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.

Chemical composition of DSDP and ODP cherts

Rare earth element (REE), major, and trace element abundances and relative fractionations in forty nodular cherts sampled by the Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) indicate that the REE composition of chert records the interplay between terrigenous sources and scavenging from the local seawater. Major and (non-REE) trace element ratios indicate that the aluminosilicate fraction within the chert is similar to NASC (North American Shale Composite), with average Pacific chert including ~7% NASC-like particles, Indian chert ~11% NASC, Atlantic chert ~17% NASC, and southern high latitude (SHL) chert 53% NASC. Using La as a proxy for sum REE, approximations of excessive La (the amount of La in excess of that supplied by the detrital aluminosilicate fraction) indicate that Pacific chert contains the greatest excessive La (85% of total La) and SHL chert the least (38% of total La). As shown by interelement associations, this excessive La is most likely an adsorbed component onto aluminosilicate and phosphatic phases. Accordingly, chert from the large Pacific Ocean, where deposition occurs relatively removed from significant terrigenous input, records a depositional REE signal dominated by adsorption of dissolved REEs from seawater. Pacific chert Ce/Ce* <<1 and normative La/Yb ~ 0.8-1, resulting from adsorption of local Ce-depleted seawater and preferential adsorption of LREEs from seawater (e.g., normative La/Yb ~0.4), which increases the normative La/Yb ratio recorded in chert. Chert from the Atlantic basin, a moderately sized ocean basin lined by passive margins and with more terrigenous input than the Pacific, records a mix of adsorptive and terrigenous REE signals, with moderately negative Ce anomalies and normative La/Yb ratios intermediate to those of the Pacific and those of terrigenous input. Chert from the SHL region is dominated by the large terrigenous input on the Antarctic passive margin, with inherited Ce/Ce* ~1 and inherited normative La/Yb values of ~1.2-1.4. Ce/Ce* does not vary with age, either throughout the entire data base or within a particular basin. Overall, Ce/Ce* does not correlate with P2O5 concentrations, even though phosphatic phases may be an important REE carrier.

Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Middle to late Miocene oxygen isotope stratigraphy of ODP site 1085 (SE Atlantic): new constrains on Miocene climate variability and sea-level fluctuations

The middle Miocene delta18O increase represents a fundamental change in earth's climate system due to a major expansion and permanent establishment of the East Antarctic Ice Sheet accompanied by some effect of deepwater cooling. The long-term cooling trend in the middle to late Miocene was superimposed by several punctuated periods of glaciations (Mi-Events) characterized by oxygen isotopic shifts that have been related to the waxing and waning of the Antarctic ice-sheet and bottom water cooling. Here, we present a high-resolution benthic stable oxygen isotope record from ODP Site 1085 located at the southwestern African continental margin that provides a detailed chronology for the middle to late Miocene (13.9-7.3 Ma) climate transition in the eastern South Atlantic. A composite Fe intensity record obtained by XRF core scanning ODP Sites 1085 and 1087 was used to construct an astronomically calibrated chronology based on orbital tuning. The oxygen isotope data exhibit four distinct delta18O excursions, which have astronomical ages of 13.8, 13.2, 11.7, and 10.4 Ma and correspond to the Mi3, Mi4, Mi5, and Mi6 events. A global climate record was extracted from the oxygen isotopic composition. Both long- and short-term variabilities in the climate record are discussed in terms of sea-level and deep-water temperature changes. The oxygen isotope data support a causal link between sequence boundaries traced from the shelf and glacioeustatic changes due to ice-sheet growth. Spectral analysis of the benthic delta18O record shows strong power in the 400-kyr and 100-kyr bands documenting a paleoceanographic response to eccentricity-modulated variations in precession. A spectral peak around 180-kyr might be related to the asymmetry of the obliquity cycle indicating that the response of the dominantly unipolar Antarctic ice-sheet to obliquityinduced variations probably controlled the middle to late Miocene climate system. Maxima in the delta18O record, interpreted as glacial periods, correspond to minima in 100-kyr eccentricity cycle and minima in the 174-kyr obliquity modulation. Strong middle to late Miocene glacial events are associated with 400-kyr eccentricity minima and obliquity modulation minima. Thus, fluctuations in the amplitude of obliquity and eccentricity seem to be the driving force for the middle to late Miocene climate variability.

