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.

Temperature and salinity reconstruction for sediment core GeoB3313-1

We reconstructed changes of temperature, salinity, and productivity within the southern Peru-Chile Current during the last 8000 years from a high-resolution sediment core recovered at 41°S using alkenones, isotope ratios of planktic foraminifera, biogenic opal, and organic carbon. Paleotemperatures and paleosalinities reached maximum values at ~5500 years ago and thereafter declined to modern values, whereas paleoproductivity continuously increased throughout the last 8000 years. We ascribe these long-term Holocene trends primarily to latitudinal shifts of the Antarctic Circumpolar Current (ACC). The concurrence with shifts in the position of the Southern Westerlies points to a common response of atmospheric and oceanographic circulation patterns off southern Chile. Millennial- to centennial-scale fluctuations of paleotemperatures and paleosalinities, on the other hand, lag displacements in the position of the Southern Westerlies but reveal a significant correlation to short-term temperature changes in Antarctica, indicating a high-latitude control of the ACC at these timescales.

Plutonium and americium concentrations in sea water and in sinking particles

Vertical fluxes of 239+240Pu and 241Am and temporal changes in their inventories in the northwestern Mediterranean Sea have been examined through high-resolution water column sampling coupled with direct measurements of the vertical flux of particle-bound transuranics using time-series sediment traps. Water column profiles of both radionuclides showed well-defined sub-surface maxima (2391240Pu between 100-400 m; 241Am at 100-200 m and 800 m), the depths of which are a result of the different biogeochemical scavenging behavior of the two radionuclides. Comparison of deep water column (0-2,000 m) transuranic inventories with those derived from earlier measurements demonstrate that the total 2391240Pu inventory had not substantially changed between 1976-1990 whereas 241Am had decreased by approximately 24%. Enhanced scavenging of 241Am and a resultant, more rapid removal from the water column relative to 239+240Pu was also supported by the observation of elevated Am/Pu activity ratios in sinking particles collected in sediment traps at depth. Direct measurements of the downward flux of particulate 239+240Pu and 241Am compared with transuranic removal rates derived from observed total water column inventory differences over time, show that particles sinking out of deep waters (1,000-2,000 m) could account for 26-72% of the computed total annual 239+240Pu loss and virtually all of the 241Am removal from the water column. Upper water column (0-200 m) residence times based on direct flux measurements ranged from 20-30 yr for 239+240Pu and 5-10 yr for 241Am. The observation that 241Am/239+240Pu activity ratios in unfiltered Mediterranean seawater are six times lower than those in the north Pacific suggests the existence of a specific mechanism for enhanced scavenging and removal of 241Am from the generally oligotrophic waters of the open Mediterranean. It is proposed that atmospheric inputs of aluminosilicate particles transported by Saharan dust events which frequently occur in the Mediterranean region could enhance the geochemical scavenging and resultant removal of 241Am to the sediments.

Temperature reconstruction of sediment cores from the northeastern Arabian Sea

In order to reconstruct the monsoonal variability during the late Holocene we investigated a complete, annually laminated sediment record from the oxygen minimum zone (OMZ) off Pakistan for oxygen isotopes of planktic foraminifera and alkenone-derived sea surface temperatures (SST). Significant SST changes of up to 3°C which cannot be explained by changes in the alkenone-producing coccolithophorid species (inferred from the Gephyrocapsa oceanica / Emiliania huxleyi ratio) suggest that SST changes are driven by changes in the monsoon strength. Our high-(decadal)-resolution data indicate that the late Holocene in the northeastern Arabian Sea was not characterized by a stable uniform climate, as inferred from the Greenland ice cores, but by variations in the dominance of the SW monsoon conditions with significant effects on temperatures. Highest SST fluctuations of up to 3.0°C and 2.5°C were observed for the time interval from 4600 to 3300 years B.P. and during the past 500 years. The significant, short-term SST changes during the past 500 years might be related to climatic instabilities known from the northern latitudes ("Little Ice Age") and confirm global effects. Surface salinity values, reconstructed from delta18O records after correction for temperature-related oxygen isotope fractionation, suggest that in general, the past 5000 years were characterized by higher-than-recent evaporation and more intense SW monsoon conditions. However, between 4600 and 3700 years B.P., evaporation dropped, SW monsoon weakened, and NE monsoon conditions were comparatively enhanced. For the past 1500 years we infer strongly fluctuating monsoon conditions. Comparisons of reconstructed salinity records with ice accumulation data from published Tibetan ice core and Tibetan tree ring width data reveal that during the past 2000 years, enhanced evaporation in the northeastern Arabian Sea correlates with periods of increased ice accumulation in Tibet, and vice versa. This suggests a strong climatic relationship between both monsoon-controlled areas.

