Sulfur speciation in bottom sediments from deep-sea basins of the Atlantic Ocean

Distribution of reduced sulfur forms in vertical sediment sections in deep-sea basins of the Atlantic Ocean is under study. Presence of weak sulfate reduction process resulted from low concentrations of reactive organic matter and differing by characteristic features of the initial stage of development. Interpretation of results is given on the base of consideration of dynamic redox equilibrium in the system: reduced sulfur - dissolved oxygen.

Aprubt climate change events in the Northeastern Atlantic Ocean

The western Iberian margin has been one of the key locations to study abrupt glacial climate change and associated interhemispheric linkages. The regional variability in the response to those events is being studied by combining a multitude of published and new records. Looking at the trend from Marine Isotope Stage (MIS) 10 to 2, the planktic foraminifer data, conform with the alkenone record of Martrat et al. [2007], shows that abrupt climate change events, especially the Heinrich events, became more frequent and their impacts in general stronger during the last glacial cycle. However, there were two older periods with strong impacts on the Atlantic meridional overturning circulation (AMOC): the Heinrich-type event associated with Termination (T) IV and the one occurring during MIS 8 (269 to 265 ka). During the Heinrich stadials of the last glacial cycle, the polar front reached the northern Iberian margin (ca. 41°N), while the arctic front was located in the vicinity of 39°N. During all the glacial periods studied, there existed a boundary at the latter latitude, either the arctic front during extreme cold events or the subarctic front during less strong coolings or warmer glacials. Along with these fronts sea surface temperatures (SST) increased southward by about 1°C per one degree of latitude leading to steep temperature gradients in the eastern North Atlantic and pointing to a close vicinity between subpolar and subtropical waters. The southern Iberian margin was always bathed by subtropical water masses - surface and/ or subsurface ones -, but there were periods when these waters also penetrated northward to 40.6°N. Glacial hydrographic conditions were similar during MIS 2 and 4, but much different during MIS 6. MIS 6 was a warmer glacial with the polar front being located further to the north allowing the subtropical surface and subsurface waters to reach at minimum as far north as 40.6°N and resulting in relative stable conditions on the southern margin. In the vertical structure, the Greenland-type climate oscillations during the last glacial cycle were recorded down to 2465 m during the Heinrich stadials, i.e. slightly deeper than in the western basin. This deeper boundary is related to the admixing of Mediterranean Outflow Water, which also explains the better ventilation of the intermediate-depth water column on the Iberian margin. This compilation revealed that latitudinal, longitudinal and vertical gradients existed in the waters along the Iberian margin, i.e. in a relative restricted area, but sufficient paleo-data exists now to validate regional climate models for abrupt climate change events in the northeastern North Atlantic Ocean.

Stable isotope ratios on 3 sediment cores from Tagus prodelta off Lisbon

A high-resolution sedimentary sequence recovered from the Tagus prodelta has been studied with the objective to reconstruct multi-decadal to centennial-scale climate variability on the western Iberian Margin and to discuss the observations in a wider oceanographic and climatic context. Between ca. 100 BC and AD 400 the foraminiferal fauna and high abundance of Globorotalia inflata indicate advection of subtropical waters via the Azores Current and the winter-time warm Portugal Coastal Current. Between ca. AD 400 and 1350, encompassing the Medieval Climate Anomaly (MCA), enhanced upwelling is indicated by the planktonic foraminiferal fauna, in particular by the high abundance of upwelling indicator species Globigerina bulloides. Relatively light d18O values and high sea surface temperature (SST) (reconstructed from foraminiferal assemblages) point to upwelling of subtropical Eastern North Atlantic Central Water. Between ca. AD 1350 and 1750, i.e. most of the Little Ice Age, relatively heavy d18O values and low reconstructed SST, as well as high abundances of Neogloboquadrina incompta, indicate the advection of cold subpolar waters to the area and a southward deflection of the subpolar front in the North Atlantic, as well as changes in the mode of the North Atlantic Oscillation. In addition, the assemblage composition together with the other proxy data reveals less upwelling and stronger river input than during the MCA. Stronger Azores Current influence on the Iberian Margin and strong anthropogenic effect on the climate after AD 1750 is indicated by the foraminiferal fauna. The foraminiferal assemblage shows a significant change in surface water conditions at ca. AD 1900, including enhanced river runoff, a rapid increase in temperature and increased influence of the Azores Current. The Tagus record displays a high degree of similarity to other North Atlantic records, indicating that the site is influenced by atmospheric-oceanic processes operating throughout the North Atlantic, as well as by local changes.

