) and total organic carbon (TOC) back to 25 kyr B.P. were performed on a gravity core from the upper continental slope off Cape Yubi (Morocco). The observed discrepancy between the two potential paleoproductivity proxies, Batot and TOC, initiated supplementary examinations of the pore water, the geochemistry of the clay fraction, X-ray diffraction analyses, and the application of a sequential Ba extraction method of selected samples. Additionally, we analyzed down-core samples of the planktonic foraminifera Turborotalita quinqueloba and Globorotalia inflata for their Ba/Ca ratios. These analyses, which were performed for the first time on these species, were used to reconstruct past oceanic Ba concentrations. We suggest that in the study area, which is characterized by high accumulation rates, the preserved TOC content is a valuable proxy for past primary productivity, whereas the solid phase Batot contents appear to be affected by other mechanisms and factors. Peaks of total barium content in the clay fraction and of Ba/Ca ratios in the planktonic foraminifera shells found during the Younger Dryas and the Heinrich 1 event are likely to result from increased meltwater influx into the northern North Atlantic. We suggest that Ba-enriched meltwater was transmitted by the eastern boundary current system from higher latitudes to the region of the Canary Islands. Total barium contents of the clay fraction (Batot,clay) and Ba/Ca in planktonic foraminifera shells seem to be reliable proxies for this discharge of meltwater.

(Table 2) Comparison of annual mass fluxes measured with shallower and deeper sediment traps off Cape Blanc (CB)

The ocean off NW Africa is the second most important coastal upwelling system with a total annual primary production of 0.33 Gt of carbon per year (Carr in Deep Sea Res II 49:59-80, 2002). Deep ocean organic carbon fluxes measured by sediment traps are also fairly high despite low biogenic opal fluxes. Due to a low supply of dissolved silicate from subsurface waters, the ocean off NW Africa is characterized by predominantly carbonate-secreting primary producers, i.e. coccolithophorids. These algae which are key primary producers since millions of years are found in organic- and chlorophyll-rich zooplankton fecal pellets, which sink rapidly through the water column within a few days. Particle flux studies in the Mauretanian upwelling area (Cape Blanc) confirm the hypothesis of Armstrong et al. (Deep Sea Res II 49:219-236, 2002) who proposed that ballast availability, e.g. of carbonate particles, is essential to predict deep ocean organic carbon fluxes. The role of dust as ballast mineral for organic carbon, however, must be also taken into consideration in the coastal settings off NW Africa. There, high settling rates of larger particles approach 400 m day**-1, which may be due to a particular composition of mineral ballast. An assessment of particle settling rates from opal-production systems in the Southern Ocean of the Atlantic Sector, in contrast, provides lower values, consistent with the assumptions of Francois et al. (Global Biogeochem Cycles 16(4):1087, 2002). Satellite chlorophyll distributions, particle distributions and fluxes in the water column off NW Africa as well as modelling studies suggest a significant lateral flux component and export of particles from coastal shelf waters into the open ocean. These transport processes have implications for paleo-reconstructions from sediment cores retrieved at continental margin settings.

Particle camera and settling chamber measurements at site PC (GeoB11834-3) and SC (GeoB12914-4) off Cape Blanc/Mauritania

Particles sinking out of the euphotic zone are important vehicles of carbon export from the surface ocean. Most of the particles produce heavier aggregates by coagulating with each other before they sink. We implemented an aggregation model into the biogeochemical model of Regional Oceanic Modelling System (ROMS) to simulate the distribution of particles in the water column and their downward transport in the Northwest African upwelling region. Accompanying settling chamber, sediment trap and particle camera measurements provide data for model validation. In situ aggregate settling velocities measured by the settling chamber were around 55 m d**-1. Aggregate sizes recorded by the particle camera hardly exceeded 1 mm. The model is based on a continuous size spectrum of aggregates, characterised by the prognostic aggregate mass and aggregate number concentration. Phytoplankton and detritus make up the aggregation pool, which has an averaged, prognostic and size dependent sinking. Model experiments were performed with dense and porous approximations of aggregates with varying maximum aggregate size and stickiness as well as with the inclusion of a disaggregation term. Similar surface productivity in all experiments has been generated in order to find the best combination of parameters that produce measured deep water fluxes. Although the experiments failed to represent surface particle number spectra, in the deep water some of them gave very similar slope and spectrum range as the particle camera observations. Particle fluxes at the mesotrophic sediment trap site off Cape Blanc (CB) have been successfully reproduced by the porous experiment with disaggregation term when particle remineralisation rate was 0.2 d**-1. The aggregation-disaggregation model improves the prediction capability of the original biogeochemical model significantly by giving much better estimates of fluxes for both upper and lower trap. The results also point to the need for more studies to enhance our knowledge on particle decay and its variation and to the role that stickiness play in the distribution of vertical fluxes.

Radiocarbon measurements and loose-sediment quantification of seafloor sediment samples off northern Mauritania

Heterozoan carbonates are typical for extratropical sedimentary systems. However, under mesotrophic to eutrophic conditions, heterozoan carbonates also form in tropical settings. Nevertheless, such heterozoan tropical sedimentary systems are rare in the modern world and therefore are only poorly understood to date. Here a carbonate depositional system is presented where nutrient-rich upwelling waters push onto a wide shelf. These waters warm up in the shelf, giving rise to the production and deposition of tropical heterozoan facies. The carbonate facies on this shelf are characterized by a mixture of tropical and cosmopolitan biogenic sedimentary grains. Study of facies and taxonomy are the key for identifying and characterizing tropical heterozoan carbonates and for distinguishing them from their coolwater counterparts, in particular in the past where the oceanography cannot be determined directly.