Stable carbon and oxygen isotope composition of Late Cretaceous benthic foraminifera from the southern South Atlantic

The stable carbon and oxygen isotope composition of different benthic foraminiferal species of the latest Campanian and earliest Maastrichtian from Ocean Drilling Project Hole 690C (Weddell Sea, southern South Atlantic, ~1800 m paleowater depth) have been investigated. The total range of measured isotope values of all samples exceeds ~4 per mil for delta 13C and 1.1 per mil for delta 18O. Carbon isotope values of proposed deep infaunal species are generally similar or only slightly lower when compared to proposed epifaunal to shallow infaunal species. Interspecific differences vary between samples probably reflecting temporal changes in organic carbon fluxes to the sea floor. Constantly lower delta 13C values for Pullenia marssoni and Pullenia reussi suggest the deepest habitat for these species. The strong depletion of delta 13C values by up to 3 per mil within lenticulinids may be attributed to a deep infaunal microhabitat, strong vital effects, or different feeding strategy when compared to other species or modern lenticulinids. The mean delta 18O values reveal a strong separation of epifaunal to shallow infaunal and deep infaunal species. Epifaunal to shallow infaunal species are characterized by low delta 18O values, deep infaunal species by higher values. This result possibly reflects lower metabolic rates and longer life cycles of deep infaunal species or the operating of a pore water [CO3]2- effect on the benthic foraminiferal stable isotopes. Pyramidina szajnochae shows an enrichment of oxygen isotopes with test size comprising a total of 0.6 per mil between 250 and 1250 µm shell size. Although delta 13C lacks a corresponding trend these data likely represent the presence of changes in metabolic rates during ontogenesis. These results demonstrate the general applicability of multi-species stable isotope measurements of pristine Cretaceous benthic foraminifera to reconstruct past microhabitats and to evaluate biological and environmental effects on the stable isotope composition.

Micropaleontological investigation of Late Albanian Col de Palluel

The Niveau Breistroffer black shale succession in the Vocontian Basin (SE France) is the regional equivalent of the widely distributed Late Albian Oceanic Anoxic Event 1d. The studied black shale-rich interval at the Col de Palluel section is 6.28 m thick and comprises four black shale units with up to 2.5 wt% total organic carbon (TOC) intercalated with marlstones. Calcareous nannofossil, palynomorph, planktic Foraminifera and stable isotopic data from the Niveau Breistroffer succession suggest that short-term climate changes influenced its deposition, with relatively warm and humid climate during black shale formation in comparison with relatively cool and dry climatic conditions during marlstone deposition. An increase in the terrigenous/marine ratio of palynomorphs indicates enhanced humidity and higher runoff during black shale formation. A nutrient index based on calcareous nannofossils and the abundance pattern of small (63-125 µm) hedbergellid Foraminifera show short-term changes in the productivity of the surface water. Surface-water productivity was reduced during black shale formation and increased during marlstone deposition. A calcareous nannofossil temperature index and bulk-rock oxygen isotope data indicate relative temperature changes, with warmer surface waters for black shale samples. At these times, warm-humid climate and reduced surface-water productivity were accompanied by greater abundances of 'subsurface'-dwelling calcareous nannofossils (nannoconids) and planktic Foraminifera (rotaliporids). These taxa presumably indicate more stratified surface-water conditions. We suggest that the formation of the Niveau Breistroffer black shales occurred during orbitally induced increase in monsoonal activity that led to increasing humidity during periods of black shale formation. This, in turn, caused a decrease in low-latitude deep-water formation and probably an increase in surface-water stratification. The combination of these two mechanisms caused depleted O2 concentrations in the bottom water that increased the preservation potential of organic matter

