Oxygen Utilization and Downward Carbon Flux in an Oxygen-Depleted Eddy in the Eastern Tropical North Atlantic

The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40-100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, under water gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg-1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0-70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg-1 day-1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m-2 day-1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.

Palynological counts (dinoflagellate cysts) and foraminiferal geochemistry (d18O, d18C, Mg/Ca) of the Pliocene-Pleistocene transition in the North Atlantic

The position of the North Atlantic Current (NAC) during the intensification of Northern Hemisphere glaciation (iNHG) has been evaluated using dinoflagellate cyst assemblages and foraminiferal geochemistry from a ~260 kyr interval straddling the base of the Quaternary System from two sites: eastern North Atlantic Deep Sea Drilling Project Site 610 in the path of the present NAC and central North Atlantic Integrated Ocean Drilling Program Site U1313 in the subtropical gyre. Stable isotope and foraminiferal Mg/Ca analyses confirm cooling near the marine isotope stage (MIS) G7-G6 transition (2.74 Ma). However, a continued dominance of the dinoflagellate cyst Operculodinium centrocarpum sensu Wall and Dale (1966) indicates an active NAC in the eastern North Atlantic for a further 140 kyr. At MIS 104 (~2.60 Ma), a profound dinoflagellate cyst assemblage turnover indicates NAC shutdown in the eastern North Atlantic, implying elevated atmospheric pressure over the Arctic and a resulting shift in the westerlies that would have driven the NAC. These findings challenge recent suggestions that there was no significant southward shift of the NAC or the Arctic Front during iNHG, and reveal a fundamental climatic reorganization near the base of the Quaternary.

Age determination of sediment cores from the North Atlantic

Evidence from North Atlantic deep sea cores reveals that abrupt shifts punctuated what is conventionally thought to have been a relatively stable Holocene climate. During each of these episodes, cool, ice-bearing waters from north of Iceland were advected as far south as the latitude of Britain. At about the same times, the atmospheric circulation above Greenland changed abruptly. Pacings of the Holocene events and of abrupt climate shifts during the last glaciation are statistically the same; together, they make up a series of climate shifts with a cyclicity close to 1470 +/- 500 years. The Holocene events, therefore, appear to be the most recent manifestation of a pervasive millennial-scale climate cycle operating independently of the glacial-interglacial climate state. Amplification of the cycle during the last glaciation may have been linked to the North Atlantic's thermohaline circulation.

Particle fluxes of the bathypelagic sediment trap CVOO-3 in the eastern tropical North Atlantic for the period December 2009 until May 2011

