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.

Paleotemperatures, stable isotopes and alkenones of samples from the South Atlantic

Carbon dioxide is one of the most important greenhouse gases which are increasing in atmospheric concentration due to human activities. For using natural CO2 dynamics as a key to understanding the climatic consequences of anthropogenic pCO2 rise, the ocean plays an important role due to its much larger carbon pool compared to the atmosphere. By studying the ratio of stable carbon isotopes in organic matter from marine sediments, it is possible to estimate the partial pressure of CO2 in surface waters during ancient times. The organic compound C37:2 alkenone, whose sole origin is from autotrophic marine algae, was chosen for d13C analysis and its isotopic composition used to reconstruct past PCO2 levels in the surface layer of the eastern Angola Basin for the last 200,000 years. In addition to the variation of ancient concentrations of dissolved CO2 ([CO2(aq)] = ce), the effect of carbon demand which depends on algal growth rate was considered. Here to, carbon isotopic fractionation of C37:2 alkenones (ep) in core-top sediments from the equatorial and the South Atlantic was calibrated against pre-industrial [CO2(aq)] and phosphate concentrations in surface waters. From these data, a variable b = (25 per mil - ep) * ce which reflects intracellular carbon demand was calculated. This variable b correlates with the ambient concentration of seawater phosphate and depends on growth rates. The bulk sediment d15N was used as a proxy parameter for calculating ancient b-values, taking into account that d15N in core-top sediments is correlated to phosphate concentration in modern surface waters. On this basis, the alkenone d13C record of GeoB1016-3 documents a permanent oceanic source for atmospheric carbon dioxide during the last 200,000 years. As a consequence of using d15N derived b-values instead of b = constant, the Angola Basin appears to have been an even stronger CO2 source during glacial periods than at present. Qualitatively similar results were reported by Jasper et al. (1994) for the central Equatorial Pacific. These observations suggest that enhanced productivity of low-latitude upwelling areas during glacial periods is not responsible for the lower CO2 content of the glacial atmosphere.

Stable oxygen isotope composition of benthic foraminifera from sediments of the Skagerrak, North Sea

Benthic foraminiferal tests of a sediment core from southwestern Skagerrak (northeastern North Sea, 420 m water depth) were investigated for their ratio of stable oxygen isotopes. During modern times sudden drops in temperature and salinity of Skagerrak deep waters point to advection-induced cascades of colder and denser central North Sea waters entering the Skagerrak. These temperature drops, which are recorded in benthic foraminiferal tests via the stable oxygen isotopic composition, were used to reconstruct deep-water renewal in the Skagerrak. In a second step we will show that, at least during the last 1200 years, Skagerrak deep-water renewal is triggered by the negative phase of the North Atlantic Oscillation (NAO). The NAO exerts a strong influence on the climate of northwestern Europe. It is currently under debate if the long-term variability of the NAO is capable of influencing Northern Hemisphere climate on long timescales. The data presented here cannot reinforce these speculations. Our data show that most of the 'Little Ice Age' was dominated by comparably warm deep-water temperatures. However, we did find extraordinary strong temperature differences between central North Sea waters and North Atlantic water masses during this time interval.