Biogeochemistry of sediments in the Aegean Sea

Biochemical composition of sedimentary organic matter (OM), vertical fluxes and bacterial distribution were studied at 15 stations (95-2270 m depth) in the Aegean Sea during spring and summer. Downward fluxes of labile OM were significantly higher in the northern than in the southern part and were higher in summer than in spring. Primary inputs of OM were not related to sedimentary OM concentrations, which had highest values in summer. Sedimentary chlorophyll-a concentrations were similar in the northern and southern parts. Carbohydrates, the main component of sedimentary OM, were about 1.2 times higher in the southern part than in the northern, without significant temporal changes. Total proteins were higher in summer and about double in the northern part. Sedimentary proteins appeared more dependent upon the downward flux of phytopigment than of proteins. Sedimentary OM was characterised by a relatively large fraction of soluble compounds and showed better quality in the northern part. The lack of a depth-related pattern in sedimentary OM and the similar concentrations in the two areas suggest that differences in sedimentary OM quality in the Aegean basin are dependent on system productivity; the bulk of sedimentary OM is largely conservative. Sedimentary bacterial density was about double in the northern part and higher in spring than in summer, but bacterial size was about three times higher in summer, resulting in a larger bacterial biomass in summer. Bacterial density was coupled with total and protein fluxes, indicating a rapid bacterial response to pelagic production. Bacterial biomass was significantly correlated with sedimentary protein and phytopigment concentrations, indicating a clear response to accumulation of labile OM in the sediments. In all cases bacteria accounted for <5% of the organic C and N pools. The efficiency of benthic bacteria in exploiting protein pools, estimated as amounts of protein available per unit bacterial biomass, indicates a constant ratio of about 70 µg proteins/µg C. This suggests a similar bacterial efficiency all over the area studied, unaffected by different trophic conditions.

Stable isotope record and distribution of foraminifera in sediment core GeoB3004-1

Fluctuations in the abundance of selected foraminiferal indicator species and diversity allowed the reconstruction of changes in deepwater oxygenation and monsoon-driven organic matter fluxes in the deep western Arabian Sea during the last 190 kyr. Times of maximum surface production coincide with periods of intensified SW monsoon as shown by the abundance of Globigerina bulloides and enhanced carbonate corrosion. Benthic ecosystem variability in the deep Arabian Sea is not exclusively driven by variations in monsoonal upwelling and related organic matter supply to the seafloor but also by changes in deepwater ventilation. Deepening of the base of the oxygen minimum zone (OMZ) below 1800 m water depth is strongly coherent on the precessional band but lags proxies of SW monsoon strength by 4 to 6 kyr. The "out-of-phase" relationship between OMZ deepening and maximum SW monsoon strength is explained by temporal changes in the advection of oxygen-rich deepwater masses of North Atlantic and Antarctic origin. This process affected the remineralization and burial efficiency of organic matter in the deep Arabian Sea, resulting in the observed phase lag between maximum monsoon strength and organic carbon preservation.

