Stable oxygen isotope record and Mg/Ca ratios at the Mid-Pleistocene Climate Transition, ODP Site 181-1123

Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.

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.

Element abundances and Nd isotopic composition in boninite and tholeiite from DSDP Hole 60-458

Boninites are unusual high MgO-high SiO2 volcanic rocks found in several western Pacific island arcs. Their high Mg/(Mg + total Fe) (0.55-0.83) and compatible element contents (Ni = 70-450 ppm, Cr = 200-1800 ppm) indicate equilibration with mantle peridotite, but their low TiO2 contents (0.1-0.5%) indicate severe depletion of this source. K, Rb, Sr and Ba abundances in boninites are typical of primitive arc basalts, but ratios such as Ti/Zr and La/Yb are variable (Ti/Zr = 23-67, (La/Yb)e.f. = 0.6-4.7). Evidence for both enrichment and depletion of incompatible elements suggests that boninites are derived from refractory peridotite which has been metasomatically enriched in LREE, Zr, Sr, Ba and alkalis. Wide variations in 143Nd/144Nd (0.51262-0.51296) are correlated with La/Sm, Sm/Nd and Ti/Zr, which enables identification of components in the boninite source. Possible LREE depleted components have relative REE and Ti abundances like those in depleted peridotites and high 143Nd/144Nd ratios which reach MORB-like values. Possible LREE enriched components have relative REE abundances similar to those in metasomatized mantle peridotite nodules, and low 143Nd/144Nd ratios which indicate either sedimentary sources or mantle sources with recent to ancient LREE enrichment. Relative abundances of Ba and Sr in boninites decrease with increasing LREE enrichment and suggest a non-sedimentary source for the LREE enriched material. Enrichment in Ba, Sr and alkalis may result from a third component derived from subducted oceanic crust. Two models can account for the successive generation of boninites and arc tholeiites within a single area: 1) boninites can be derived from the peridotite residue of earlier arc tholeiite generation which is metasomatically enriched in LREE before boninite volcanism, or 2) arc tholeiites and boninites can be derived from a variably depleted peridotite source which has been pervasively enriched in LREE. Areas of fertile peridotite would yield tholeiites while refractory areas would yield boninites.

(Figure 2) Organic carbon content, stable isotope ratios, TEX86 index and sea surface temperature reconstruction for the early Aptian of ODP Hole 198-1207B

The Cretaceous has long been recognized as a time when greenhouse conditions were fueled by elevated atmospheric CO2 and accompanied by perturbations of the global carbon cycle described as oceanic anoxic events (OAEs). Yet, the magnitude and frequency of temperature change during this interval of warm and equable climate are poorly constrained. Here we present a high-resolution record of sea-surface temperatures (SSTs) reconstructed using the TEX86 paleothermometer for a sequence of early Aptian organic-rich sediments deposited during the first Cretaceous OAE (OAE1a) at Shatsky Rise in the tropical Pacific. SSTs range from ~30 to ~36 °C and include two prominent cooling episodes of ~4 °C. The cooler temperatures reflect significant temperature instability in the tropics likely triggered by changes in carbon cycling induced by enhanced burial of organic matter. SST instability recorded during the early Aptian in the Pacific is comparable to that reported for the late Albian-early Cenomanian in the Atlantic, suggesting that such climate perturbations may have recurred during the Cretaceous with concomitant consequences for biota and the marine environment.

Nd, Pb, and Be isotopes of ferromanaganese crusts of the South Pacific

The application of radiogenic isotopes to the study of Cenozoic circulation patterns in the South Pacific Ocean has been hampered by the fact that records from only equatorial Pacific deep water have been available. We present new Pb and Nd isotope time series for two ferromanganese crusts that grew from equatorial Pacific bottom water (D137-01, 'Nova', 7219 m water depth) and southwest Pacific deep water (63KD, 'Tasman', 1700 m water depth). The crusts were dated using 10Be/9Be ratios combined with constant Co-flux dating and yield time series for the past 38 and 23 Myr, respectively. The surface Nd and Pb isotope distributions are consistent with the present-day circulation pattern, and therefore the new records are considered suitable to reconstruct Eocene through Miocene paleoceanography for the South Pacific. The isotope time series of crusts Nova and Tasman suggest that equatorial Pacific deep water and waters from the Southern Ocean supplied the dissolved trace metals to both sites over the past 38 Myr. Changes in the isotopic composition of crust Nova are interpreted to reflect development of the Antarctic Circumpolar Current and changes in Pacific deep water circulation caused by the build up of the East Antarctic Ice Sheet. The Nd isotopic composition of the shallower water site in the southwest Pacific appears to have been more sensitive to circulation changes resulting from closure of the Indonesian seaway.