Benthic foraminifera accumulation rate and benthic foraminiferal productivity proxies at ODP Site 165-999 in the Caribbean (Appendix A)

This study tests the hypothesis that the late Miocene to early Pliocene constriction and closure of the Central American Seaway (CAS), connecting the tropical Atlantic and East quatorial Pacific (EEP), caused a decrease in productivity in the Caribbean, due to decreased coastal upwelling and an end to the connection with high-productivity tropical Pacific waters. The present study compared paleoceanographic proxies for the interval between 8.3 and 2.5 Ma in 47 samples from south Caribbean ODP Site 999 with published data on EEP DSDP Site 503. Proxies for Site 999 include the relative abundance of benthic foraminiferal species representing bottom current velocity and the flux of organic matter to the sea floor, the ratio of infaunal/epifaunal benthic foraminiferal species and benthic foraminifer accumulation rates (BFARs). In addition, we calculated % resistant planktic foraminifers species and used the previously published % sand fraction and benthic carbon isotope values from Site 999. During early shoaling of the Isthmus (8.3-7.9 Ma) the Caribbean was under mesotrophic conditions, with little ventilation of bottom waters and low current velocity. The pre-closure interval (7.6-4.2 Ma) saw enhanced seasonal input of phytodetritus with even more reduced ventilation, and enhanced dissolution between 6.8 and 4.8 Ma. During the post-closure interval (4.2-2.5 Ma) in the Caribbean, paleoproductivity decreased, current velocity was reduced, and ventilation improved, while the seasonality of phytodetrital input was reduced dramatically, coinciding with the establishment of the Atlantic-Pacific salinity contrast at 4.2 Ma. Our data support the hypothesis that late Miocene constriction of the CAS at 7.9 Ma and its closure at 4.2 Ma caused a gradual decrease in paleoproductivity in the Caribbean, consistent with decreased current velocity and seasonality of the phytodetrital input.

Palynofacies analysis of sediments in the eastern Equatorial Atlantic

Analyses of the palynofacies and sporomorph thermal alteration indices (TAI) of sediments from Ocean Drilling Program (ODP) Sites 959 to 962 in the Cote d'Ivoire-Ghana Transform Margin, West Africa were undertaken to (1) determine the source and depositional conditions of the organic matter in the sediments, (2) refine a paleobathymetric curve derived from other data for Site 959, which drilled the most continuous sedimentary sequence from Pleistocene to Albian and (3) interpret the paleothermal history of the area. Twelve types of dispersed organic matter were identified: amorphous organic matter (AOM), marine palynomorphs, algae, resins, black debris, yellow-brown fragments, black-brown fragments, cuticles, plant tissue, wood, sporomorphs and fungi, The relative abundances of these organic matter components at each site were analyzed using cluster analysis, resulting in the identification of seven palynofacies assemblages at Site 959, five each at sites 960 and 961, and four at Site 962. Amorphous organic matter (which is chiefly marine derived), black debris and wood have played the most significant role in defining palynofacies assemblages. The palynofacies assemblages show some correlation with lithologic units, sediment sources and depositional environments. Previous palynofacies studies in passive margins have demonstrated that changes in the ratio of AOM to terrestrial organic matter are related primarily to proximal-distal positions of depositional environments relative to the shoreline. However, this assumption does not always hold true for a transform margin where tectonic factors play an important role in the organic matter distribution, at least in the early stages of evolution. Lithofacies, CCD paleodepths for the North Atlantic, trace fossil association, benthic foraminifera and palynofacies data were the criteria used for reconstructing a paleobathymetric curve for Site 959. A cyclicity in the organic matter distribution of the Upper Miocene to Lower Pliocene pelagic sediments could be related to fluctuations in productivity of biosiliceous and calcareous organisms, and sedimentation rates. A drastic increase in the amount of AOM and a decrease in black debris and wood in the carbonate and clastic rocks (Lithologic Unit IV) overlying the tectonized Albian sediments (Lithologic Unit V) at Sites 959 and 960 coincide with the presence of an unconformity. Qualitative color analysis of palynomorphs was undertaken for all sites, although the main focus was on Site 959 where detailed organic geochemical data were available. At Site 959, TAI values indicate an immature stage of organic maturation (<2) down to the black claystones of Lithologic Unit III at about 918.47 mbsf. Below this, samples show an increase with depth to a moderately mature stage (>2 except for the claystone samples between 1012.52 and 1036.5 mbsf, and one limestone sample at 1043.4 mbsf), reaching peak levels of 2.58 to 3.0 in the tectonized Albian sediments below the unconformity. These TAI values show a positive correlation with the Tma x values derived from Rock-Eval pyrolysis data. The highest values recorded in the basal tectonized units at all the sites (Sites 960-962 have mean values between 2.25 and 3.13) may be related to high heat flow during the intracontinental to syntransform basin stage in the region.