Coral-algae metabolism and diurnal changes in the CO2-carbonate system of bulk sea water

Precise measurements were conducted in continuous flow seawater mesocosms located in full sunlight that compared metabolic response of coral, coral-macroalgae and macroalgae systems over a diurnal cycle. Irradiance controlled net photosynthesis (Pnet), which in turn drove net calcification (Gnet), and altered pH. Pnet exerted the dominant control on [CO3]2- and aragonite saturation state (Omega arag) over the diel cycle. Dark calcification rate decreased after sunset, reaching zero near midnight followed by an increasing rate that peaked at 03:00 h. Changes in Omega arag and pH lagged behind Gnet throughout the daily cycle by two or more hours. The flux rate Pnet was the primary driver of calcification. Daytime coral metabolism rapidly removes dissolved inorganic carbon (DIC) from the bulk seawater and photosynthesis provides the energy that drives Gnet while increasing the bulk water pH. These relationships result in a correlation between Gnet and Omega arag, with Omega arag as the dependent variable. High rates of H+ efflux continued for several hours following mid-day peak Gnet suggesting that corals have difficulty in shedding waste protons as described by the Proton Flux Hypothesis. DIC flux (uptake) followed Pnet and Gnet and dropped off rapidly following peak Pnet and peak Gnet indicating that corals can cope more effectively with the problem of limited DIC supply compared to the problem of eliminating H+. Over a 24 h period the plot of total alkalinity (AT) versus DIC as well as the plot of Gnet versus Omega arag revealed a circular hysteresis pattern over the diel cycle in the coral and coral-algae mesocosms, but not the macroalgae mesocosm. Presence of macroalgae did not change Gnet of the corals, but altered the relationship between Omega arag and Gnet. Predictive models of how future global changes will effect coral growth that are based on oceanic Omega arag must include the influence of future localized Pnet on Gnet and changes in rate of reef carbonate dissolution. The correlation between Omega arag and Gnet over the diel cycle is simply the response of the CO2-carbonate system to increased pH as photosynthesis shifts the equilibria and increases the [CO3]2- relative to the other DIC components of [HCO3]- and [CO2]. Therefore Omega arag closely tracked pH as an effect of changes in Pnet, which also drove changes in Gnet. Measurements of DIC flux and H+ flux are far more useful than concentrations in describing coral metabolism dynamics. Coral reefs are systems that exist in constant disequilibrium with the water column.

Depth integrated nitrogen fixation from the northern Benguela upwelling system during METEOR cruise M100/1

Nitrogen fixation data from the cruise number M100 with research vessel "Meteor" from 01.09.-01.10.2013 (1st leg from Walvis Bay to Walvis Bay) in front of Namibia. Samples taken by CTD- rosette sampler from different depths and incubated in glass bottles (270-1070 ml) at light intensities that resemble the in situ light intensities of the sampling depth after 15N2 gas was injected to the sample. After the incubation time of 24 hours, the complete bottle content was filtered onto a pre-combusted Whatman GF/F filter. Filters were frozen, transported to the institute on dry ice and measured in a mass spectrometer for Delta 15N. The principle of the method was described by Montoya et al. (1996) and calculation was done according to their spread sheet. From the data of the single depths, the nitrogen fixation per square meter within the upper 40 m of the water column was calculated. The methods are described in detail in a paper submitted by Wasmund et al. in 2014 to be printed in 2015. Some results are surprisingly below zero. This occurs if the Delta 15N of the blank is higher than the measurement after incubation. It indicates that no nitrogen fixation occurred. Due to natural variability, the variability of the nitrogen fixation data is high. In an overall estimate, also over several cruises, negative and positive values compensate more or less, suggesting that nitrogen fixation is insignificant in the waters in front of northern Namibia and southern Angola.

Seawater carbonate chemistry and processes during experiments with crabs Chionoecetes tanneri and Cancer magister, 2007

Rising levels of atmospheric carbon dioxide could be curbed by large-scale sequestration of CO2 in the deep sea. Such a solution requires prior assessment of the impact of hypercapnic, acidic seawater on deep-sea fauna. Laboratory studies were conducted to assess the short-term hypercapnic tolerance of the deep-sea Tanner crab Chionoecetes tanneri, collected from 1000 m depth in Monterey Canyon off the coast of central California, USA. Hemolymph acid- base parameters were monitored over 24 h of exposure to seawater equilibrated with ~1% CO2 (seawater PCO2 ~6 torr or 0.8 kPa, pH 7.1), and compared with those of the shallow-living Dungeness crab Cancer magister. Short-term hypercapnia-induced acidosis in the hemolymph of Chionoecetes tanneri was almost uncompensated, with a net 24 h pH reduction of 0.32 units and a net bicarbonate accumulation of only 3 mM. Under simultaneous hypercapnia and hypoxia, short-term extracellular acidosis in Chionoecetes tanneri was completely uncompensated. In contrast, Cancer magister fully recovered its hemolymph pH over 24 h of hypercapnic exposure by net accumulation of 12 mM bicarbonate from the surrounding medium. The data support the hypothesis that deep-sea animals, which are adapted to a stable environment and exhibit reduced metabolic rates, lack the short-term acid-base regulatory capacity to cope with the acute hypercapnic stress that would accompany large-scale CO2 sequestration. Additionally, the data indicate that sequestration in oxygen-poor areas of the ocean would be even more detrimental to deep-sea fauna.