Seawater carbonate chemistry and biological processes during experiments with four species of marine diatoms

The effect of pCO2 on carbon acquisition and intracellular assimilation was investigated in the three bloom-forming diatom species, Eucampia zodiacus (Ehrenberg), Skeletonema costatum (Greville) Cleve, Thalassionema nitzschioides (Grunow) Mereschkowsky and the non-bloom-forming Thalassiosira pseudonana (Hust.) Hasle and Heimdal. In vivo activities of carbonic anhydrase (CA), photosynthetic O2 evolution, CO2 and HCO3? uptake rates were measured by membrane-inlet mass spectrometry (MIMS) in cells acclimated to pCO2 levels of 370 and 800 ?atm. To investigate whether the cells operate a C4-like pathway, activities of ribulose-1,5-bisphosphate carboxylase (RubisCO) and phosphoenolpyruvate carboxylase (PEPC) were measured at the mentioned pCO2 levels and a lower pCO2 level of 50 ?atm. In the bloom-forming species, extracellular CA activities strongly increased with decreasing CO2 supply while constantly low activities were obtained for T. pseudonana. Half-saturation concentrations (K1/2) for photosynthetic O2 evolution decreased with decreasing CO2 supply in the two bloom-forming species S. costatum and T. nitzschioides, but not in T. pseudonana and E. zodiacus. With the exception of S. costatum, maximum rates (Vmax) of photosynthesis remained constant in all investigated diatom species. Independent of the pCO2 level, PEPC activities were significantly lower than those for RubisCO, averaging generally less than 3%. All examined diatom species operate highly efficient CCMs under ambient and high pCO2, but differ strongly in the degree of regulation of individual components of the CCM such as Ci uptake kinetics and extracellular CA activities. The present data do not suggest C4 metabolism in the investigated species.

CO2 concentration and stable isotope ratios of three Antarctic ice cores covering the period from 149.4 - 1.5 kyr before 1950

We present new d13C measurements of atmospheric CO2 covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in d13C(atm) of 0.5 permil occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in d13C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO2]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of d13C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.

Stable isotope ratios on planktonic foraminifer N. pachyderma of surface sediments from the Arctic Ocean (Table 1)

Planktic foraminifers Neogloboquadrina pachyderma (sin.) from 87 eastern and central Arctic Ocean surface sediment samples were analyzed for stable oxygen and carbon isotope composition. Additional results from 52 stations were taken from the literature. The lateral distribution of delta18O (18O/16O) values in the Arctic Ocean reveals a pattern of roughly parallel, W-E stretching zones in the Eurasian Basin, each ~0.5 per mil wide on the delta18O scale. The low horizontal and vertical temperature variability in the Arctic halocline waters (0-100 m) suggests only little influence of temperature on the oxygen isotope distribution of N. pachyderma (sin.). The zone of maximum delta18O values of up to 3.8 per mil is situated in the southern Nansen Basin and relates to the tongue of saline (> 33%.) Atlantic waters entering the Arctic Ocean through the Fram Strait. delta18O values decrease both to the Barents Shelf and to the North Pole, in accordance with the decreasing salinities of the halocline waters. In the Nansen Basin, a strong N-S delta18O gradient is in contrast with a relatively low salinity change and suggests contributions from different freshwater sources, i.e. salinity reduction from sea ice meltwater in the south and from light isotope waters (meteoric precipitation and river-runoff) in the northern part of the basin. North of the Gakkel Ridge, delta18O and salinity gradients are in good accordance and suggest less influence of sea ice melting processes. The delta13C (13C/12C) values of N. pachyderma (sin.) from Arctic Ocean surface sediment samples are generally high (0.75-0.95 per mil). Lower values in the southern Eurasian Basin appear to be related to the intrusion of Atlantic waters. The high delta13C values are evidence for well ventilated surface waters. Because the perennial Arctic sea ice cover largely prevents atmosphere-ocean gas exchange, ventilation on the seasonally open shelves must be of major importance. Lack of delta13C gradients along the main routes of the ice drift from the Siberian shelves to the Fram Strait suggests that primary production (i.e. CO2 consumption) does probably not change the CO2 budget of the Arctic Ocean significantly.