Particle fluxes at the Cape Verde Ocean Observatory (CVOO) in the eastern tropical North Atlantic for the period December 2009 until May 2011 are discussed based on bathypelagic sediment trap time-series data collected at 1290 and 3439 m water depth. The typically oligotrophic particle flux pattern with weak seasonality is modified by the appearance of a highly productive and low oxygen (minimum concentration below 2 µmol kg**-1 at 40 m depth) anticyclonic modewater eddy (ACME) in winter 2010. The eddy passage was accompanied by unusually high mass fluxes of up to 151 mg m**-2 d**-1, lasting from December 2009 to May 2010. Distinct biogenic silica (BSi) and organic carbon flux peaks of ~15 and 13.3 mg m**-2 d**-1, respectively, were observed in February-March 2010 when the eddy approached the CVOO. The flux of the lithogenic component, mostly mineral dust, was well correlated with that of organic carbon, in particular in the deep trap samples, suggesting a tight coupling. The lithogenic ballasting obviously resulted in high particle settling rates and, thus, a fast transfer of epi-/meso-pelagic signatures to the bathypelagic traps. We suspect that the two- to three-fold increase in particle fluxes with depth as well as the tight coupling of mineral dust and organic carbon in the deep trap samples might be explained by particle focusing processes within the deeper part of the eddy. Molar C : N ratios of organic matter during the ACME passage were around 18 and 25 for the upper and lower trap samples, respectively. This suggests that some productivity under nutrient (nitrate) limitation occurred in the euphotic zone of the eddy in the beginning of 2010 or that a local nitrogen recycling took place. The d15N record showed a decrease from 5.21 to 3.11 per mil from January to March 2010, while the organic carbon and nitrogen fluxes increased. The causes of enhanced sedimentation from the eddy in February/March 2010 remain elusive, but nutrient depletion and/or an increased availability of dust as a ballast mineral for organic-rich aggregates might have contributed. Rapid remineralisation of sinking organic-rich particles could have contributed to oxygen depletion at shallow depth. Although the eddy formed in the West African coastal area in summer 2009, no indications of coastal flux signatures (e.g. from diatoms) were found in the sediment trap samples, confirming the assumption that the suboxia developed within the eddy en route. However, we could not detect biomarkers indicative of the presence of anammox (anaerobic ammonia oxidation) bacteria or green sulfur bacteria thriving in photic zone suboxia/hypoxia, i.e. ladderane fatty acids and isorenieratene derivatives, respectively. This could indicate that suboxic conditions in the eddy had recently developed and/or the respective bacterial stocks had not yet reached detection thresholds. Another explanation is that the fast-sinking organic-rich particles produced in the surface layer did not interact with bacteria from the suboxic zone below. Carbonate fluxes dropped from -52 to 21.4 mg m**-2 d**-1 from January to February 2010, respectively, mainly due to reduced contribution of shallow-dwelling planktonic foraminifera and pteropods. The deep-dwelling foraminifera Globorotalia menardii, however, showed a major flux peak in February 2010, most probably due to the suboxia/hypoxia. The low oxygen conditions forced at least some zooplankton to reduce diel vertical migration. Reduced "flux feeding" by zooplankton in the epipelagic could have contributed to the enhanced fluxes of organic materials to the bathypelagic traps during the eddy passage. Further studies are required on eddy-induced particle production and preservation processes and particle focusing.

(Table 1) Basement penetration, recovery, and lithology of crustal DSDP holes in the North Atlantic Ocean

Oceanic crustal drilling by R. V. Glomar Challenger at 15 sites in the North Atlantic has led to a complex picture of the upper half kilometer of the crust. Elements of the picture include the absence of the source for linear magnetic anomalies, marked episodicity of volcanic activity, ubiquitous low temperature alteration and evidence for large scale tectonic disturbance. Comparison sections in the Pacific and much deeper crustal drilling are needed to attack problems arising from the North Atlantic results.

Geochemical and physical sediment properties of sediment cores from the Portuguese shelf

Marine sediments from the Portuguese shelf are influenced by environmental changes in the surrounding continental and marine environment. These are largely controlled by the North Atlantic Oscillation, but additional impacts may arise from episodic tsunamis. In order to investigate these influences, a high resolution multi-proxy study has been carried out on a 5.4 m long gravity core and five box cores from the Tagus prodelta on the western Portuguese margin, incorporating geochemical (Corg/Ntotal ratios, d13Corg, d15N, d18O, Corg and CaCO3 content) and physical sediment properties (magnetic susceptibility, grain-size). Subsurface data of the five box cores indicate no major effect of early postdepositional alteration. Surface data show a higher fraction of terrigenous organic material close to the river mouth and in the southern prodelta. Gravity core GeoB 8903 covers the last 3.2 kyrs with a temporal resolution of at least 0.1 cm/yr. Very high sedimentation rates between 69 and 140 cm core depth indicate a possible disturbance of the record by the AD1755 tsunami, although no evidence for a disturbance is observed in the data. Sea surface temperature and salinity on the prodelta, the local budget of marine NO3- as well as the provenance of organic matter remained virtually constant during the past 3.2 kyrs. A positive correlation between magnetic susceptibility (MS) and North Atlantic Oscillation (NAO) is evident for the past 250 years, coinciding with a negative correlation between mean grain-size and NAO. This is assigned to a constant riverine supply of fine material with high MS, which is diluted by the riverine input of a coarser, low-MS component during NAO negative, high-precipitation phases. End-member modelling of the lithic grain-size spectrum supports this, revealing a third, coarse lithic component. The high abundance of this coarse end-member prior to 2 kyr BP is interpreted as the result of stronger bottom currents, concentrating the coarse sediment fraction by winnowing. As continental climate was more arid prior to 2 kyr BP (Subboreal), the coarse end-member may also consist of dust from local sources. A decrease in grain-size and CaCO3 content after 2 kyr BP is interpreted as a result of decreasing wind strength. The onset of a fining trend and a further decrease in CaCO3 around AD900 occurs simultaneous to climatic variations, reconstructed from eastern North Atlantic records. A strong increase in MS between AD1400 and AD1500 indicates higher lithic terrigenous input, caused by deforestation in the hinterland.

