Stable isotopic and carbonate cyclicity in deep sea sediments from different DSDP Holes

Oxygen and carbon isotopic variability of the dominant (<38 µm) carbonate fraction within bedded, organic-carbon rich Lower Cretaceous sediment intervals from various DSDP sites are closely correlated with preservational changes in the carbonates. Isotopic fluctuations are absent where carbonate contents vary little and where the carbonate fraction is dominated by biogenic phytoplankton remains. Within each of the studied intervals oxygen and carbon isotopic ratios become increasingly more negative in samples with carbonate contents higher than about 60% in which the proportion of diagenetic microcarbonate increases rapidly. Carbon isotopic ratios show a trend towards positive values in samples with carbonate contents of less than 40% and strong signs of dissolution. The taxonomic composition of nannofossil assemblages varies little within single intervals, despite significant differential diagenesis among individual beds; this points towards ecological stability of oceanic surface waters during the deposition of alternating beds. Bedding is, however, closely related to changing bioturbation intensity, indicating repeated fluctuations of the deep-water renewal rates and oxygen supply. Various microbial decomposition processes of organic matter leading to bed-specific differential carbonate diagenesis resulted in an amplification of primary bedding features and are considered responsible for most of the observed fluctuations in the stable isotopic ratios and carbonate contents.

Foraminiferal Mg/Ca and Mn/Ca ratios across the Eocene-Oligocene transition

Constraining the magnitude of high-latitude temperature change across the Eocene-Oligocene transition (EOT) is essential for quantifying the magnitude of Antarctic ice-sheet expansion and understanding regional climate response to this event. To this end, we constructed high-resolution stable oxygen isotope (d18O) and magnesium/calcium (Mg/Ca) records from planktic and benthic foraminifera at four Ocean Drilling Program (ODP) sites in the Southern Ocean. Planktic foraminiferal Mg/Ca records from the Kerguelen Plateau (ODP Sites 738, 744, and 748) show a consistent pattern of temperature change, indicating 2-3 °C cooling in direct conjunction with the first step of a two-step increase in benthic and planktic foraminiferal d18O values across the EOT. In contrast, benthic Mg/Ca records from Maud Rise (ODP Site 689) and the Kerguelen Plateau (ODP Site 748) do not exhibit significant temperature change. The contrasting temperature histories derived from the planktic and benthic Mg/Ca records are not reconcilable, since vertical d18O gradients remained nearly constant at all sites between 35.0 and 32.5 Ma. Based on the coherency of the planktic Mg/Ca records from the Kerguelen Plateau sites and complications with benthic Mg/Ca paleothermometry at low temperatures, the planktic Mg/Ca records are deemed the most reliable measure of Southern Ocean temperature change. We therefore interpret a uniform cooling of 2-3 °C in both deep surface (thermocline) waters and intermediate deep waters of the Southern Ocean across the EOT. Cooling of Southern Ocean surface waters across the EOT was likely propagated to the deep ocean, since deep waters were primarily sourced on the Antarctic margin throughout this time interval. Removal of the temperature component from the observed foraminiferal d18O shift indicates that seawater d18O values increased by 0.6 ± 0.15 per mil across the EOT interval, corresponding to an increase in global ice volume to a level equivalent with 60-130% modern East Antarctic ice sheet volume.

Species-specific consequences of ocean acidification for the calcareous tropical green algae Halimeda, 2011

Ocean acidification (OA), resulting from increasing dissolved carbon dioxide (CO2) in surface waters, is likely to affect many marine organisms, particularly those that calcify. Recent OA studies have demonstrated negative and/or differential effects of reduced pH on growth, development, calcification and physiology, but most of these have focused on taxa other than calcareous benthic macroalgae. Here we investigate the potential effects of OA on one of the most common coral reef macroalgal genera,Halimeda. Species of Halimeda produce a large proportion of the sand in the tropics and are a major contributor to framework development on reefs because of their rapid calcium carbonate production and high turnover rates. On Palmyra Atoll in the central Pacific, we conducted a manipulative bubbling experiment to investigate the potential effects of OA on growth, calcification and photophysiology of 2 species of Halimeda. Our results suggest that Halimeda is highly susceptible to reduced pH and aragonite saturation state but the magnitude of these effects is species specific. H. opuntiasuffered net dissolution and 15% reduction in photosynthetic capacity, while H. taenicola did not calcify but did not alter photophysiology in experimental treatments. The disparate responses of these species to elevated CO2 partial -pressure (pCO2) may be due to anatomical and physiological differences and could represent a shift in their relative dominance in the face of OA. The ability for a species to exert biological control over calcification and the species specific role of the carbonate skeleton may have important implications for the potential effects of OA on ecological function in the future.