Stable isotope ratios and chemistry on corals from the Caribbean Sea

Instrumental climate data are limited in length and only available with low spatial coverage before the middle of the 20th century. This is too short to reliably determine and interpret decadal and longer scale climate variability and to understand the underlying mechanisms with sufficient accuracy. A proper knowledge of past variability of the climate system is needed to assess the anthropogenic impact on climate and ecosystems, and also important with regard to long-range climate forecasting. Highly-resolved records of past climate variations that extend beyond pre-industrial times can significantly help to understand long-term climate changes and trends. Indirect information on past environmental and climatic conditions can be deduced from climate-sensitive proxies. Large colonies of massive growing tropical reef corals have been proven to sensitively monitor changes in ambient seawater. Rapid skeletal growth, typically ranging between several millimeters to centimeters per year, allows the development of proxy records at sub-seasonal resolution. Stable oxygen isotopic composition and trace elemental ratios incorporated in the aragonitic coral skeleton can reveal a detailed history of past environmental conditions, e.g., sea surface temperature (SST). In general, coral-based reconstructions from the tropical Atlantic region have lagged behind the extensive work published using coral records from the Indian and Pacific Oceans. Difficulties in the analysis of previously utilized coral archives from the Atlantic, typically corals of the genera Montastrea and Siderastrea, have so far exacerbated the production of long-term high-resolution proxy records. The objective of this study is the evaluation of massive fast-growing corals of the species Diploria strigosa as a new marine archive for climate reconstructions from the tropical Atlantic region. For this purpose, coral records from two study sites in the eastern Caribbean Sea (Guadeloupe, Lesser Antilles; and Archipelago Los Roques, Venezuela) were examined. At Guadeloupe, a century-long monthly resolved multi-proxy coral record was generated. Results present the first d18O (Sr/Ca)-SST calibration equations for the Atlantic braincoral Diploria strigosa, that are robust and consistent with previously published values using other coral species from different regions. Both proxies reflect local variability of SST on a sub-seasonal scale, which is a precondition for studying seasonally phase-locked climate variations, as well as track variability on a larger spatial scale (i.e., in the Caribbean and tropical North Atlantic). Coral Sr/Ca reliably records local annual to interannual temperature variations and is higher correlated to in-situ air temperature than to grid-SST. The warming calculated from coral Sr/Ca is concurrent with the strong surface temperature increase at the study site during the past decades. Proxy data show a close relationship to major climate signals from the tropical Pacific and North Atlantic (the El Niño Southern Oscillation (ENSO) and the North Atlantic Oscillation (NAO)) affecting the seasonal cycle of SST in the North Tropical Atlantic (NTA). Coral oxygen isotopes are also influenced by seawater d18O (d18Osw) which is linked to the hydrological cycle, and capture large-scale climate variability in the NTA region better than Sr/Ca. Results from a quantitative comparison between extreme events in the two most prominent modes of external forcing, namely the ENSO and NAO, and respective events recorded in seasonal coral d18O imply that SST variability at the study site is highly linked to Pacific and North Atlantic variability, by this means supporting the assumptions of observational- and model-based studies which suggest a strong impact of ENSO and NAO forcings onto the NTA region through a modulation of trade wind strength in winter. Results from different spectral analysis tools suggest that interannual climate variability recorded by the coral proxies is II largely dictated by Pacific ENSO forcing, whereas at decadal and longer timescales the influence of the NAO is dominan. tThe Archipelago Los Roques is situated in the southeastern Caribbean Sea, north of the Venezuelan coast. Year-to-year variations in monthly resolved coral d18O of a nearcentury- long Diploria strigosa record are significantly correlated with SST and show pronounced multidecadal variations. About half of the variance in coral d18O can be explained by variations in seawater d18O, which can be estimated by calculating the d18Oresidual via subtracting the SST component from measured coral d18O. The d18Oresidual and a regional precipitation index are highly correlated at low frequencies, suggesting that d18Osw variations are primarily atmospheric-driven. Warmer SSTs at Los Roques broadly coincide with higher precipitation in the southeastern Caribbean at multidecadal time scales, effectively strengthening the climate signal in the coral d18O record. The Los Roques coral d18O record displays a strong and statistically significant relationship to different indices of hurricane activity during the peak of the Atlantic hurricane season in boreal summer and is a particularly good indicator of decadal-multidecadal swings in the latter indices. In general, the detection of long-term changes and trends in Atlantic hurricane activity is hampered due to the limited length of the reliable instrumental record and the known inhomogeneity in the observational databases which result from changes in observing practice and technology over the years. The results suggest that coral-derived proxy data from Los Roques can be used to infer changes in past hurricane activity on timescales that extend well beyond the reliable record. In addition, the coral record exhibits a clear negative trend superimposed on the decadal to multidecadal cycles, indicating a significant warming and freshening of surface waters in the genesis region of tropical cyclones during the past decades. The presented coral d18O time series provides the first and, so far, longest continuous coral-based record of hurricane activity. It appears that the combination of both signals (SST and d18Osw) in coral d18O leads to an amplification of large-scale climate signals in the record, and makes coral d18O even a better proxy for hurricane activity than SST alone. Atlantic hurricane activity naturally exhibits strong multidecadal variations that are associated with the Atlantic Multidecadal Oscillation (AMO), the major mode of lowfrequency variability in the North Atlantic Ocean. However, the mechanisms underlying this multidecadal variability remain controversial, primarily because of the limited instrumental record. The Los Roques coral d18O displays strong multidecadal variability with a period of approximately 60 years that is closely related to the AMO, making the Archipelago Los Roques a very sensitive location for studying low-frequency climate variability in the Atlantic Ocean. In summary, the coral records presented in this thesis capture different key climate variables in the north tropical Atlantic region very well, indicating that fast-growing Diploria strigosa corals represent a promising marine archive for further proxy-based reconstructions of past climate variability on a range of time scales.

