Growth rates and stable carbon and oxygen isotope record of corals from the Red Sea

Monthly delta18O records of 2 coral colonies (Porites cf. lutea and P. cf. nodifera) from different localities (Aqaba and Eilat) from the northern Gulf of Aqaba, Red Sea, were calibrated with recorded sea surface temperatures (SST) between 1988 and 2000. The results show high correlation coefficients between SST and delta18O. Seasonal variations of coral delta18O in both locations could explain 91% of the recorded SST. Different delta18O/SST relations from both colonies and from the same colonies were obtained, indicating that delta18O from coral skeletons were subject to an extension rate effect. Significant delta18O depletions are associated with high extension rates and higher values with low extension rates. The relation between coral skeletal delta18O and extension rate is not linear and can be described by a simple exponential model. An inverse relationship extends over extension rates from 1 to 5 mm/yr, while for more rapidly growing corals and portions of colonies the relation is constant and the extension rate does not appear to have a significant effect. We recommend that delta18O values be obtained from fast-growing corals or from portions in which the isotopic disequilibrium is fairly constant (extension rate >5 mm/yr). The results show that interspecific differences in corals may produce a significant delta18O profile offset between 2 colonies that is independent of environmental and extension-rate effects. We conclude that the rate of skeletal extension and the species of coral involved have an important influence on coral delta18O and must be considered when using delta18O records for paleoclimatic reconstructions.

U and Th concentrations and isotope ratios of samples from ODP Leg 166

Constraining the history of seawater (234U/238U) is important because this ratio is used to assess the validity of U/Th ages, and because it provides information about the past rate of physical weathering on the continents. This study makes use of U-rich slope sediments from the Bahamas in an attempt to reconstruct seawater (234U/238U) for the last 800 kyr. For the last 360 kyr, U/Th dating of these sediments provides ages and initial (234U/238U) values. Sixty-seven samples, largely from marine highstands, have initial (234U/238U) which scatter somewhat about the modern seawater value (~1.145) but neither this scatter nor the average value increases with age of sample. These data contrast with published coral data and suggest that seawater (234U/238U) has remained within 15? of the modern value for the last 360 kyr. This confirms the rejection of coral U/Th ages where the initial (234U/238U) is significantly different from modern seawater. Data from older highstands, dated with delta18O stratigraphy or by the presence of the Brunhes/Matuyama (B/M) reversal at 780 kyr, allow seawater (234U/238U) to be assessed prior to the range of the 230Th chronometer. Unfortunately, diagenetic scatter in the data between the B/M reversal and 360 kyr is rather large, probably relating to low U concentrations for these samples. But there is no indication of a trend in seawater (234U/238U) with age. High U samples from close to the B/M reversal show less diagenetic scatter and an initial (234U/238U) that averages 1.102. This lower value can be explained by lower seawater (234U/238U) at the time of the B/M reversal, or by progressive loss of 234U from the sediment by alpha-recoil. A simple box model is presented to illustrate the response of seawater (234U/238U) to variations in riverine input, such as might be caused by changes in continental weathering. Comparison of the Bahamas (234U/238U) data with model results indicates that riverine (234U/238U) has not varied by more than 65? for any 100 kyr period during the last 360 kyr. It also indicates that the ratio of physical to chemical weathering on the continents has not been higher than at present for any extended period during the last 800 kyr.

Calcium and sodium concentrations of the Talos Dome ice core, Antarctica

In this study we report on new non-sea salt calcium (nssCa2+, mineral dust proxy) and sea salt sodium (ssNa+, sea ice proxy) records along the East Antarctic Talos Dome deep ice core in centennial resolution reaching back 150 thousand years (ka) before present. During glacial conditions nssCa2+ fluxes in Talos Dome are strongly related to temperature as has been observed before in other deep Antarctic ice core records, and has been associated with synchronous changes in the main source region (southern South America) during climate variations in the last glacial. However, during warmer climate conditions Talos Dome mineral dust input is clearly elevated compared to other records mainly due to the contribution of additional local dust sources in the Ross Sea area. Based on a simple transport model, we compare nssCa2+ fluxes of different East Antarctic ice cores. From this multi-site comparison we conclude that changes in transport efficiency or atmospheric lifetime of dust particles do have a minor effect compared to source strength changes on the large-scale concentration changes observed in Antarctic ice cores during climate variations of the past 150 ka. Our transport model applied on ice core data is further validated by climate model data. The availability of multiple East Antarctic nssCa2+ records also allows for a revision of a former estimate on the atmospheric CO2 sensitivity to reduced dust induced iron fertilisation in the Southern Ocean during the transition from the Last Glacial Maximum to the Holocene (T1). While a former estimate based on the EPICA Dome C (EDC) record only suggested 20 ppm, we find that reduced dust induced iron fertilisation in the Southern Ocean may be responsible for up to 40 ppm of the total atmospheric CO2 increase during T1. During the last interglacial, ssNa+ levels of EDC and EPICA Dronning Maud Land (EDML) are only half of the Holocene levels, in line with higher temperatures during that period, indicating much reduced sea ice extent in the Atlantic as well as the Indian Ocean sector of the Southern Ocean. In contrast, Holocene ssNa+ flux in Talos Dome is about the same as during the last interglacial, indicating that there was similar ice cover present in the Ross Sea area during MIS 5.5 as during the Holocene.