Iron in the Sargasso Sea

We report iron measurements for water column and aerosol samples collected in the Sargasso Sea during July-August 2003 (summer 2003) and April-May 2004 (spring 2004). Our data reveal a large seasonal change in the dissolved iron (dFe) concentration of surface waters in the Bermuda Atlantic Time-series Study region, from ~1-2 nM in summer 2003, when aerosol iron concentrations were high (mean 10 nmol/m**3), to ~0.1-0.2 nM in spring 2004, when aerosol iron concentrations were low (mean 0.64 nmol/m**3). During summer 2003, we observed an increase of ~0.6 nM in surface water dFe concentrations over 13 days, presumably due to eolian iron input; an estimate of total iron deposition over this same period suggests an effective solubility of 3-30% for aerosol iron. Our summer 2003 water column profiles show potentially growth-limiting dFe concentrations (0.02-0.19 nM) coinciding with a deep chlorophyll maximum at 100-150 m depth, where phytoplankton biomass is typically dominated by Prochlorococcus during late summer.

(Table 2) Taxonomic composition of diatoms from bottom deposits of the Kronotsky Bay

Eocene diatom and silicoflagellate complexes from deposits of the Kronotsky Bay are presented. Pro tempore they are the most ancient finds of fossil phytoplankton with silica skeletons in the Northwest Pacific. More than 130 diatom species belonging to 59 genera and 24 silicoflagellate species belonging to 5 genera have been determined. Three Middle Eocene complexes (of the Lisitzinia kanayai, Lisitzinia inconspicua var. trilobata, and Praecymatosira monomembranaceae zones) and one presumably Middle-Late Eocene complex (of the zone with Rylandsia conniventa) of diatoms have been identified. For the first time a large silicoflagellate complex attributable to the Dictyocha hexacantha zone is presented. It is assumed that the complexes formed mainly in bathyal conditions at relatively high (close to sub-tropical) temperatures of surface waters.

Tintinnids of the western Arabian Sea

The results of an investigation of tintinnids from the western Arabian Sea are described. A total of 134 closing-net samples was obtained from 22 stations of the German "Meteor" expedition 1964/1965. Distribution charts of the dominant species of tintinnids from the study area are presented as well as a list of the world-wide distribution of these species as derived from the literature. Tintinnids were most abundant in the surface waters. The layer from 0 - 25 m yielded a maximum 94.3% and a minimum of 61.3% of the tintinnids present from 0 - 175 m; the mean was 80%. There was no significant difference in the vertical distribution between day and night stations nor was there any indication of the influence of the thermocline upon vertical distribution of tintinnids. TS-diagrams show different water types in the western Arabian Sea. Temperatur-salinity-tintinnid -diagrams indicate regional patterns in the distribution of various species of tintinnids. Some tintinnids can be used as indicator species: Climacocylis scalaria, Parundella lohmanni and Amphorella amphora were typical for the Somali Current whereas Rhabdonella apophysata and Branditella palliata indicated the presence of East African Coastal Current water. The concentration of tintinnids in the upper 25 m raged between 4,800 and 39,300 individuals/m**3 (mean 19,000/m**3). Plasma volume of tintinnids was calculated to permit comparison of different links in the food chain. There was a mean of 51 mm**3/m**2 in the upper layer, equivalent to a concentration of 2 mm**3/m**3. Carbon values were computed from the plasma volume of tintinnids, phytoplankton and larger zooplankton. The ratio of phytoplankton plus microzooplankton carbon to large zooplankton carbon was 1 : 0.8 in the Somali Current, 1 : 0.4 in the East African Coastal Current and 1 : 1.2 in the mixing zone of these current systems. Tintinnids are one of the first links in the food chain. It is very likely that a part of the organic detritus and of the nanoplankton is transfered to large herbivores or omnivores via tintinnids and other protozoans. This mechanism might be especially effective during seasons when large phytoplankters are not available in the ocean.