Sedimentology and stable oxygen isotope ratios of foraminifera from cores of the Porcupine Seabight, Northeast Atlantic

Large carbonate mound structures have been discovered in the northern Porcupine Seabight (Northeast Atlantic) at depths between 600 and 1000 m. These mounds are associated with the growth of deep-sea corals Lophelia pertusa and Madrepra oculata. In this study, three sediment cores have been analysed. They are from locations close to Propeller Mound, a 150 m high ridge-like feature covered with a cold-water coral ecosystem at its upper flanks. The investigations are concentrated on grain-size analyses, carbon measurements and on the visual description of the cores and computer tomographic images, to evaluate sediment content and structure. The cores portray the depositional history of the past ~31 kyr BP, mainly controlled by sea-level fluctuations and the climate regime with the advance and retreat of the Irish Ice Sheet onto the Irish Mainland Shelf. A first advance of glaciers is indicated by a turbiditic release slightly older than 31 kyr BP, coherent with Heinrich event 3 deposition. During Late Marine Isotope Stage 3 (MIS 3) and MIS 2 shelf erosion prevailed with abundant gravity flows and turbidity currents. A change from glaciomarine to hemipelagic contourite sedimentation during the onset of the Holocene indicates the establishment of the strong, present-day hydrodynamic regime at intermediate depths. The general decrease in accumulation of sediments with decreasing distance towards Propeller Mound suggests that currents (turbidity currents, gravity flows, bottom currents) had a generally stronger impact on the sediment accumulation at the mound base for the past ~31 kyr BP, respectively.

Benthic foraminifera, stable isotope ratios and carbon concentrations of sediment cores from Propeller Mound and Porcupine Srabight

On- and off-mound sediment cores from Propeller Mound (Hovland Mound province, Porcupine Seabight) were analysed to understand better the evolution of a carbonate mound. The evaluation of benthic foraminiferal assemblages from the off-mound position helps to determine the changes of the environmental controls on Propeller Mound in glacial and interglacial times. Two different assemblages describe the Holocene and Marine Isotope Stage (MIS) 2 and late MIS 3 (~31 kyr BP). The different assemblages are related to changes in oceanographic conditions, surface productivity and the waxing and waning of the British Irish Ice Sheet (BIIS) during the last glacial stages. The interglacial assemblage is related to a higher supply of organic material and stronger current intensities in water depth of recent coral growth. During the last glaciation the benthic faunas showed high abundances of cassidulinid species, implying cold bottom waters and a reduced availability of organic matter. High sedimentation rates and the domination of Elphidium excavatum point to shelf erosion related to sea-level lowering (~50 m) and the progradation of the BIIS onto the shelf. A different assemblage described for the on-mound core is dominated by Discanomalina coronata, Gavelinopsis translucens, Planulina ariminensis, Cibicides lobatulus and to a lower degree by Hyrrokkin sarcophaga. These species are only found or show significantly higher relative abundances in on-mound samples and their maximum contribution in the lower part of the record indicates a higher coral growth density on Propeller Mound in an earlier period. They are less abundant during the Holocene, however. This dataset portrays the boundary conditions of the habitable range for the cold-water coral Lophelia pertusa, which dominates the deep-water reefal ecosystem on the upper flanks of Propeller Mound. The growth of this ecosystem occurs during interglacial and interstadial periods, whereas a retreat of corals is documented in the absence of glacial sediments on-mound. Glacial conditions with cold intermediate waters, a weak current regime and high sedimentation rates provide an unfavourable environmental setting for Lophelia corals to grow. A Late Pleistocene decrease is observed in the mound growth for Propeller Mound, which might face its complete burial in the future, as it already happened to the buried mounds of the Magellan Mound province further north.