Lake Son Kol geochemistry, µXRF, biogeochemistry and pollen record

In general, a moderate drying trend is observed in mid-latitude arid Central Asia since the Mid-Holocene, attributed to the progressively weakening influence of the mid-latitude Westerlies on regional climate. However, as the spatio-temporal pattern of this development and the underlying climatic mechanisms are yet not fully understood, new high-resolution paleoclimate records from this region are needed. Within this study, a sediment core from Lake Son Kol (Central Kyrgyzstan) was investigated using sedimentological, (bio)geochemical, isotopic, and palynological analyses, aiming at reconstructing regional climate development during the last 6000 years. Biogeochemical data, mainly reflecting summer moisture conditions, indicate predominantly wet conditions until 4950 cal. yr BP, succeeded by a pronounced dry interval between 4950 and 3900 cal. yr BP. In the following, a return to wet conditions and a subsequent moderate drying trend until present times are observed. This is consistent with other regional paleoclimate records and likely reflects the gradual Late Holocene diminishment of the amount of summer moisture provided by the mid-latitude Westerlies. However, climate impact of the Westerlies was apparently not only restricted to the summer season but also significant during winter as indicated by recurrent episodes of enhanced allochthonous input through snowmelt, occurring before 6000 cal. yr BP and at 5100-4350, 3450-2850, and 1900-1500 cal. yr BP. The distinct ~1500-year periodicity of these episodes of increased winter precipitation in Central Kyrgyzstan resembles similar cyclicities observed in paleoclimate records around the North Atlantic, likely indicating a hemispheric-scale climatic teleconnection and an impact of North Atlantic Oscillation (NAO) variability in Central Asia.

Stable oxygen isotope record from Greenland ice cores

Twenty ice cores drilled in medium to high accumulation areas of the Greenland ice sheet have been used to extract seasonally resolved stable isotope records. Relationships between the seasonal stable isotope data and Greenland and Icelandic temperatures as well as atmospheric flow are investigated for the past 150-200 years. The winter season stable isotope data are found to be influenced by the North Atlantic Oscillation (NAO) and very closely related to SW Greenland temperatures. The linear correlation between the first principal component of the winter season stable isotope data and Greenland winter temperatures is 0.71 for seasonally resolved data and 0.83 for decadally filtered data. The summer season stable isotope data display higher correlations with Stykkisholmur summer temperatures and North Atlantic SST conditions than with SW Greenland temperatures. The linear correlation between Stykkisholmur summer temperatures and the first principal component of the summer season stable isotope data is 0.56, increasing to 0.66 for decadally filtered data. Winter season stable isotope data from ice core records that reach more than 1400 years back in time suggest that the warm period that began in the 1920s raised southern Greenland temperatures to the same level as those that prevailed during the warmest intervals of the Medieval Warm Period some 900-1300 years ago. This observation is supported by a southern Greenland ice core borehole temperature inversion. As Greenland borehole temperature inversions are found to correspond better with winter stable isotope data than with summer or annual average stable isotope data it is suggested that a strong local Greenland temperature signal can be extracted from the winter stable isotope data even on centennial to millennial time scales.

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.