Seawater carbonate chemistry and physiological and mechanical properties of the starfish Asterias rubens in a laboratory experiment

The increase in atmospheric CO2 due to anthropogenic activity results in an acidification of the surface waters of the oceans. Its impact will depend on the considered organisms and ecosystems. The intertidal may harbor organisms pre-adapted to the upcoming changes as they face tidal pH and temperature fluctuations. However, these environments will be more affected as shallow waters will face the highest decrease in seawater pH. In this context, the effects of reduced environmental pH on the physiology and tube feet mechanical properties of the intertidal starfish Asterias rubens, a top predator, were investigated during 15 and 27 days. A. rubens showed a respiratory acidosis with its coelomic fluid pH always lower than that of seawater. This acidosis was most pronounced at pH 7.4. Notwithstanding, the starfish showed no significant variations in RNA/DNA ratio of different tissues and in tube feet strength. However, respiration rates were significantly lower for individuals maintained at reduced seawater pH. Within the ocean acidification context, the present results suggest that A. rubens withstands the effects of reduced seawater pH, at least for medium term exposures.

Seawater carbonate chemistry and buffer capacity of the coelomic fluid in echinoderms in a laboratory experiment

The increase in atmospheric CO2 due to anthropogenic activity results in an acidification of the surface waters of the oceans. The impact of these chemical changes depends on the considered organisms. In particular, it depends on the ability of the organism to control the pH of its inner fluids. Among echinoderms, this ability seems to differ significantly according to species or taxa. In the present paper, we investigated the buffer capacity of the coelomic fluid in different echinoderm taxa as well as factors modifying this capacity. Euechinoidea (sea urchins except Cidaroidea) present a very high buffer capacity of the coelomic fluid (from 0.8 to 1.8 mmol/kg SW above that of seawater), while Cidaroidea (other sea urchins), starfish and holothurians have a significantly lower one (from -0.1 to 0.4 mmol/kg SW compared to seawater). We hypothesize that this is linked to the more efficient gas exchange structures present in the three last taxa, whereas Euechinoidea evolved specific buffer systems to compensate lower gas exchange abilities. The constituents of the buffer capacity and the factors influencing it were investigated in the sea urchin Paracentrotus lividus and the starfish Asterias rubens. Buffer capacity is primarily due to the bicarbonate buffer system of seawater (representing about 63% for sea urchins and 92% for starfish). It is also partly due to coelomocytes present in the coelomic fluid (around 8% for both) and, in P. lividus only, a compound of an apparent size larger than 3 kDa is involved (about 15%). Feeding increased the buffer capacity in P. lividus (to a difference with seawater of about 2.3 mmol/kg SW compared to unfed ones who showed a difference of about 0.5 mmol/kg SW) but not in A. rubens (difference with seawater of about 0.2 for both conditions). In P. lividus, decreased seawater pH induced an increase of the buffer capacity of individuals maintained at pH 7.7 to about twice that of the control individuals and, for those at pH 7.4, about three times. This allowed a partial compensation of the coelomic fluid pH for individuals maintained at pH 7.7 but not for those at pH 7.4.

Maastrichtian calcareous nannofossils of Kronsmoor-Section

The latest Campanian-earliest Maastrichtian interval is well known as a period of intense climate cooling. This cooling caused a distinctive bipolar biogeographic distribution of calcareous nannofossil assemblages: High latitude settings were dominated by newly evolving endemic taxa, former cosmopolitan species disappeared at the same time and equatorial communities experienced an invasion of cool water taxa. The impact of this cooling on northern mid-latitude assemblages is, however, less well known. In order to overcome this gap we studied the Kronsmoor section (northwest Germany). This section provides a continuous upper Campanian - lower Maastrichtian succession with moderately to well preserved nannofossils. Uppermost Campanian assemblages are dominated by Prediscosphaera cretacea; other common taxa include Prediscosphaera stoveri, Watznaueria barnesiae and Micula staurophora. The lower Maastrichtian is characterized by lower numbers of P. cretacea and frequent Kamptnerius magnificus, Arkhangelskiella cymbiformis and Cribrosphaerella ehrenbergii. These changes reflect, in part, the Campanian-Maastrichtian boundary cooling since some successful taxa (e.g. K. magnificus) are related to cool surface waters. Other shifts in the nannofossil communities were perhaps the result of a changing nutrient regime. Stronger latitudinal gradients may have increased wind velocities and thus the eolian input of ferruginous dust required by N-fixing bacteria. The enhanced high latitude deep-water formation probably changed the bottom-water environment in disfavor of denitrificating organisms. A decline of chemical weathering and fluviatile transport may have reduced the amount of bioavailable phosphate. These processes led to an increased nitrate and a decreased phosphate content shifting the nutrient regime from nitrate towards phosphate limitation.