Oxygen and carbon isotope measurements of North Atlantic from IODP Hole 307-U1317E

Recent deep-ocean exploration has revealed unexpectedly widespread and diverse coral ecosystems in deep water on continental shelves, slopes, seamounts, and ridge systems around the world. Origin and growth history of these cold-water coral mounds are poorly known, owing to a lack of complete stratigraphic sections through them. Here we show high-resolution oxygen isotope records of planktic foraminifers from the base to the top of Challenger Mound, southwest of Ireland, which was drilled during Integrated Ocean Drilling Program Expedition 307. Challenger Mound began to grow during isotope stage 92 (2.24 million years ago (Ma)), immediately after the onset of Northern Hemisphere glaciation and the initiation of modern stratification in the northeast Atlantic. Mound initiation was likely due to reintroduction of Mediterranean Outflow Water (MOW) and ensuing development of a density gradient with overlying northeastern Atlantic water (NEAW), where organic matter was prone to be stagnated and fueled the coral ecosystem. Coral growth continued for 11 glacial-interglacial cycles until isotopic stage 72 (1.82 Ma) with glacial siliciclastic input from the continental margin. After a long hiatus that separates the lower mound and the upper mound, coral growth restored for a short time in isotope stages 19-18 (0.8-0.7 Ma) in which sediments were either eroded or not deposited during a full glacial stage. The development pattern of the water mass interface between MOW and NEAW might have changed, because of the fluctuations of the MOW production which is responsible for the amplitude in ice volume oscillations from the low-amplitude 41 ka cycles for the lower mound to the high-amplitude 100 ka cycles for the upper mound. The average sedimentation and CaCO3 production rates of the lower mound were evaluated 27 cm/ka and 31.1 g/cm2/ka, respectively.

(Table 1) Elemental composition of benthic foraminifera from South Atlantic core top samples

The ocean plays a major role in the global carbon cycle, and attempts to reconstruct past changes in the marine carbonate system are increasing. The speciation of dissolved uranium is sensitive to variations in carbonate system parameters, and previous studies have shown that this is recorded in the uranium-to-calcium ratio (U/Ca) of the calcite shells of planktonic foraminifera. Here we test whether U/Ca ratios of deep-sea benthic foraminifera are equally suited as an indicator of the carbonate system. We compare U/Ca in two common benthic foraminifer species (Planulina wuellerstorfi and Cibicidoides mundulus) from South Atlantic core top samples with the calcite saturation state (Delta [CO3**2-] = [CO3**2-]in situ - [CO3**2-]sat) of the ambient seawater and find significant negative correlations for both species. Compared with planktonic foraminifera, the sensitivity of U/Ca in benthic foraminifera to changes in Delta [CO3**2-] is about 1 order of magnitude higher. Although Delta [CO3**2-] exerts the dominant control on the average foraminiferal U/Ca, the intertest and intratest variability indicates the presence of additional factors forcing U/Ca.