Geochemistry in the mid Atlantic Ocean ridge basalts

The main objective of Leg 82 of the Glomar Challenger was to document mantle heterogeneity in the vicinity of, and away from, a so-called hot spot: the Azores Triple Junction. One of the geochemical tools that permits, at least in part, the recognition of mantle heterogeneities uses hygromagmaphile elements, those elements that have an affinity for the liquid. This tool is presented in terms of an extended Coryell-Masuda plot, which incorporates within the rare earth elements the hygromagmaphile transition elements Th, Ta, Zr, Hf, Ti, Y, and V. The extended Coryell-Masuda plot is used to summarize our knowledge of mantle heterogeneity along the ridge axis at zero-age. It is also used by choosing those hygromagmaphile elements that can be analyzed on board by X-ray fluorescence spectrometry to give preliminary information on the enriched or depleted character of recovered samples. Shore-based results, which include analyses of most of the hygromagmaphile elements measured either by X-ray spectrometry or neutron activation analysis, confirm the shipboard data. From the point of view of comparative geochemistry, the variety of basalts recovered during Leg 82 provides a good opportunity to test and verify the classification of the hygromagmaphile elements. Analyses from Leg 82 provide new data about the relationship between extended rare earth patterns (enriched or depleted) that can be estimated either by La/Sm ratio or Nb/Zr (or Ta/Hf) ratios: samples from Hole 556 are depleted (low Nb/Zr ratio) but have a high 206Pb/ 204Pb (19.5) ratio; in Hole 558 a moderately enriched basalt unit with a La/Sm (= Nb/Zr) ratio (chondrite normalized) of 2 has a high 206Pb/204Pb (20) ratio. One of the most interesting results of Leg 82 lies in the crossing patterns of extended Coryell-Masuda plots for basalts from the same hole. This result enhances the notion of local mantle heterogeneity versus regional mantle heterogeneity and is confirmed by isotope data; it also favors a model of short-lived, discrete magma chambers. The data tend to confirm the Hayes Fracture Zone as a southern limit for the influence of Azores-type mantle. Nevertheless, north of the Hayes Fracture Zone, the influence of a plumelike mantle source is not simple and probably requires an explanation more complex than a contribution from a single fixed hot spot.

Sea surface temperature reconstruction for sediment core M35003-4 in the western tropical North Atlantic

Planktonic foraminiferal census counts are used to construct high-resolution sea surface temperature (SST) and subsurface (thermocline) temperature records at a core site in the Tobago Basin, Lesser Antilles. The record is used to document climatic variability at this tropical site in comparison to middle- and high-latitude sites and to test current concepts of cross-equatorial heat transports as a major player in interhemispheric climate variability. Temperatures are estimated using transfer function and modern analog techniques. Glacial - maximum cooling of 2.5°-3°C is indicated; maximum cooling by 4°C is inferred for isotope stage 3. The SST record displays millennial-scale variability with temperature jumps of up to 3°C and closely tracks the structure of ice-core Dansgaard/Oeschger cycles. SST variations in part of the record run opposite to the SST evolution at high northern latitude sites, pointing to thermohaline circulation and marine heat transport as an important factor driving SST in the tropical and high-latitude Atlantic, both on orbital and suborbital timescales.

(Table 1) Age determination of North Atlantic sediment cores

Stable isotope, trace metal, alkenone paleothermometry, and radiocarbon methods have been applied to sediment cores in the western subpolar North Atlantic between Hudson Strait and Cape Hatteras to reveal the history of climate in that region over the past ~11 kyr. We focus on cores from the Laurentian Fan, which is known to have rapid and continuous accumulation of hemipelagic sediment. Although results among our various proxy data are not always in agreement, the weight of the evidence (alkenone sea surface temperature (SST), d18O and abundance of Globigerinoides ruber) indicates a continual cooling of surface waters over Laurentian Fan, from about 18°C in the early Holocene to about 8°C today. Alternatively, Mg/Ca data on planktonic foraminifera indicate no systematic change in Holocene SST. The inferred long-term decrease in SST was probably driven by decreasing seasonality of Northern Hemisphere insolation. Two series of proxy data show the gradual cooling was interrupted by a two-step cold pulse that began 8500 years ago, and lasted about 700 years. Although this event is associated with the final deglaciation of Hudson Bay, there is no d18O minimum anywhere in the Labrador Sea, yet there is some evidence for it as far south as Cape Hatteras. Finally, although the 8200 year B.P. event has been implicated in decreasing North Atlantic ventilation, and hence widespread temperature depression on land and at sea, we find inconsistent evidence for a change at that time in deep ocean nutrient content at ~4 km water depth.