Stable isotope analysis on planktic foraminifera in sediment cores from the eastern Mediterranean sapropel formation

During the late Pleistocene, sapropels (layers of organic-carbon rich sediment) formed throughout the entire Eastern Mediterranean Basin in close association with glacial/interglacial transitions. The current theory for the mechanism of sapropel formation involves a density stratification of the water column, due to the invasion of a large quantity of low-saline water, which resulted in oxygen depletion of the bottom waters. Most workers believe that this low-salinity water was glacial meltwater that entered the Mediterranean via the Black Sea and a series of interconnected glacial lakes, but the suggestion also has been made that the freshwater originated from the Nile River. In this study the oxygen isotope values of planktonic foraminifera,Globigerinoides ruber, have been examined in six gravity cores and one piston core from the southern Levantine Basin, and compared with the oxygen isotope records ofG. ruber from other areas of the Eastern Mediterranean. This study deals mainly with the latest sapropel which was deposited approximately 7000 to 9000 years ago. Results indicate that Nile discharge probably does reduce salinities somewhat in the immediate area surrounding the mouth of the Nile, but this water is rapidly mixed with the highly saline waters of the easternmost Mediterranean. Using a mixing equation and surface water salinity limitations, an approximate oxygen isotope balance of surface waters was calculated for the time of latest sapropel deposition. This calculation shows that neither Nile River discharge nor Black Sea input (nor both together) are large enough to account for the large-scale oxygen isotope depletion associated with latest sapropel deposition in the Eastern Mediterranean. This suggests that part of the isotopic change at Termination I is probably due to increased surface water salinities during the last glacial maximum. In addition, evidence from the timing of sapropel 1 deposition and the dissolved oxygen balance indicates that deposition of the latest sapropel is associated with increased surface water production of biogenic material, as much as three times higher than that of present day.

Planktonic foraminifera in the Arabian Sea

Variations in primary productivity (PP) have been reconstructed in eutrophic, mesotrophic and oligotrophic parts of the Arabian Sea over the past 135 000 years applying principal component analysis and transfer function to planktic foraminiferal assemblages. Temporal variation in paleoproductivity is most pronounced in the mesotrophic northern (NAST site) and oligotrophic eastern (EAST site) Arabian Sea, and comparatively weak in the western eutrophic GeoB 3011-1 site in the upwelling area off Oman. Higher PP during interglacials (250-320 g C/m**2 year) than during cold stages (210-270 g C/m**2 year) at GeoB 3011-1 could have been caused by a strengthened upwelling during intensified summer monsoons and increased wind velocities. At NAST, during interglacials, PP is estimated to exceed g C/m**2 year 1, and during glacials to be as low as 140-180 g C/m**2 year. These fluctuations may result from a (1) varying impact of filaments that are associated to the Oman coastal upwelling, and (2) from open-ocean upwelling associated to the Findlater Jet. At EAST, highest productivity of about 380 g C/m**2 year is documented for the transition from isotope stage 5 to 4. We suggest that during isotope stages 2, 4, 5.2, the transition 5/4, and the end of stage 6, deep mixing of surface waters was caused by moderate to strong winter monsoons, and induced an injection of nutrients into the euphotic layer leading to enhanced primary production. The deepening of the mixed layer during these intervals is confirmed by an increased concentration of deep-dwelling planktic foraminiferal species. A high-productivity event in stage 3, displayed by estimated PP values, and by planktic foraminifera and radiolaria flux and accumulation rate, likely resulted from a combination of intensified SW monsoons with moderate to strong NE monsoons. Differential response of Globigerina bulloides, Globigerinita glutinata and mixed layer species to the availability of food is suited to subdivide productivity regimes on a temporal and spatial scale.

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).

Nitrogen isotope gradients off Peru and Ecuador related to upwelling, productivity, nutrient uptake and oxygen deficiency