Seismic reflection data, calcium/iron ratios, stable istopes, and magnetic susceptibility of sediment cores from the Pen Duick Escarpment, Gulf of Cadiz

Here we present a case study of three cold-water coral mounds in a juvenile growth stage on top of the Pen Duick Escarpment in the Gulf of Cadiz; Alpha, Beta and Gamma mounds. Although cold-water corals are a common feature on the adjacent cliffs, mud volcanoes and open slope, no actual living cold-water coral has been observed. This multidisciplinary and integrated study comprises geophysical, sedimentological and (bio)geochemical data and aims to present a holistic view on the interaction of both environmental and geological drivers in cold-water coral mound development in the Gulf of Cadiz. Coring data evidences (past or present) methane seepage near the Pen Duick Escarpment. Several sources and pathways are proposed, among which a stratigraphic migration through uplifted Miocene series underneath the escarpment. The dominant morphology of the escarpment has influenced the local hydrodynamics within the course of the Pliocene, as documented by the emplacement of a sediment drift. Predominantly during post-Middle Pleistocene glacial episodes, favourable conditions were present for mound growth. An additional advantage for mound formation near the top of Pen Duick Escarpment is presented by seepage-related carbonate crusts which might have offered a suitable substrate for coral settling. The spatially and temporally variable character and burial stage of the observed open reef frameworks, formed by cold-water coral rubble, provides a possible model for the transition from cold-water coral reef patches towards juvenile mound. These rubble "graveyards" not only act as sediment trap but also as micro-habitat for a wide range of organisms. The presence of a fluctuating Sulphate-Methane Transition Zone has an important effect on early diagenetic processes, affecting both geochemical and physical characteristics, transforming the buried reef into a solid mound. Nevertheless, the responsible seepage fluxes seem to be locally variable. As such, the origin and evolution of the cold-water coral mounds on top of the Pen Duick Escarpment is, probably more than any other NE Atlantic cold-water coral mound province, located on the crossroads of environmental (hydrodynamic) and geological (seepage) pathways.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

Chemistry and stable isotope record of sediment core GeoB4905-4

Evidence of rapid climatic oscillations like those observed in the Greenland ice cores and sediments from high latitudes of the northern Atlantic have been recognized in the pulses of terrigenous material to continental margin sediments off Cameroon. Fe/Ca ratios used as a parameter to quantify the relative proportions of terrigenous fluxes versus marine carbonate monitor the variability of the west African monsoon. They reveal the history of abrupt changes in precipitation over western and central Africa during the past 52 kyr. These rapid changes are particularly pronounced during the last glacial period and occur at timescales of a few thousand years. Stable oxygen isotope (delta18O) records of Globigerinoides ruber (pink) show high negative values reflecting periods of high monsoon precipitation. The Fe/Ca pattern is very similar to the Dansgaard-Oeschger cycles from the Greenland ice cores. The good correspondence between the warm interstadials of the Dansgaard-Oeschger cycles from the GISP2 ice core records and the high pulses of Fe/Ca sedimentation in our core suggest a strong teleconnection between the low-latitude African climate and the high-latitude northern hemisphere climate oscillations during the last glacial. This climatic link is probably vested in the west African monsoonal fluctuation that alters tropical sea surface temperatures, thermohaline circulations and in turn net export of heat from the south to the north Atlantic, coupled with the variability of the low-latitude southeast trade winds.

Radiocarbon, stable isotopic compositions and seawater chemical properties of Black Sea core-top sediments and CTD stations

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotope analysis to examine the time-scales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea core-top sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment ?15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates either contribution from N2-fixation or direct uptake of ammonium from deeper waters. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.