Organic carbon and nitrogen, sediment composition, and clay mineralogy of Deep Sea Drilling Project Site 603, western Atlantic Ocean

Sediment and interstitial water samples recovered during DSDP Leg 93 at Site 603 (lower continental rise off Cape Hatteras) were analyzed for a series of geochemical facies indicators to elucidate the nature and origin of the sedimentary material. Special emphasis was given to middle Cretaceous organic-matter-rich turbidite sequences of Aptian to Turanian age. Organic carbon content ranges from nil in pelagic claystone samples to 4.2% (total rock) in middle Cretaceous carbonaceous mudstones of turbiditic origin. The organic matter is of marine algal origin with significant contributions of terrigenous matter via turbidites. Maturation indices (vitrinite reflectance) reveal that the terrestrial humic material is reworked. Maturity of autochthonous material (i.e., primary vitrinite) falls in the range of 0.3 to 0.6% Carbohydrate, hydrocarbon, and microscopic investigations reveal moderate to high microbial degradation. Unlike deep-basin black shales of the South and North Atlantic, organic-carbon-rich members of the Hatteras Formation lack trace metal enrichment. Dissolved organic carbon (DOC) in interstitial water samples ranges from 34.4 ppm in a sandstone sample to 126.2 ppm in an organic-matter-rich carbonaceous claystone sample. One to two percent of DOC is carbohydratecarbon.

Diatom isotope data (d18Odiatom and d30Sidiatom) from IODP Site 303-U1304 (North Atlantic)

The Last Interglacial (LIG), corresponding to Marine Isotope Stage (MIS) 5e, provides a reference of interglacial climate variability in the absence of anthropogenic forcing. Using an expanded section of the LIG gained at Integrated Ocean Drilling Program Site U1304 in the Subarctic Atlantic, we demonstrate that the early MIS 5e was marked by oceanographic conditions conducive for high diatom production and accumulation. The appearance of diatom-dominated laminated oozes ~3 k.y. after the beginning of MIS 5e at ca. 125 ka coincides with a shift to higher d30Sidiat values together with the dominance of Thalassiothrix longissima, indicative of increased nutrient availability and silicic acid utilization in surface waters. Though the Subarctic Front provided the physical conditions for high diatom production and deposition, these processes alone are insufficient to explain the high rates of siliceous productivity and the formation of diatomaceous sediments. Instead, the additional presence of an increased nutrient pool provided by Subantarctic Mode Water played the decisive role in initiating and sustaining diatom production. The high diatom productivity and the occurrence of diatomaceous sediments in the late Quaternary challenge the current hypothesis of a silica-depleted North Atlantic during the LIG.

(Table 3) Oxygen and carbon isotopic record of living (Rose Bengal Stained) benthic foraminifera of North Atlantic surface sediments

Variation of the d13C of living (Rose Bengal stained) deep-sea benthic foraminifera is documented from two deep-water sites (~2430 and ~3010 m) from a northwest Atlantic Ocean study area 275 km south of Nantucket Island. The carbon isotopic data of Hoeglundina elegans and Uvigerina peregrina from five sets of Multicorer and Soutar Box Core samples taken over a 10-month interval (March, May, July, and October 1996 and January 1997) are compared with an 11.5 month time series of organic carbon flux to assess the effect of organic carbon flux on the carbon isotopic composition of dominant taxa. Carbon isotopic data of Hoeglundina elegans at 3010 m show 0.3 per mil lower mean values following an organic carbon flux maximum resulting from a spring phytoplankton bloom. This d13C change following the spring bloom is suggested to be due to the presence of a phytodetritus layer on the seafloor and the subsequent depletion of d13C in the pore waters within the phytodetritus and overlying the sediment surface. Carbon isotopic data of H. elegans from the 2430 m site show an opposite pattern to that found at 3010 m with a d13C enrichment following the spring bloom. This different pattern may be due to spatial variation in phytodetritus deposition and resuspension or to a limited number of specimens recovered from the March 1996 cruise. The d13C of Uvigerina peregrina at 2430 m shows variation over the 10 month interval, but an analysis of variance shows that the variability is more consistent with core and subcore variability than with seasonal changes. The isotopic analyses are grouped into 100 µm size classes on the basis of length measurements of individual specimens to evaluate d13C ontogenetic changes of each species. The data show no consistent patterns between size classes in the d13C of either H. elegans or U. peregrina. These results suggest that variation in organic carbon flux does not preferentially affect particular size classes, nor do d13C ontogenetic changes exist within the >250 to >750 µm size range for these species at this locality. On the basis of the lack of ontogenetic changes a range of sizes of specimens from a sample can be used to reconstruct d13C in paleoceanographic studies. The prediction standard deviation, which is composed of cruise, core, subcore, and residual (replicate) variability, provides an estimate of the magnitude of variability in fossil d13C data; it is 0.27 per mil for H. elegans at 3010 m and 0.4 per mil for U. peregrina at the 2430 m site. Since these standard deviations are based on living specimens, they should be regarded as minimum estimates of variability for fossil data based on single specimen analyses. Most paleoceanographic reconstructions are based on the analysis of multiple specimens, and as a result, the standard error would be expected to be reduced for any particular sample. The reduced standard error resulting from the analysis of multiple specimens would result in the seasonal and spatial variability observed in this study having little impact on carbon isotopic records.

