Geochemistry measured on sediment core GeoB12309-5

Laminated sediment records from the oxygen minimum zone in the Arabian Sea offer unique ultrahigh-resolution archives for deciphering climate variability in the Arabian Sea region. Although numerous analytical techniques are available it has become increasingly popular during the past decade to analyze relative variations of sediment cores' chemical signature by non-destructive X-ray fluorescence (XRF) core scanning. We carefully selected an approximately 5 m long sediment core from the northern Arabian Sea (GeoB12309-5: 24°52.3' N; 62°59.9' E, 956 m water depth) for a detailed, comparative study of high-resolution techniques, namely non-destructive XRF core scanning (0.8 mm resolution) and ICP-MS/OES analysis on carefully selected, discrete samples (1 mm resolution). The aim of our study was to more precisely define suitable chemical elements that can be accurately analyzed and to determine which elemental ratios can be interpretated down to sub-millimeter-scale resolutions. Applying the Student's t-test our results show significantly correlating (1% significance level) elemental patterns for all S, Ca, Fe, Zr, Rb, and Sr, as well as the K/Ca, Fe/Ti and Ti/Al ratios that are all related to distinct lithological changes. After careful consideration of all errors for the ICP analysis we further provide respective factors of XRF Core Scanner software error's underestimation by applying Chi-square-tests, which is especially relevant for elements with high count rates. As demonstrated by these new, ultra-high resolution data core scanning has major advantages (high-speed, low costs, few sample preparation steps) and represents an increasingly required alternative over the time consuming, expensive, elaborative, and destructive wet chemical analyses (e.g., by ICP-MS/OES after acid digestions), and meanwhile also provides high-quality data in unprecedented resolution.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Strong shift from HCO3- to CO2 uptake in Emiliania huxleyi with acidification: new approach unravels acclimation versus short-term pH effects

Effects of ocean acidification on Emiliania huxleyi strain RCC 1216 (calcifying, diploid life-cycle stage) and RCC 1217 (non-calcifying, haploid life-cycle stage) were investigated by measuring growth, elemental composition, and production rates under different pCO2 levels (380 and 950 µatm). In these differently acclimated cells, the photosynthetic carbon source was assessed by a (14)C disequilibrium assay, conducted over a range of ecologically relevant pH values (7.9-8.7). In agreement with previous studies, we observed decreased calcification and stimulated biomass production in diploid cells under high pCO2, but no CO2-dependent changes in biomass production for haploid cells. In both life-cycle stages, the relative contributions of CO2 and HCO3 (-) uptake depended strongly on the assay pH. At pH values =< 8.1, cells preferentially used CO2 (>= 90 % CO2), whereas at pH values >= 8.3, cells progressively increased the fraction of HCO3 (-) uptake (~45 % CO2 at pH 8.7 in diploid cells; ~55 % CO2 at pH 8.5 in haploid cells). In contrast to the short-term effect of the assay pH, the pCO2 acclimation history had no significant effect on the carbon uptake behavior. A numerical sensitivity study confirmed that the pH-modification in the (14)C disequilibrium method yields reliable results, provided that model parameters (e.g., pH, temperature) are kept within typical measurement uncertainties. Our results demonstrate a high plasticity of E. huxleyi to rapidly adjust carbon acquisition to the external carbon supply and/or pH, and provide an explanation for the paradoxical observation of high CO2 sensitivity despite the apparently high HCO3 (-) usage seen in previous studies.

Seawater carbonate chemistry and proportion of different dissolution levels in live juvenile Limacina helicina antarctica from the natural environment and ship-board incubations

The carbonate chemistry of the surface ocean is rapidly changing with ocean acidification, a result of human activities. In the upper layers of the Southern Ocean, aragonite-a metastable form of calcium carbonate with rapid dissolution kinetics-may become undersaturated by 2050. Aragonite undersaturation is likely to affect aragonite-shelled organisms, which can dominate surface water communities in polar regions. Here we present analyses of specimens of the pteropod Limacina helicina antarctica that were extracted live from the Southern Ocean early in 2008. We sampled from the top 200 m of the water column, where aragonite saturation levels were around 1, as upwelled deep water is mixed with surface water containing anthropogenic CO2. Comparing the shell structure with samples from aragonite-supersaturated regions elsewhere under a scanning electron microscope, we found severe levels of shell dissolution in the undersaturated region alone. According to laboratory incubations of intact samples with a range of aragonite saturation levels, eight days of incubation in aragonite saturation levels of 0.94-1.12 produces equivalent levels of dissolution. As deep-water upwelling and CO2 absorption by surface waters is likely to increase as a result of human activities, we conclude that upper ocean regions where aragonite-shelled organisms are affected by dissolution are likely to expand.