Planktonic foraminiferal oxygen isotopes of ODP Site 143-865 samples

Cool tropical sea surface temperatures (SSTs) are reported for warm Paleogene greenhouse climates based on the d18O of planktonic foraminiferal tests. These results are difficult to reconcile with models of greenhouse gas-forced climate. It has been suggested that this "cool tropics paradox" arises from postdepositional alteration of foraminiferal calcite, yielding erroneously high d18O values. Recrystallization of foraminiferal tests is cryptic and difficult to quantify, and the compilation of robust d18O records from moderately altered material remains challenging. Scanning electron microscopy of planktonic foraminiferal chamber-wall cross sections reveals that the basal area of muricae, pustular outgrowths on the chamber walls of species belonging to the genus Morozovella, contain no mural pores and may be less susceptible to postdepositional alteration. We analyzed the d18O in muricae bases of morozovellids from the central Pacific (Ocean Drilling Program Site 865) by ion microprobe using 10 ?m pits with an analytical reproducibility of ±0.34 per mil (2 standard deviations). In situ measurements of d18O in these domains yield consistently lower values than those published for conventional multispecimen analyses. Assuming that the original d18O is largely preserved in the basal areas of muricae, this new d18O record indicates Early Paleogene (~49-56 Ma) tropical SSTs in the central Pacific were 4°-8°C higher than inferred from the previously published d18O record and that SSTs reached at least ~33°C during the Paleocene-Eocene thermal maximum. This study demonstrates the utility of ion microprobe analysis for generating more reliable paleoclimate records from moderately altered foraminiferal tests preserved in deep-sea sediments.

Stable isotope analysis of Porites coral core EILAT-1

The environmental interpretation of the 13C/12C variations in the skeletons of massive corals is still a matter of debate. A 19-year seasonal skeletal 13C/12C record of a shallow-water Pontes coral from the northern Red Sea (Gulf of Aqaba) documents interannual events of extraordinarily large plankton blooms, indicated by anomalous 13C depletions in the coral skeleton. These blooms are caused by deep vertical water mass mixing, convectively driven in colder winters, which results in increased supplies of nutrients to the surface waters. The deep vertical mixings can sometimes be driven by the cooling occurring throughout the Middle East after large tropical volcanic eruptions. We therefore have evidence in our coral skeletal 13C/12C record for an indirect volcanic signal of the eruptions of El Chichón (1982) and Mount Pinatubo (1991). Deep mixing induced 13C/12C variations of the dissolved inorganic carbon in the surface waters can be neglected at this location. We therefore suggest that the 13C skeletal depletions can be best explained by changes in the coral's autotrophy-heterotrophy diet, through increased heterotrophic feeding on Zooplankton during the blooms. Increased feeding on 13C-depleted Zooplankton or increased heterotrophy at the expense of autotrophy can both result in a 13C-depleted coral skeleton. However, this suggestion requires more testing. If our conclusions are substantiated, seasonal skeletal 13C/12C records of corals which change from autotrophy under normal conditions to increased heterotrophy during bloom events may be used as indicators of ocean paleoproductivity at interannual resolution, available from no other source.

Age model and stable oxygen isotope mean values of ice core SZ99 from Akademii Nauk ice cap on Severnaya Zemlya

Between 1999 and 2001, a 724 m long ice core was drilled on Akademii Nauk, the largest glacier on Severnaya Zemlya, Russian Arctic. The drilling site is located near the summit. The core is characterized by high melt-layer content. The melt layers are caused by melting and even by rain during the summer. We present high-resolution data of density, electrical conductivity (dielectrical profiling), stable water isotopes and melt-layer content for the upper 136 m (120 m w.e.) of the ice core. The dating by isotopic cycles and electrical conductivity peak identification suggests that this core section covers approximately the past 275 years. Singularities of volcanogenic and anthropogenic origin provide well-defined additional time markers. Long-term temperatures inferred from 12 year running mean averages of d18O reach their lowest level in the entire record around 1790. Thereafter the d18O values indicate a continuously increasing mean temperature on the Akademii Nauk ice cap until 1935, interrupted only by minor cooling episodes. The 20th century is found to be the warmest period in this record.

Stable oxygen and carbon isotope ratios and paleotemperature reconstructions from Inoceramus in Cretaceous sediments of DSDP Sites

Inoceramus is an epibenthic bivalve which lived in a wide variety of paleoenvironments encompassing a broad range of paleodepths. A survey of all Cretaceous sediments from Deep Sea Drilling Project legs 1-69 and 75 revealed over 500 Inoceramus specimens at twenty sites. Of these, 47 well-preserved Late Cretaceous specimens from the South Atlantic, Pacific and Indian Oceans were analyzed for oxygen and carbon isotopes. The specimens exhibit small internal isotopic variability and oxygen isotopic paleotemperatures that are consistent with a deep-sea habitat. Paleotemperatures ranging from 5 to 16°C show that Late Cretaceous oceans were significantly warmer than the present oceans. The data suggest that deep water was formed both by cooling at high latitudes and by evaporation in the subtropics.

Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.