Distribution of coccoliths in surface sediments of the south-eastern South Atlantic Ocean

Recent coccoliths from 52 surface sediment samples recovered from the south-eastern South Atlantic were examined qualitatively and quantitatively in order to assess the controlling mechanisms for their distribution patterns, such as ecological and preservational factors, and their role as carbonate producers. Total coccolith abundances range from 0.2 to 39.9 coccoliths*10**9/ g sediment. Four assemblages can be delineated by their coccolith content characterising the northern Benguela, the middle to southern Benguela, the Walvis Ridge and the deeper water. Distinctions are based on multivariate ordination techniques applied on the relative abundances of the most abundant taxa, Emiliania huxleyi, Calcidiscus leptoporus, Gephyrocapsa spp., Coccolithus pelagicus and subtropical to tropical species. The coccolith distribution seems to be temperature and nutrient controlled co-varying with the seaward extension of the upwelling filament zone in the Benguela. A preservation index (CEX') based on the differential dissolution behaviour of the delicate E. huxleyi and Gephyrocapsa ericsonii versus the robust C. leptoporus is applied in order to detect the position of the coccolith lysocline. Although some samples were recognised as dissolution-affected, the distribution of the coccoliths in the surface-sediments reflects the different oceanographic surface-water conditions. Mass estimations of the coccolith carbonate reveal coccoliths to be only minor contributors to the carbonate preserved in the surface sediments. The mean computed coccolith carbonate content is 17 wt.%, equivalent to a mean contribution of 23% to the bulk carbonate.

Abundance of calcareous dinoflagellates of sediment cores from the South Atlantic Ocean

Despite the increasing interest in the South Atlantic Ocean as a key area of the heat exchange between the southern and the northern hemisphere, information about its palaeoceanographic conditions during transitions from glacial to interglacial stages, the so-called Terminations, are not well understood. Herein we attempt to increase this information by studying the calcareous dinoflagellate cysts and the shells of Thoracosphaera heimii (calcareous cysts) of five Late Quaternary South Atlantic Ocean cores. Extremely high accumulation rates of calcareous cysts at the Terminations might be due to a combined effect of increased cyst production and better preservation as result of calm, oligotrophic conditions in the upper water layers. Low relative abundance of Sphaerodinella albatrosiana compared with Sphaerodinella tuberosa in the Cape Basin may be the result of the relatively colder environmental conditions in this region compared with the equatorial Atlantic Ocean with high relative abundance of S. albatrosiana. Furthermore, the predominance of S. tuberosa during glacials and interglacials at the observed site of the western Atlantic Ocean reflects decreased salinity in the upper water layer.

Stable carbon and oxygen isotope ratios of benthic foraminifera from the East Atlantic Ocean

The glacial to interglacial delta13C records of the benthic foraminifera Cibicidoides wuellerstorfi and the Uvigerina peregrina group from deep-sea cores cannot be adjusted by a generally valid constant. The delta13C values of the U. peregrina group largely correlate with the accumulation rates of organic carbon, suggesting a local "habitat effect"; those of C. wuellerstorfi vary independently with respect to the carbon flux and record fluctuations in the delta13C of the ambient bottom water isotopic composition.

Chemical composition of a manganese nodule from the Blake Plateau, Atlantic Ocean

The area surveyed during project AMC-11-67 was the portion of the Blake Plateau between latitude 30°00'N and 33°00'N and between the 100 to 1000 fathom curves. The survey was conducted from 3 October until 18 October 1967. Survey operations included dredgings, camera and multi-sensor lowerings. A collection of manganese and phosphate concretions as well as coral and sediment samples were examined by the ESSA(NOAA) Atlantic Oceanographic Laboratories. Chemical analyses were conducted at the NASA Manned Spacecraft Center, Houston by Richard A. Laidley for X-Ray Fluorescence Analysis and H. Costello for Atomic Absorption Analysis. Later the whole collection of samples was transferred to the Smithsonian National Museum of Natural History were it is available for study (see, http://mineralsciences.si.edu/collections.htm).

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.

Zn/Sr record of the Last Interglacial Transition in South Atlantic Ocean sediments

We examined the zinc content of diatom frustules as an indicator of past changes in surface seawater Zn2+ concentration. Zn/Si data of samples from three cores located in the South Atlantic sector of the Southern Ocean spanning the last interglacial-glacial transition are presented. Changes in the Zn/Si record are linked to changes in the surface water Zn2+ concentration. The source of variation in Zn2+ concentration appears to be via changes in deep water upwelling and circulation. We rule out changes in phytoplankton productivity and aeolian dust input as a source of variation in the Zn/Si record. Likewise, the Zn/Si data are not linked to shifts in the diatom species composition of the sediment or sediment preservation effects. The Zn/Si results presented do not support the zinc hypothesis. There is no link between the uptake of CO2 by phytoplankton, as inferred from the d13C record, and the Zn/Si record.

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.