(Appendix A) Relative abundance of Emiliania huxleyi in sediment cores of the North Atlantic

The coccolithophore species Emiliania huxleyi is characterized by a wide range of sizes, which can be easily distinguished in the light microscope. In this study we have quantified the abundance of large (coccoliths > 4 µm in maximum length) E. huxleyi specimens during the last 25 kyr in sedimentary records from eleven cores and drill sites in the NE Atlantic and W Mediterranean Sea, to prove its usefulness in the reconstruction of water mass dynamics and biostratigraphic potential. During the Last Glacial Maximum this large form, a cold-water indicator, was common in the NE Atlantic and Mediterranean, and its regional variation in abundance indicates a displacement of the climatic zones southwards in agreement with the development of ice sheets and sea ice in the Northern Hemisphere during this period. On the other hand, the gradient between northern and southern surface water masses in the Subtropical Gyre appears to have been more pronounced than at present, while the Portugal and Canary Currents were more intense. In the western Mediterranean basin temperatures were cooler than in the adjacent Atlantic, provoking a quasi-endemism of these specimens until the end of Heinrich Event 1. This may have been due to a restriction in the communication between the Atlantic and Mediterranean through the Strait of Gibraltar, the arrival of cold surface water and the amplification of cooling after the development of ice sheets in the Northern Hemisphere. During the deglaciation, large E. huxleyi specimens decreased in abundance at medium and low latitudes, but were still numerous close to the Subarctic region during the Holocene. In transitional waters this decrease to present day abundances occurred after Termination Ib. The abrupt change in abundance of this large E. huxleyi form is proposed as a new biostratigraphic event to characterize the Holocene in mid- to low-latitude water masses in the North Atlantic, although this horizon seems to be diachronous by 5 kyr from tropical to subarctic regions, in agreement with the gradual onset of warm conditions.

Oxygen and hydrogen isotopes measured in the Northeast Atlantic

Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 d18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, dD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5 per mil for d18O and 0 to 2 per mil for dD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high d18O (0.5-1.1 per mil) and dD (3-6 per mil) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (d18O: -0.1 to 0.5 per mil; dD: -1 to 4 per mil) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed d18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0.46 described previously by Pierre et al. (1994, J. Mar. Syst. 5 (2), 159-170.) for the tropical to subtropical Northeast Atlantic. This slope decreases to 0.46 for the subtropical North Atlantic Central Water (NACW) and the MOW and to 0.32 for the surface waters of the upper 50 m. The dD-salinity mixing lines have estimated slopes of 3.01 for the complete data, 1.26 for the MOW, 3.47 for the NACW, and 2.63 for the surface waters. The slopes of the d18O-dD relationship are significantly lower than the one for the Global Meteoric Water Line with 5.6 for the complete data set, 2.30 for the MOW, 4.79 for the NACW, and 3.99 for the surface waters. The lower slopes in all the relationships clearly reflect the impact of the evaporation surplus in the subtropics.

Cenozoic sediments facies and geochemistry of ODP Hole 103-637A

The late Cenozoic deposits recovered at ODP Site 637 from the Iberian Abyssal Plain near the continental margin off northwestern Spain include three main facies groups. Turbidites are the dominant facies association (two-thirds of the total thickness), followed by pelagites (one-fourth), and subordinate amounts of contourites (one-tenth). Slump deposits occur locally in the upper Miocene and middle Pliocene. Turbidity currents and pelagic settling were the significant sediment depositional processes from the Pliocene to the Pleistocene, whereas bottom currents predominated during the late Miocene. Fine-grained, base-cut-out turbidites, normally starting with the Td division, are the most abundant sequence type. The pelagites include both carbonate-rich pelagic and hemipelagic facies. The two types of contourites, sandy and calcareous-rich or fine-grained terrigenous, record two types of bottom-current processes. The Cenozoic deposits at Site 637 show a general upward transition from contourites in the upper Miocene to turbidites in the Pliocene-Quaternary. The entire section is rhythmically bedded and has a poorly developed cyclic pattern defined by variations in the total carbonate content. The low sedimentation rates also show the same cyclicity, with lower values for the late Miocene and late Pliocene. This evolution reflects the predominant depositional processes and the dissolution of carbonates by a lower CCD during the late Miocene.

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.