Eolian accumulation rates of ODP Leg 121 holes

The late Cenozoic history of eolian sedimentation in the eastern Indian Ocean was developed from samples recovered during drilling of Sites 752, 754, and 756. Temporal changes in the mass accumulation rate of eolian material reflect major climatic shifts in the southern African source region. A significant drop in dust mass flux values occurs near the end of the lower Oligocene. Younger sediments are characterized by a gradual reduction in dust accumulation rates until the middle Miocene after which values remain consistently low throughout the late Cenozoic, although a slight increase in eolian accumulation rate occurs near 2.5 Ma. This pattern of dust mass flux appears related to the supply of dust-sized particles in the source region and represents a shift in the climatic regime of southern Africa to increasingly more arid conditions throughout the late Cenozoic.

Updated bathymetric chart of the East Aral Sea

The Aral Sea is located in an arid region with much sand and salt deposits in the surrounding barren open land. Hence, significant displacements of sediments into the lakebed by the action of wind, water, gravity, or snow are likely. The bathymetry of the lake was last observed in the 1960s, and within the last half century, the structure of the lakebed has changed. Based on satellite observations of the temporal changes of shoreline (Landsat optical remote sensing) and water level (multi-mission satellite altimetry) over more than one decade an updated bathymetric chart for the East Basin of the Aral Sea has been generated. During this time, the geometry of the shallow East Basin experienced strong fluctuations due to the occurrence of periods of drying and strong inflow. By the year 2014 the East Basin fell dry. The dynamic behavior of the basin allowed for estimating the lake's bathymetry from a series of satellite-based information. The river mouth made its impression in the present East Aral Sea, because its shrinking led to the inflow of much sediment into the lake's interior. In addition, salt deposits along the shorelines increased the corresponding elevation, a phenomenon that is more pronounced in the reduced lakebed because of increased salinity. It must be noted that height estimates from satellite altimetry were only possible down to a minimum elevation of 27 m above sea level due to a lack of reliable altimetry data over the largely reduced water surface. In order to construct a complete bathymetric chart of the lakebed of the East Aral Sea heights below 27 m were obtained solely from Landsat optical images following the SRB (Selected Region Boundary) approach as described by Singh et al. (2015).

Age determination of North Atlantic sediment cores

Records of planktonic foraminiferal shell weights for Globigerina bulloides, covering Termination I from four proximal sites at waters depths from 1150 to 4045 m in the northeast Atlantic, demonstrate the influence of dissolution superimposed upon initial shell weight variability. Records of shell weight, unaffected by dissolution, may be used as a reference for interpreting deeper records in terms of preservation history. Combining records of planktonic shell weight (and benthic d13C) from shallow and deep sites suggests that maximum oceanic stratification and incursion of southern sourced deep waters in the North Atlantic occurred at about 18-20 ka, defining the glacial mode of Atlantic circulation. Reduced stratification and enhanced preservation in deeper waters reflect conditions during Heinrich event 1. A state similar to the modern mode of Atlantic circulation was attained by about 10 ka.

Physical oceanography during two METEOR cruises in the subpolar North Atlantic

The detection of multi-decadal trends in the oceanic oxygen content and its possible attribution to global warming is protracted by the presence of a substantial amount of interannual to decadal variability, which hitherto is poorly known and characterized. Here we address this gap by studying interannual to decadal changes of the oxygen concentration in the Subpolar Mode Water (SPMW), the Intermediate Water (IW) and the Mediterranean Outflow Water (MOW) in the eastern North Atlantic. We use data from a hydrographic section located in the eastern North Atlantic at about 48°N repeated 12 times over a period of 19 years from 1993 through 2011, with a nearly annual resolution up to 2005. Despite a substantial amount of year-to-year variability, we observe a long-term decrease in the oxygen concentration of all three water masses, with the largest changes occurring from 1993 to 2002. During that time period, the trends were mainly caused by a contraction of the subpolar gyre associated with a northwestward shift of the Subpolar Front (SPF) in the eastern North Atlantic. This caused SPMW to be ventilated at lighter densities and its original density range being invaded by subtropical waters with substantially lower oxygen concentrations. The contraction of the subpolar gyre reduced also the penetration of IW of subpolar origin into the region in favor of an increased northward transport of IW of subtropical origin, which is also lower in oxygen. The long-term oxygen changes in the MOW were mainly affected by the interplay between circulation and solubility changes. Besides the long-term signals, mesoscale variability leaves a substantial imprint as well, affecting the water column over at least the upper 1000 m and laterally by more than 400 km. Mesoscale eddies induced changes in the oxygen concentration of a magnitude that can substantially alias analyses of long-term changes based on repeat hydrographic data that are being collected at intervals of typically 10 years.