Seawater carbonate chemistry and biological processes of Amphisorus hemprichii, Amphisorus kudakajimensis and Calcarina gaudichaudii during experiments, 2011

Ocean acidification, which like global warming is an outcome of anthropogenic CO2emissions, severely impacts marine calcifying organisms, especially those living in coral reef ecosystems. However, knowledge about the responses of reef calcifiers to ocean acidification is quite limited, although coral responses are known to be generally negative. In a culture experiment with two algal symbiont-bearing, reef-dwelling foraminifers, Amphisorus kudakajimensis and Calcarina gaudichaudii, in seawater under five different pCO2 conditions, 245, 375, 588, 763 and 907 µatm, maintained with a precise pCO2-controlling technique, net calcification of A. kudakajimensis was reduced under higher pCO2, whereas calcification of C. gaudichaudii generally increased with increased pCO2. In another culture experiment conducted in seawater in which bicarbonate ion concentrations were varied under a constant carbonate ion concentration, calcification was not significantly different between treatments in Amphisorus hemprichii, a species closely related to A. kudakajimensis, or in C. gaudichaudii. From these results, we concluded that carbonate ion and CO2 were the carbonate species that most affected growth ofAmphisorus and Calcarina, respectively. The opposite responses of these two foraminifer genera probably reflect different sensitivities to these carbonate species, which may be due to their different symbiotic algae.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Stable carbon and oxygen isotope ratios of Planulina wuellerstorfi from sediments of the Vema Channel

Oxygen- and carbon-isotopic analyses have been performed on the benthic foraminifer Planulina wuellerstorfi in seven Late Quaternary cores from the Vema Channel-Rio Grande Rise region. The cores are distributed over the water-depth interval of 2340 to 3939 m, which includes the present transition from North Atlantic Deep Water (NADW) to Antarctic Bottom Water (AABW). The carbon-isotopic records in the cores vary as a function of water depth. The shallowest and deepest cores show no significant glacial-interglacial difference in delta13C. Four of the five cores presently located in the NADW have benthic foraminiferal delta13C that is lower during glacial isotopic stages. Based on bathymetric gradients in delta13C, we conclude that, like today, there were two water masses present in the Vema Channel during glacial intervals: a water mass enriched in 13C overlying another water mass depleted in 13C. The largest gradient of change of delta13C with depth, however, occurred at 2.7 km, ~1 km shallower than the present position of this gradient. On the basis of paleontologic and sedimentologic evidence, we consider it unlikely that the NADW:AABW transition shallowed to this level. Reduced carbon-isotopic gradients between the deep basins of the North Atlantic and Pacific Oceans during the last glaciation suggest that production of NADW was reduced. Lower production of NADW may have modified the local abyssal circulation pattern in the Vema Channel region.

Stable oxygen isotope data of Thoracosphaera heimii in surface sediment samples of the equatorial Atlantic and South Atlantic

To investigate the potential use of the stable isotope composition of the vegetative cysts of the photosynthetic dinoflagellate Thoracosphaera heimii for quantitative palaeotemperature reconstructions a method has been developed to purify T. heimii cysts from sediment samples. Stable oxygen and carbon isotopes have been measured on T. heimii cysts from 21 surface sediment samples from the equatorial Atlantic and South Atlantic Oceans. Calculated temperatures based on the palaeotemperature equation for inorganic calcite precipitation generally reflect mean annual temperatures of the upper water column, notably of thermocline depths. Although the present results suggest that the isotopic composition of T. heimii shells might be formed in equilibrium with the seawater in which the shells are being formed, future investigations are required to determine possible effects of metabolic and kinetic processes on the fractionation process. This pilot study therefore forms the basis for future investigations on the development of this tool and the determination of a species-specific palaeotemperature equation. The wide geographic and stratigraphic distribution of T. heimii cysts in sediments, the stable position of T. heimii within the water column and the high resistance of its cysts against calcite dissolution underline its potential for a wide usability in palaeotemperature reconstructions.

Stable isotopes, radionuclides, and calculated sea surface temperature of two sediment cores in the Sicily Channel

The Eastern Mediterranean Transient (EMT) occurred in the Aegean Sea from 1988 to 1995 and is the most significant intermediate-to-deep Mediterranean overturning perturbation reported by instrumental records. The EMT was likely caused by accumulation of high salinity waters in the Levantine and enhanced heat loss in the Aegean Sea, coupled with surface water freshening in the Sicily Channel. It is still unknown whether similar transients occurred in the past and, if so, what their forcing processes were. In this study, sediments from the Sicily Channel document surface water freshening (SCFR) at 1910±12, 1812±18, 1725±25 and 1580±30 CE. A regional ocean hindcast links SCFR to enhanced deep-water production and in turn to strengthened Mediterranean thermohaline circulation. Independent evidence collected in the Aegean Sea supports this reconstruction, showing that enhanced bottom water ventilation in the Eastern Mediterranean was associated with each SCFR event. Comparison between the records and multi-decadal atmospheric circulation patterns and climatic external forcings indicates that Mediterranean circulation destabilisation occurs during positive North Atlantic Oscillation (NAO) and negative Atlantic Multidecadal Oscillation (AMO) phases, reduced solar activity and strong tropical volcanic eruptions. They may have recurrently produced favourable deep-water formation conditions, both increasing salinity and reducing temperature on multi-decadal time scales.