(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Wet tundra polygon centers and distance between polygon centroids on Samoylov Island, Lena Delta, Siberia, Russia, with links to shape files

Subgrid processes occur in various ecosystems and landscapes but, because of their small scale, they are not represented or poorly parameterized in climate models. These local heterogeneities are often important or even fundamental for energy and carbon balances. This is especially true for northern peatlands and in particular for the polygonal tundra, where methane emissions are strongly influenced by spatial soil heterogeneities. We present a stochastic model for the surface topography of polygonal tundra using Poisson-Voronoi diagrams and we compare the results with available recent field studies. We analyze seasonal dynamics of water table variations and the landscape response under different scenarios of precipitation income. We upscale methane fluxes by using a simple idealized model for methane emission. Hydraulic interconnectivities and large-scale drainage may also be investigated through percolation properties and thresholds in the Voronoi graph. The model captures the main statistical characteristics of the landscape topography, such as polygon area and surface properties as well as the water balance. This approach enables us to statistically relate large-scale properties of the system to the main small-scale processes within the single polygons.

(Table 1) Spacing of diatom abundance index and opal index at ODP Site 175-1084

An important discovery during Ocean Drilling Program Leg 175, when investigating the record of upwelling off Namibia, was the finding of a distinct Late Pliocene diatom maximum spanning the lower half of the Matuyama reversed polarity chron (MDM, Matuyama Diatom Maximum) and centered around 2.6-2.0 Ma. This maximum was observed at all sites off southwestern Africa between 20°S and 30°S, and is most strongly represented in sediments of Site 1084, off Lüderitz, Namibia. The MDM is characterized by high biogenic opal content, high numbers of diatom valves, and a diatom flora rich in Southern Ocean representatives (with Thalassiothrix antarctica forming diatom mats) as well as coastal upwelling components. Before MDM time, diatoms are rare until ca. 3.6 Ma. After the MDM, in the Pleistocene, the composition of the diatom flora points to increased importance of coastal upwelling toward the present, but is accompanied by a general decrease in opal and diatom deposition. Here we present a simple conceptual model as a first step in formalizing a possible forcing mechanism responsible for the record of opal deposition in the upwelling system off Namibia. The model takes into account Southern Ocean oceanography, and a link with deepwater circulation and deepwater nutrient chemistry which, in turn, are coupled to the evolution of North Atlantic Deep Water (NADW). The model proposes that between the MDM and the Mid-Pleistocene climate revolution, opal deposition off Namibia is not directly tied to glacial-interglacial fluctuations (as seen in the global d18O record), but that, instead, a strong deepwater link exists with increased NADW production (as seen in the deepwater d13C record) accounting for higher supply of silicate to the thermocline waters that feed the upwelling process. The opal record of Site 1084 shows affinity to eccentricity on the 400-kyr scale but not for the 100-kyr scale. This points toward long-term geologic processes for delivery of silica to the ocean.

Pliocene-Pleistocene stack of globally distributed benthic stable oxygen isotope records

We present a 5.3-Myr stack (the ''LR04'' stack) of benthic d18O records from 57 globally distributed sites aligned by an automated graphic correlation algorithm. This is the first benthic delta18O stack composed of more than three records to extend beyond 850 ka, and we use its improved signal quality to identify 24 new marine isotope stages in the early Pliocene. We also present a new LR04 age model for the Pliocene-Pleistocene derived from tuning the delta18O stack to a simple ice model based on 21 June insolation at 65 N. Stacked sedimentation rates provide additional age model constraints to prevent overtuning. Despite a conservative tuning strategy, the LR04 benthic stack exhibits significant coherency with insolation in the obliquity band throughout the entire 5.3 Myr and in the precession band for more than half of the record. The LR04 stack contains significantly more variance in benthic delta18O than previously published stacks of the late Pleistocene as the result of higher resolution records, a better alignment technique, and a greater percentage of records from the Atlantic. Finally, the relative phases of the stack's 41- and 23-kyr components suggest that the precession component of delta18O from 2.7-1.6 Ma is primarily a deep-water temperature signal and that the phase of d18O precession response changed suddenly at 1.6 Ma.

Results of an in situ stable isotope labeling study in intertidal sediment

We report the results of an in situ tracer experiment in an intertidal sediment, where bacterial carbon was tagged with stable carbon-isotope label, after the injection of 13C-glucose. The appearance of label in bacteria (based on label incorporation in bacteria-specific, phospholipid-derived fatty acids) and subsequent transfer to meiobenthos (group level) and macrobenthos (species level) was followed for 36 days. The label dynamics of benthic taxa were either fitted with a simple-isotope model or evaluated against enrichment in bacteria, to derive the importance of bacterially derived carbon for the meiobenthos and macrobenthos. Although selective uptake of bacteria was evident, as 2.4 times more bacterial carbon was grazed as expected from indiscriminate feeding, bacterial carbon accounted on average for only 0.08 and 0.11 of the carbon requirements of meiobenthic and macrobenthic taxa, respectively. Additionally, the contribution of bacterial carbon to total carbon requirements did not depend on the living/feeding depth in the sediment or organism size (evaluated over a size range of four orders of magnitude). The observed overall low contribution of bacterial carbon implies that most intertidal benthic fauna depend primarily on other carbon resources that may assert a stronger control on the structure of intertidal-sediment communities.

