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.

Hydrographical and chemical observations during an achor station in the eastern North Atlantic

Serial observations of temperature, salinity, oxygen, alkalinity and pH are presented. They were carried out during an anchor station of R.V. "Meteor" west of Cape Sao Vincente (Portugal) in the area of the maximum Mediterranean water outflow, which follows the continental slope off Portugal. Two observational results are pointed out: The Mediterranean water masses spread out into the Atlantic Ocean, consisting of two distinct layers at depth of 700 m (T=12.0 °C, S=36.15 ?) and 1250 m (T=11.3 °C, S=36.40 ?). The salinity proved to be the most significant indicator of the observed stratification. The values of dissolved oxygen content, alkalinity and pH in the very near bottom layer (1 m above the bottom at depth of 3250 m) are different from the values at depth of 15 m to 100 m above the bottom. As this phenomenon is not observed for the salinity, the changes may be interpreted in terms of chemical and biological processes at the sediment-water interface.

Middle Eocene to Pleistocene calcareous nannofossils of ODP Leg 113 holes

Long sequences of Upper Cretaceous through Quaternary sediments rich in calcareous and siliceous microfossils were recovered at Ocean Drilling Program Sites 689 and 690 on Maud Rise off East Antarctica. These sites have become the southernmost anchor in the Atlantic Basin for bio-, magneto-, chemostratigraphic, and paleobiogeographic studies. ODP Sites 692 and 693 on the Weddell Sea margin of East Antarctica and Site 696 on the South Orkney microcontinent of West Antarctica yielded calcareous nannofossils within some stratigraphic intervals. Sites 691, 692, 694, 695, and 697 did not recover Cenozoic calcareous nannofossils. Calcareous nannofossil biostratigraphy suggests a major hiatus across the Paleogene/Neogene boundary at Sites 689 and 690, and two additional hiatuses in the middle Eocene-lower Oligocene section at Site 690. Correlation with magnetostratigraphy reveals: the last occurrence (LO) of Reticulofenestra umbilica at Maud Rise is over 1 m.y. younger than that at the middle-latitude sites; the LO of Isthmolithus recurvus is synchronous in the middle-latitude and high-latitude areas (about 34.8 Ma); Reticulofenestra oamaruensis ranges from 38.0 to 36.0 Ma at Maud Rise; Reticulofenestra reticulata has a shorter range at Maud Rise (42.1 to 38.9 Ma) than at the middle-latitude DSDP Site 516; the range of Chiasmolithus oamaruensis is diachronous over different latitudes; and the LO of Chiasmolithus solitus is a good datum at 41.3 Ma from 30°S to 65°S in the South Atlantic Ocean. Comparison of calcareous nannofossil abundances in a latitudinal transect shows: Reticulofenestra bisecta is a temperate-water species and its LO, which crosses below that of Chiasmolithus altus at Maud Rise, is not applicable for the Paleogene/Neogene boundary in high southern latitude areas; Clausicoccus fenestratus is rare or absent at Maud Rise and can not be used as a marker; Coccolithus formosus is a warm-water species which disappeared earlier toward higher latitudes. Calcareous nannofossil assemblages indicate that by at least the middle Eocene, surface water temperatures became considerably lower in the high southern latitudes than in the middle-latitude areas and that there have been more extreme cold events in the high latitudes during the Neogene. Bicolumnus ovatus n. gen., n. sp. is proposed in this paper.

Pleistocene chronology of sediments from the Lomonosov Ridge

Despite its importance in the global climate system, age-calibrated marine geologic records reflecting the evolution of glacial cycles through the Pleistocene are largely absent from the central Arctic Ocean. This is especially true for sediments older than 200 ka. Three sites cored during the Integrated Ocean Drilling Program's Expedition 302, the Arctic Coring Expedition (ACEX), provide a 27 m continuous sedimentary section from the Lomonosov Ridge in the central Arctic Ocean. Two key biostratigraphic datums and constraints from the magnetic inclination data are used to anchor the chronology of these sediments back to the base of the Cobb Mountain subchron (1215 ka). Beyond 1215 ka, two best fitting geomagnetic models are used to investigate the nature of cyclostratigraphic change. Within this chronology we show that bulk and mineral magnetic properties of the sediments vary on predicted Milankovitch frequencies. These cyclic variations record "glacial" and "interglacial" modes of sediment deposition on the Lomonosov Ridge as evident in studies of ice-rafted debris and stable isotopic and faunal assemblages for the last two glacial cycles and were used to tune the age model. Potential errors, which largely arise from uncertainties in the nature of downhole paleomagnetic variability, and the choice of a tuning target are handled by defining an error envelope that is based on the best fitting cyclostratigraphic and geomagnetic solutions.