We present new nitrogen isotope data from the water column and surface sediments for paleo-proxy validation collected along the Peruvian and Ecuadorian margins between 1°N and 18°S. Productivity proxies in the bulk sediment (organic carbon, total nitrogen, biogenic opal, C37 alkenone concentrations) and 15N/14N ratios were measured at more than 80 locations within and outside the present-day Peruvian oxygen minimum zone (OMZ). Microbial N-loss to N2 in subsurface waters under O2 deficient conditions leaves a characteristic 15N-enriched signal in underlying sediments. We find that phytoplankton nutrient uptake in surface waters within the high nutrient, low chlorophyll (HNLC) regions of the Peruvian upwelling system influences the sedimentary signal as well. How the d15Nsed signal is linked to these processes is studied by comparing core-top values to the 15N/14N of nitrate and nitrite (d15N[NOx]) in the upper 200 m of the water column. Between 1°N and 10°S, subsurface O2 is still high enough to suppress N-loss keeping d15NNOx values relatively low in the subsurface waters. However d15N[NOx] values increase toward the surface due to partial nitrate utilization in the photic zone in this HNLC portion of the system. d15N[sed] is consistently lower than the isotopic signature of upwelled [NO3]-, likely due to the corresponding production of 15N depleted organic matter. Between 10°S and 15°S, the current position of perennial upwelling cells, HNLC conditions are relaxed and biological production and near-surface phytoplankton uptake of upwelled [NO3]- are most intense. In addition, subsurface O2 concentration decreases to levels sufficient for N-loss by denitrification and/or anammox, resulting in elevated subsurface d15N[NOx] values in the source waters for coastal upwelling. Increasingly higher production southward is reflected by various productivity proxies in the sediments, while the north-south gradient towards stronger surface [NO3]- utilization and subsurface N-loss is reflected in the surface sediment 15N/14N ratios. South of 10°S, d15N[sed] is lower than maximum water column d15N[NOx] values most likely because only a portion of the upwelled water originates from the depths where highest d15N[NOx] values prevail. Though the enrichment of d15N[NOx] in the subsurface waters is unambiguously reflected in d15N[sed] values, the magnitude of d15N[sed] enrichment depends on both the depth of upwelled waters and high subsurface d15N[NOx] values produce by N-loss. Overall, the degree of N-loss influencing subsurface d15N[NOx] values, the depth origin of upwelled waters, and the degree of near-surface nitrate utilization under HNLC conditions should be considered for the interpretation of paleo d15N[sed] records from the Peruvian oxygen minimum zone.

Benthic foraminifera in sapropels of the eastern Mediterranean Sea

High-resolution benthic foraminiferal and geochemical investigations were carried out across sapropels S5 and S6 from two sediment cores in the Levantine Sea to evaluate the impact of climatic and environmental changes on benthic ecosystems during times of sapropel formation. The faunal successions indicate that eutrophication and/or oxygen reduction started several thousand years prior to the onset of sapropel formation, suggesting an early response of the bathyal ecosystems to climatic changes. Severest oxygen depletions appear in the early phases of sapropel formation. The initial reduction of deep-water ventilation is caused by a warming and fresh water-induced stratification of Eastern Mediterranean surface waters. During the late phase of S5 formation improved oxygenation is restricted to middle bathyal ecosystems, indicating that at least some formation of subsurface water took place. During S6 formation oxygen depletions and eutrophication were less severe and more variable than during S5 formation. Estimated oxygen contents were low dysoxic at middle bathyal to anoxic at lower bathyal depths during the early phase of S6 formation but never dropped to anoxic values in its late phase. The high benthic ecosystem variability during S6 formation suggests that water column stratification at deep-water formation sites was in a very unstable mode and susceptible to minor temperature fluctuations at a millennial time-scale.

Stable carbon isotope record of planktonic foraminifera and organic matter from sediment cores in the Gulf of Aqaba

The stable carbon isotopic composition of the planktonic foraminifera Globigerinoides sacculifer and G. ruber (white) and sedimentary organic matter from the northern Gulf of Aqaba have been investigated to estimate changes in delta13CDIC in surface waters during the last 1,000 years. The high sedimentation rates at the core sites (about 54 cm/Kyear) provide high temporal resolution (~10 years). Recent sediments at the top of the cores reflect conditions younger than 1950. The delta13C records of the planktonic foraminifera from three multicores display similar trends, showing a uniform and consistent pattern before the 1750s, and a gradual decrease of approximately 0.63? over the last two centuries. This decrease seems to track the decrease of delta13CDIC in surface waters, which is mainly caused by the increase of anthropogenic input of 13C-depleted CO2 into the atmosphere. Similarly, a trend towards lighter values of the carbon isotopic composition of sedimentary organic matter (delta13Corg) during the last 200 years supports the interpretation obtained from the planktonic foraminiferal delta13C. Furthermore, direct measurements of seawater show that delta13C of the dissolved inorganic carbon (DIC) in the northern Gulf of Aqaba has decreased by about 0.44 per mil during the period 1979-2000. The average annual decrease is 0.021 per mil, which is similar to that observed globally. The delta13C values of planktonic foraminifera combined with organic matter delta13C from marine sediments are good indicators for reconstructing past changes in atmospheric CO2 concentrations from the northern Gulf of Aqaba.