Experimental data of CO2, CO3, Omega calcite saturation, pH values, alpha and epsilon fractionation factors, and Dd18O calctite-water

The oxygen isotopic composition (d18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy calibration a challenging task. Understanding these secondary or "vital" effects is crucial for increasing proxy accuracy. We present data from laboratory experiments showing that oxygen isotope fractionation during calcification in the coccolithophore Calcidiscus leptoporus and the calcareous dinoflagellate Thoracosphaera heimii is dependent on carbonate chemistry of seawater in addition to its dependence on temperature. A similar result has previously been reported for planktonic foraminifera, supporting the idea that the [CO3]2- effect on d18O is universal for unicellular calcifying planktonic organisms. The slopes of the d18O/[CO3]2- relationships range between -0.0243 per mil/(µmol/kg) (calcareous dinoflagellate T. heimii) and the previously published -0.0022 per mil/(µmol/kg) (non-symbiotic planktonic foramifera Orbulina universa), while C. leptoporus has a slope of -0.0048 per mil/(µmol/kg). We present a simple conceptual model, based on the contribution of d18O-enriched [HCO3]- to the [CO3]2- pool in the calcifying vesicle, which can explain the [CO3]2- effect on d18O for the different unicellular calcifiers. This approach provides a new insight into biological fractionation in calcifying organisms. The large range in d18O/[CO3]2- slopes should possibly be explored as a means for paleoreconstruction of surface [CO3]2-, particularly through comparison of the response in ecologically similar planktonic organisms.

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

Geochemistry and petrology of ODP Leg 121 basalts

Basement lavas from Sites 756, 757, and 758 on Ninetyeast Ridge are tholeiitic basalts. Lavas from Sites 756 and 757 appear to be subaerial eruptives, but the lowermost flows from Hole 758A are pillow lavas. In contrast to the compositional variation during the waning stages of Hawaiian volcanism, no alkalic lavas have been recovered from Ninetyeast Ridge and highly evolved lavas were recovered from only one of seven drill sites (DSDP Site 214). All lavas from Site 758 have relatively high MgO contents (8-10 wt%), and they are less evolved than lavas from Sites 756 and 757. Although abundances of alkali metals in these Ninetyeast Ridge basalts were significantly modified by postmagmatic alteration, abundances of other elements reflect magmatic processes. At Site 757 most of the lavas are Plagioclase cumulates, but lava compositions require two compositionally distinct, AhCb-rich parental magmas, perhaps segregated at relatively low mantle pressures. In addition, at both Sites 756 and 758 more than one compositionally distinct parental magma is required. The compositions of these Ninetyeast Ridge lavas, especially those from Site 758, require a source component with a depleted composition; specifically, the abundance ratios Th/Ta, Th/La, Ba/Nb, Ba/La, and La/Ce in these lavas are generally less than the ratios inferred for primitive mantle. Lavas from Ninetyeast Ridge and the Kerguelen Archipelago have very different chondrite-normalized REE patterns, with lower light REE/heavy REE (LREE/HREE) ratios in lavas from Ninetyeast Ridge. However, lavas from Sites 757 and 758 have Pb isotope ratios that overlap with the field defined by lavas from the Kerguelen Archipelago (Weis and Frey, this volume). Therefore, these Ninetyeast Ridge lavas contain more of a component that is relatively depleted in LREE and other highly incompatible elements, but have similar amounts of the component that controls radiogenic Pb isotopes. A model involving mixing between components related to a depleted source and an enriched plume source has been proposed for the oldest Kerguelen Archipelago basalts and Ninetyeast Ridge lavas. Although the incompatible element characteristics of the Ninetyeast Ridge lavas are intermediate between depleted MORB and Kerguelen Archipelago basalts, these data are not consistent with a simple two-component mixing process. A more complex model is required.

A coupled model for carbon and radiocarbon evolution during the last deglaciation, link to model results

Changes in the ventilation of the Southern Ocean are thought to play an important role on deglacial carbon and radiocarbon evolution, but have not been tested within a coupled climate-carbon model. Here, we present such a simulation based on a simple scenario of transient deglacial sinking of brines - sea-ice salt rejections - around Antarctica, which modulates Southern Ocean ventilation. This experiment is able to reproduce deglacial atmospheric changes in carbon and radiocarbon but also ocean radiocarbon records measured in the Atlantic, Southern and Pacific Oceans. Simulated for the first time in a fully coupled climate-carbon model including radiocarbon, our modeling results suggest that the deglacial changes in atmospheric carbon dioxide and radiocarbon were achieved by means of a breakdown in the glacial brine-induced stratification of the Southern Ocean.