Palaeolake Rehwiese, NE-Germany, Younger Dryas varved data set RW09

The first 1400-year floating varve chronology for north-eastern Germany covering the late Allerød to the early Holocene has been established by microscopic varve counts from the Rehwiese palaeolake sediment record. The Laacher See Tephra (LST), at the base of the studied interval, forms the tephrochronological anchor point. The fine laminations were examined using a combination of micro-facies and ?-XRF analyses and are typical of calcite varves, which in this case provide mainly a warm season signal. Two varve types with different sub-layer structures have been distinguished: (I) complex varves consisting of up to four seasonal sub-layers formed during the Allerød and early Holocene periods, and, (II) simple two sub-layer type varves only occurring during the Younger Dryas. The precision of the chronology has been improved by varve-to-varve comparison of two independently analyzed sediment profiles based on well-defined micro-marker layers. This has enabled both (1) the precise location of single missing varves in one of the sediment profiles, and, (2) the verification of varve interpolation in disturbed varve intervals in the parallel core. Inter-annual and decadal-scale variability in sediment deposition processes were traced by multi-proxy data series including seasonal layer thickness, high-resolution element scans and total organic and inorganic carbon data at a five-varve resolution. These data support the idea of a two-phase Younger Dryas, with the first interval (12,675 - 12,275 varve years BP) characterised by a still significant but gradually decreasing warm-season calcite precipitation and a second phase (12,275 - 11,640 varve years BP) with only weak calcite precipitation. Detailed correlation of these two phases with the Meerfelder Maar record based on the LST isochrone and independent varve counts provides clues about regional differences and seasonal aspects of YD climate change along a transect from a location proximal to the North Atlantic in the west to a more continental site in the east.

Sediments in Arctic sea ice

Despite the Arctic sea ice cover's recognized sensitivity to environmental change, the role of sediment inclusions in lowering ice albedo and affecting ice ablation is poorly understood. Sea ice sediment inclusions were studied in the central Arctic Ocean during the Arctic 91 expedition and in the Laptev Sea (East Siberian Arctic Region Expedition 1992). Results from these investigations are here combined with previous studies performed in major areas of ice ablation and the southern central Arctic Ocean. This study documents the regional distribution and composition of particle-laden ice, investigates and evaluates processes by which sediment is incorporated into the ice cover, and identifies transport paths and probable depositional centers for the released sediment. In April 1992, sea ice in the Laptev Sea was relatively clean. The sediment occasionally observed was distributed diffusely over the entire ice column, forming turbid ice. Observations indicate that frazil and anchor ice formation occurring in a large coastal polynya provide a main mechanism for sediment entrainment. In the central Arctic Ocean sediments are concentrated in layers within or at the surface of ice floes due to melting and refreezing processes. The surface sediment accumulation in central Arctic multi-year sea ice exceeds by far the amounts observed in first-year ice from the Laptev Sea in April 1992. Sea ice sediments are generally fine grained, although coarse sediments and stones up to 5 cm in diameter are observed. Component analysis indicates that quartz and clay minerals are the main terrigenous sediment particles. The biogenous components, namely shells of pelecypods and benthic foraminiferal tests, point to a shallow, benthic, marine source area. Apparently, sediment inclusions were resuspended from shelf areas before and incorporated into the sea ice by suspension freezing. Clay mineralogy of ice-rafted sediments provides information on potential source areas. A smectite maximum in sea ice sediment samples repeatedly occurred between 81°N and 83°N along the Arctic 91 transect, indicating a rather stable and narrow smectite rich ice drift stream of the Transpolar Drift. The smectite concentrations are comparable to those found in both Laptev Sea shelf sediments and anchor ice sediments, pointing to this sea as a potential source area for sea ice sediments. In the central Arctic Ocean sea ice clay mineralogy is significantly different from deep-sea clay mineral distribution patterns. The contribution of sea ice sediments to the deep sea is apparently diluted by sedimentary material provided by other transport mechanisms.

Upper Cretaceous-Paleogene stratigraphy of ODP Sites 113-689 and 113-690

This contribution summarizes the biostratigraphy of planktonic foraminifers, calcareous nannofossils, and benthic foraminifers, in combination with the magnetostratigraphy, carbon and oxygen isotope stratigraphy of benthic foraminifers, and CaCO3 stratigraphy for the Maestrichtian through Paleogene calcareous sequences recovered at Sites 689 and 690 on Maud Rise (at about 65°S, eastern Weddell Sea, Antarctica). These data represent the southernmost calciumcarbonate record available for that interval, and thus extend the biostratigraphic and isotopic database to higher latitudes. Sites 689 and 690 form the southernmost anchor of a north-south transect through the Atlantic Ocean for Paleogene biostratigraphy and chemostratigraphy.