Stable isotope analysis of Porites coral core from the Andaman Islands

North Atlantic climate variations are reflected in sedimentary records from the northern Indian Ocean in which two basins, the Arabian Sea and the Bay of Bengal, are strongly affected by the monsoon. Contrary to the Bay of Bengal the Arabian Sea plays an important role in the global marine nitrogen cycle. In its mid-water oxygen minimum zone (OMZ) bioavailable fixed nitrogen is reduced to nitrogen gas (NO3- - > N2), whereas oxygen concentrations are slightly above the threshold of nitrate reduction in the OMZ of the Bay of Bengal. A coral colony (Porites lutea) growing south of Port Blair on the Andaman Islands in the Bay of Bengal was studied for its response to changes in the monsoon system and its link to temperature changes in the North Atlantic Ocean, between 1975 and 2006. Its linear extension rates, d13C and d18O values measured within the coral skeleton reveal a strong seasonality, which seems to be caused by the monsoon-driven reversal of the surface ocean circulation. The sampling site appears to be influenced by low salinity Bay of Bengal Water during the NE monsoon (boreal winter) and by the high salinity Arabian Sea Water during the SW monsoon in summer. The high salinity Arabian Sea Water circulates along with the Summer Monsoon Current (S-MC) from the Arabia Sea into the Bay of Bengal. Decreasing d18O and reconstructed salinity values correlate to the increasing SSTs in the North Atlantic Ocean indicating a reduced influence of the S-MC at the sampling site in the course of northern hemispheric warming. During such periods oxygen-depletion became stronger in the OMZ of the Arabian Sea as indicated by the sedimentary records. A reduced propagation of oxygen-depleted high salinity Arabian Sea Water into the Bay of Bengal could be a mechanism maintaining oxygen concentration above the threshold of nitrate reduction in the OMZ of the Bay of Bengal in times of global warming.

Bolboforma abundance in ODP Hole 162-982A and DSDP Hole 12-116 sediments

Although they are fossils of uncertain origin, bolboforms are the best calcareous microfossil group for Neogene biostratigraphy in the North Atlantic. Fifty-two Bolboforma species were observed at the Hatton-Rockall Basin in Ocean Drilling Program Holes 982A (26 samples) and 982B (301 samples) and in Deep Sea Drilling Project Hole 116 (71 samples). The sequence investigated spans the interval from lower Miocene to upper Pliocene. Fourteen zones/subzones were identified and correlated with the calcareous nannoplankton zones, the planktonic foraminifer biostratigraphy, and the time (Ma). The last occurrence of the genus Bolboforma can be dated to 2.84 Ma. Different Bolboforma specimens of middle Miocene age, observed in upper Miocene and upper middle Miocene sediments at Site 982, document redeposition of sediment from the Rockall Bank into the Hatton-Rockall Basin during the latest middle Miocene and late Miocene.

Bolboforma in Paleogene sediments of the Subantarctic

Sediments from ODP Holes 699A, 700B, 702B, 703A, and 704B were studied in order to determine and to understand the distribution of Bolboforma. Ten Bolboforma taxa were detected in the 294 samples analyzed. Based on Bolboforma species, a zonation correlated to the paleomagnetic record is proposed for the late middle Eocene to early Oligocene. Four biozones can be defined: the Bolboforma indistincta Zone for the lower part of the upper middle Eocene sequence, the Bolboforma eocena Zone for the upper part of the upper middle Eocene to upper Eocene, the Bolboforma geomaris Zone for the upper Eocene, and the Bolboforma latdorfensis Zone for the lower Oligocene sequence.