Stable oxygen isotope ratios and grain size analyses of sediment cores from the Propeller Mound, Northeast Atlantic

The first detailed stratigraphic record from a deep-water carbonate mound in the Northeast Atlantic based on absolute datings (U/Th and AMS 14C) and stable oxygen isotope records reveals that its top sediment sequences are condensed by numerous hiatuses. According to stable isotope data, mainly sediments with an intermediate signal are preserved on the mound, while almost all fully glacial and interglacial sediments have either not been deposited or have been eroded later. The resulting hiatuses reduce the Late Pleistocene sediment accumulation at Propeller Mound to amounts smaller than the background sedimentation. The hiatuses most likely result due to the sweeping of the mound in turn with the re-establishment of vigour interglacial circulation patterns after sluggish current regimes during glacials. Thus, within the discussion if internal, fluid-driven or external environmentally driven processes control the evolution of such carbonate mounds, our findings for Propeller Mound clearly point to environmental forcing as the dominant mechanism shaping deep-water carbonate mounds in the NE Atlantic during the Late Pleistocene and Holocene.

Organic matter C and N composition and N. pachyderma stable isotope ratios of ODP Hole 188-1166A sediments

We report the results of downhole stable isotopic (d13Corg [organic carbon] and d15N) and elemental measurements (total organic carbon [TOC], total nitrogen [TN], and carbon/nitrogen [C/N]) of sedimentary organic matter (SOM) along with stable isotopic measurements (d18O and d13C) of left-coiling Neogloboquadrina pachyderma planktonic foraminifers from Ocean Drilling Program Site 1166. TOC and TN measurements indicate a large change from organic-rich preglacial sediments with primary organic matter to organic-poor early glacial and glacial sediments, with mainly recycled organic matter. Results of the stable isotopic measurements of SOM show a range of values that are typical of both marine and terrestrial organic matter, probably reflecting a mixture of the two. However, C/N values are mostly high (>15), suggesting greater input and/or preservation of terrestrial organic matter. Foraminifers are only present in glacial/glaciomarine sediments of latest Pliocene to Pleistocene age at Site 1166 (lithostratigraphic Unit I). The majority of this unit has d13Corg and TOC values that are similar to those of glacial sediments recovered at Site 1167 (lithostratigraphic Unit II) on the slope and may have the same source(s). Although the low resolution of the N. pachyderma (s.) d18O and d13C data set precludes any specific paleoclimatic interpretation, downcore variations in foraminifer d18O and d13C values of 0.5 per mil to 1 per mil amplitude may indicate glacial-interglacial changes in ice volume/temperature in the Prydz Bay region.

Fatty acid composition, element concentration and isotope ratios of sea ice algae sampled in Rijpfjorden, Svalbard

The accelerating decrease of Arctic sea ice substantially changes the growth conditions for primary producers, particularly with respect to light. This affects the biochemical composition of sea ice algae, which are an essential high-quality food source for herbivores early in the season. Their high nutritional value is related to their content of polyunsaturated fatty acids (PUFAs), which play an important role for successful maturation, egg production, hatching and nauplii development in grazers. We followed the fatty acid composition of an assemblage of sea ice algae in a high Arctic fjord during spring from the early bloom stage to post bloom. Light conditions proved to be decisive in determining the nutritional quality of sea ice algae, and irradiance was negatively correlated with the relative amount of PUFAs. Algal PUFA content decreased on average by 40 % from April to June, while algal biomass (measured as particulate carbon, C) did not differ. This decrease was even more pronounced when algae were exposed to higher irradiances due to reduced snow cover. The ratio of chlorophyll a (chl a) to C, as well as the level of photoprotective pigments, confirmed a physiological adaptation to higher light levels in algae of poorer nutritional quality. We conclude that high irradiances are detrimental to sea ice algal food quality, and that the biochemical composition of sea ice algae is strongly dependent on growth conditions.