Middle Eocene Fe and Ca counts, Ca/Fe ratios, revised splices and astronomical age models form different Sites of IODP Exp342

Accurate age models are a tool of utmost important in paleoclimatology. Constraining the rate and pace of past climate change are at the core of paleoclimate research, as such knowledge is crucial to our understanding of the climate system. Indeed, it allows for the disentanglement of the various drivers of climate change. The scarcity of highly resolved sedimentary records from the middle Eocene (Bartonian - Lutetian Stages; 47.8 - 37.8 Ma) has led to the existence of the "Eocene astronomical time scale gap" and hindered the establishment of a comprehensive astronomical time scale (ATS) for the entire Cenozoic. Sediments from the Newfoundland Ridge drilled during Integrated Ocean Drilling Program (IODP) Expedition 342 span the Eocene gap at an unprecedented stratigraphic resolution with carbonate bearing sediments. Moreover, these sediments exhibit cyclic lithological changes that allow for an astronomical calibration of geologic time. In this study, we use the dominant obliquity imprint in XRF-derived calcium-iron ratio series (Ca/Fe) from three sites drilled during IODP Expedition 342 (U1408, U1409, U1410) to construct a floating astrochronology. We then anchor this chronology to numerical geological time by tuning 173-kyr cycles in the amplitude modulation pattern of obliquity to an astronomical solution. This study is one of the first to use the 173-kyr obliquity amplitude cycle for astrochronologic purposes, as previous studies primarily use the 405-kyr long eccentricity cycle as a tuning target to calibrate the Paleogene geologic time scale. We demonstrate that the 173-kyr cycles in obliquity's amplitude are stable between 40 and 50 Ma, which means that one can use the 173-kyr cycle for astrochronologic calibration in the Eocene. Our tuning provides new age estimates for magnetochron reversals C18n.1n - C21r and a stratigraphic framework for key sites from Expedition 342 for the Eocene. Some disagreements emerge when we compare our tuning for the interval between C19r and C20r with previous tuning attempts from the South Atlantic. We therefore present a revision of the original astronomical interpretations for the latter records, so that the various astrochronologic age models for the middle Eocene in the North- and South-Atlantic are consistent.

(Table 1) Clay and non-clay mineral composition of dirty ice samples from across the Arctic

Extensive dirty ice patches with up to 7 kg/m**2 sediment concentrations in layers of up to 10 cm thickness were encountered in 2005 and 2007 in numerous areas across the central Arctic. The Fe grain fingerprint determination of sources for these sampled dirty ice floes indicated both Russian and Canadian sources, with the latter dominating. The presence of benthic shells and sea weeds along with thick layers (2-10 cm) of sediment covering 5-10 m2 indicates an anchor ice entrainment origin as opposed to suspension freezing for some of these floes. The anchor ice origin might explain the dominance of Canadian sources where only narrow flaw leads occur that would not favor suspension freezing as an entrainment process. Expandable clays, commonly used as an indicator of a Kara Sea origin for dirty sea ice, are present in moderately high percentages (>20%) in many circum-Arctic source areas, including the Arctic coasts of North America. Some differences between the Russian and the North American coastal areas are found in clay mineral abundance, primarily the much higher abundance of chlorite in North America and the northern Barents Sea as opposed to the rest of the Russian Arctic. However, sea ice clay mineralogy matched many source areas, making it difficult to use as a provenance tool by itself. The bulk mineralogy (clay and non-clay) does not match specific sources possibly due to reworking of the sediment in dirty floes through summer melting or the failure to characterize all possible source areas.

(Table 1) Age markers and errors for the last 1215 ka in IODP Exp302

Despite its importance in the global climate system, age-calibrated marine geologic records reflecting the evolution of glacial cycles through the Pleistocene are largely absent from the central Arctic Ocean. This is especially true for sediments older than 200 ka. Three sites cored during the Integrated Ocean Drilling Program's Expedition 302, the Arctic Coring Expedition (ACEX), provide a 27 m continuous sedimentary section from the Lomonosov Ridge in the central Arctic Ocean. Two key biostratigraphic datums and constraints from the magnetic inclination data are used to anchor the chronology of these sediments back to the base of the Cobb Mountain subchron (1215 ka). Beyond 1215 ka, two best fitting geomagnetic models are used to investigate the nature of cyclostratigraphic change. Within this chronology we show that bulk and mineral magnetic properties of the sediments vary on predicted Milankovitch frequencies. These cyclic variations record ''glacial'' and ''interglacial'' modes of sediment deposition on the Lomonosov Ridge as evident in studies of ice-rafted debris and stable isotopic and faunal assemblages for the last two glacial cycles and were used to tune the age model. Potential errors, which largely arise from uncertainties in the nature of downhole paleomagnetic variability, and the choice of a tuning target are handled by defining an error envelope that is based on the best fitting cyclostratigraphic and geomagnetic solutions.