Deuterium analysis of ice core GISP2

The Greenland Ice Sheet Project 2 (GISP2) core can enhance our understanding of the relationship between parameters measured in the ice in central Greenland and variability in the ocean, atmosphere, and cryosphere of the North Atlantic Ocean and adjacent land masses. Seasonal (summer, winter) to annual responses of dD and deuterium excess isotopic signals in the GISP2 core to the seesaw in winter temperatures between West Greenland and northern Europe from A.D. 1840 to 1970 are investigated. This seesaw represents extreme modes of the North Atlantic Oscillation, which also influences sea surface temperatures (SSTs), atmospheric pressures, geostrophic wind strength, and sea ice extents beyond the winter season. Temperature excursions inferred from the dD record during seesaw/extreme NAO mode years move in the same direction as the West Greenland side of the seesaw. Symmetry with the West Greenland side of the seesaw suggests a possible mechanism for damping in the ice core record of the lowest decadal temperatures experienced in Europe from A.D. 1500 to 1700. Seasonal and annual deuterium excess excursions during seesaw years show negative correlation with dD. This suggests an isotopic response to a SST/ land temperature seesaw. The isotopic record from GISP2 may therefore give information on both ice sheet and sea surface temperature variability. Cross-plots of dD and d show a tendency for data to be grouped according to the prevailing mode of the seesaw, but do not provide unambiguous identification of individual seesaw years. A combination of ice core and tree ring data sets may allow more confident identification of GA and GB (extreme NAO mode) years prior to 1840.

Lacustrine sediments from two setions in northern Greece

We investigated two lignite quarries in northern Greece for orbital and suborbital climate variability. Sections Lava and Vegora are located at the southern and northern boundaries of the Ptolemais Basin, a northwest southeast elongated intramontane basin that contains Upper Miocene to Lower Pliocene lacustrine sediments. Sediments show cyclic alterations of marl-rich (light), and coal-rich or clay-rich (dark) strata on a decimeter to meter scale. First, we established low-resolution ground-truth stratigraphy based on paleomagnetics and biostratigraphy. Accordingly, the lower 67 m and 65 m that were investigated in both sections Vegora and Lava, respectively, belong to the Upper Miocene and cover a time period of 6.85 to 6.57 and 6.46 to 5.98 Ma at sedimentation rates of roughly 14 and 22 cm/ka. In order to obtain a robust and high-resolution chronology, we then tuned carbonate minima (low L* values; high magnetic susceptibility values) to insolation minima. Besides the known dominance of orbital precession and eccentricity, we detected a robust hemi-precessional cycle in most parameters, most likely indicative for monsoonal influence on climate. Moreover, the insolation-forced time series indicate a number of millennial-scale frequencies that are statistically significant with dominant periods of 1.5-8 kyr. Evolutionary spectral analysis indicates that millennial-scale climate variability documented for the Ptolemais Basin resembles the one that is preserved in ice-core records of Greenland. Most cycles show durations of several tens of thousands of years before they diminish or cease. This is surprising because the generally argued cause for Late Quaternary millennial-scale variability is associated with the presence of large ice sheets, which cannot be the case for the Upper Miocene. Possible explanations maybe a direct response to solar forcing, an influence on the formation of North Atlantic Deep Water through the outflow of high-salinity water, or an atmospheric link to the North Atlantic Oscillation.

Abundance of phytoplankton, heterotrophic nanoflagellates and bacteria through the water column at time series station L4 in the Western English Channel. 2007-2011

The marine laboratories in Plymouth have sampled at two principle sites in the Western English Channel for over a century in open-shelf (station E1; 50° 02'N, 4° 22'W) and coastal (station L4; 50° 15'N, 4° 13'W) waters. These stations are seasonally stratified from late-April until September, and the variable biological response is regulated by subtle variations in temperature, light, nutrients and meteorology. Station L4 is characterized by summer nutrient depletion, although intense summer precipitation, increasing riverine input to the system, results in pulses of increased nitrate concentration and surface freshening. The winter nutrient concentrations at E1 are consistent with an open-shelf site. Both stations have a spring and autumn phytoplankton bloom; at station E1, the autumn bloom tends to dominate in terms of chlorophyll concentration. The last two decades have seen a warming of around 0.6°C per decade, and this is superimposed on several periods of warming and cooling over the past century. In general, over the Western English Channel domain, the end of the 20th century was around 0.5°C warmer than the first half of the century. The warming magnitude and trend is consistent with other stations across the north-west European Shelf and occurred during a period of reduced wind stress and increased levels of insolation (+20%); these are both correlated with the larger scale climatic forcing of the North Atlantic Oscillation.