d13C and d15N stable isotopes values, total nitrogen and C/N ratios of sediment core GeoB4801-1

Rising stable nitrogen isotope ratios (d15N) in dated sediment records of the German Bight/SE North Sea track river-induced coastal eutrophication over the last 2 centuries. Fully exploiting their potential for reconstructions of pristine conditions and quantitative analysis of historical changes in the nitrogen cycle from these sediment records requires knowledge on processes that alter the isotopic signal in non-living organic matter (OM) of sinking particles and sediments. In this study, we analyze the isotopic composition of particulate nitrogen (PN) in the water column during different seasons, in surface sediments, and in sediment cores to assess diagenetic influences on the isotopic composition of OM. Amino acid (AA) compositions of suspended matter, surface sediments, and dated cores at selected sites of the German Bight serve as indicators for quality and degradation state of PN. The d15N of PN in suspended matter had seasonal variances caused by two main nitrate sources (oceanic and river) and different stages of nitrate availability during phytoplankton assimilation. Elevated d15N values (> 20 per mil) in suspended matter near river mouths and the coast coincide with a coastal water mass receiving nitrate with elevated isotope signal (d15N > 10 per mil) derived from anthropogenic input. Particulate nitrogen at offshore sites fed by oceanic nitrate having a d15N between 5 and 6 per mil had low d15N values (< 2 per mil), indicative of an incipient phytoplankton bloom. Surface sediments along an offshore-onshore transect also reflect the gradient of low d15N of nitrate in offshore sites to high values near river mouths, but the range of values is smaller than between the end members listed above and integrates the annual d15N of detritus. Sediment cores from the coastal sector of the gradient show an increasing d15N trend (increase of 2.5 per mil) over the last 150 years. This is not related to any change in AA composition and thus reflects eutrophication. The d15N signals from before AD 1860 represent a good estimation of pre-industrial isotopic compositions with minimal diagenetic overprinting. Rising d13C in step with rising d15N in these cores is best explained by increasing productivity caused by eutrophication.

(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

Stable carbon and oxygen isotope ratios of benthic and planktonic foraminifera of ODP Hole 171-1049C

Ocean anoxic events were periods of high carbon burial that led to drawdown of atmospheric carbon dioxide, lowering of bottom-water oxygen concentrations and, in many cases, significant biological extinction (Arthur et al., 1990; Erbacher et al., 1996, doi:10.1130/0091-7613(1996)024<0499:EPORAO>2.3.CO;2; Kuypers et al., 1999, doi:10.1038/20659; Jenkyns, 1997; Hochuli et al., 1999, doi:10.1130/0091-7613(1999)027<0657:EOHPAC>2.3.CO;2). Most ocean anoxic events are thought to be caused by high productivity and export of carbon from surface waters which is then preserved in organic-rich sediments, known as black shales. But the factors that triggered some of these events remain uncertain. Here we present stable isotope data from a mid-Cretaceous ocean anoxic event that occurred 112 Myr ago, and that point to increased thermohaline stratification as the probable cause. Ocean anoxic event 1b is associated with an increase in surface-water temperatures and runoff that led to decreased bottom-water formation and elevated carbon burial in the restricted basins of the western Tethys and North Atlantic. This event is in many ways similar to that which led to the more recent Plio-Pleistocene Mediterranean sapropels, but the greater geographical extent and longer duration (~46 kyr) of ocean anoxic event 1b suggest that processes leading to such ocean anoxic events in the North Atlantic and western Tethys were able to act over a much larger region, and sequester far more carbon, than any of the Quaternary sapropels.