Benthic foraminiferal assemblages of the Barents Sea

Foraminiferal assemblages were studied in northern Barents Sea core ASV 880 along with oxygen and carbon isotope measurements in planktonic (N. pachyderma sin.) and benthic (E. clavatum) species. AMS C-14 measurements performed on molluscs Yoldiella spp. show that this core provides a detailed and undisturbed record of Holocene climatic changes over the last 10000 calendar years. Surface and deep waters were very cold (<0°C) at the beginning of the Holocene. C. reniforme dominated the highly diverse benthic foraminiferal assemblage. From 10 to 7.8 cal. ka BP, a warming trend culminated in a temperature optimum, which developed between 7.8 and 6.8 cal. ka BP. During this optimum, the input of Atlantic water to the Barents Sea reached its maximum. The Atlantic water mass invaded the whole Franz Victoria Trough and was present from subsurface to the bottom. No bottom water, which would form through rejection of brine during winter, was present at the core depth (388 m). The water stratification was therefore greatly reduced as compared to the present. An increase in percentage of I. helenae/norcrossi points to long seasonal ice-free conditions. The temperature optimum ended rather abruptly, with the return of cold polar waters into the trough within a few centuries. This was accompanied by a dramatic reduction of the abundance of C. reniforme. During the upper Holocene, the more opportunistic species E. clavatum became progressively dominant and the water column was more stratified. Deep water in Franz Victoria Trough contained a significant amount of cold Barents Sea bottom water as it does today, while subsurface water warmed progressively until about 3.7 cal. ka BP and reached temperatures similar to those of today. These long-term climatic changes were cut by several cold events of short duration, in particular one in the middle of the temperature optimum and another, which coincides most probably with the 8.2 ka BP cold event. Both long- and short-term climatic changes in the Barents Sea are associated with changes in the flow of Atlantic waters and the oceanic conveyor belt.

Foraminifer, coarse fraction and carbonate characteristics of sediments from ODP Leg 198 sites on Shatsky Rise

Holes 1209A and 1211A on Southern High, Shatsky Rise contain expanded, nearly continuous records of carbonate-rich sediment deposited in deep water of the equatorial Pacific Ocean during the Paleocene and Eocene. In this study, we document intervals of carbonate dissolution in these records by examining temporal changes in four parameters: carbonate content, coarse size fraction (>38 µm), benthic foraminiferal abundance, and planktonic foraminiferal fragmentation ratio. Carbonate content is not a sensitive indicator of carbonate dissolution in the studied sections, although rare intervals of low carbonate may reflect times of relatively high dissolution. The proportion of coarse size fraction does not accurately record carbonate dissolution either because the relative abundance of nannofossils largely determines the grain-size distribution. Benthic abundance and fragmentation covary (r**2 = 0.77) and are probably the best indicators for carbonate dissolution. For both holes, records of these parameters indicate two episodes of prominent dissolution. The first of these occurs in the upper Paleocene (~59-58 Ma) and the second in the middle to upper Eocene (~45-33.7 Ma). Other intervals of enhanced carbonate dissolution are located in the upper Paleocene (~56 Ma) and in the upper lower Eocene (~51 Ma). Enhanced preservation of planktonic foraminiferal assemblages marks the start of both the Paleocene and Eocene epochs.