(Table 1) TOC content, BIT, TEX86 and UK'37 indices, and sea surface temperature reconstruction for the middle Miocene to Pliocene of ODP Hole 175-1085A

The initiation of the Benguela upwelling has been dated to the late Miocene, but estimates of its sea surface temperature evolution are not available. This study presents data from Ocean Drilling Program (ODP) Site 1085 recovered from the southern Cape Basin. Samples of the middle Miocene to Pliocene were analyzed for alkenone-based (UK'37, SSTUK) and glycerol dialkyl glycerol tetraether (GDGT) based (TEX86, TempTEX) water temperature proxies. In concordance with global cooling during the Miocene, SSTUK and TempTEX exhibit a decline of about 8°C and 16°C, respectively. The temperature trends suggest an inflow of cold Antarctic waters triggered by Antarctic ice sheet expansion and intensification of Southern Hemisphere southeasterly winds. A temperature offset between both proxies developed with the onset of upwelling, which can be explained by differences in habitat: alkenone-producing phytoplankton live in the euphotic zone and record sea surface temperatures, while GDGT-producing Thaumarchaeota are displaced to colder subsurface waters in upwelling-influenced areas and record subsurface water temperatures. We suggest that variations in subsurface water temperatures were driven by advection of cold Antarctic waters and thermocline adjustments that were due to changes in North Atlantic deep water formation. A decline in surface temperatures, an increased offset between temperature proxies, and an increase in primary productivity suggest the establishment of the Benguela upwelling at 10 Ma. During the Messinian Salinity Crisis, between 7 and 5 Ma, surface and subsurface temperature estimates became similar, likely because of a strong reduction in Atlantic overturning circulation, while high total organic carbon contents suggest a "biogenic bloom." In the Pliocene the offset between the temperature estimates and the cooling trend was reestablished.

Nd isotopes an geochemistry of bulk deep sea sediments of the Atlantic Ocean

Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples. In this study we demonstrate that Nd extracted from the > 63 µm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples. In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments.

Stable oxygen isotope record of benthic foraminifera from the tropical Atlantic

Benthic foraminiferal oxygen isotope ratios from two sediment cores recovered at 426 and 1299 m water depth in the eastern and western tropical Atlantic show that a slowdown of the thermohaline circulation (THC) during Heinrich event H1 and the Younger Dryas was accompanied by rapid and intense warming of intermediate depth waters. Millennial-scale covariations of low paleosalinities in the subpolar North Atlantic with decreased benthic oxygen isotope ratios in the eastern tropical Atlantic throughout the past 10,000 years suggest that THC weakening might be related to middepth warming during the Holocene period as well. Climate model experiments simulating a strong reduction of the THC in the Atlantic Ocean under present-day and glacial conditions reveal that the increase of temperature in the middepth tropical and South Atlantic is a common feature for both climatic states, caused by a reduced ventilation of cold intermediate and deep waters in conjunction with downward mixing of heat from the thermocline. From the similarity of the paleoclimatic records with the model simulations, we infer that the characteristic pattern of temperature change in the Atlantic Ocean related to weakened thermohaline circulation can serve as an indicator of present-day and future THC slowdown.

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.

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.

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.

(Table 1) Stable isotope record of Middle Cretaceous benthic foraminifera

Preservation of planktic foraminiferal calcite has received widespread attention in recent years, but the taphonomy of benthic foraminiferal calcite and its influence on the deep-sea palaeotemperature record have gone comparatively unreported. Numerical modeling indicates that the carbonate recrystallization histories of deep-sea sections are dominated by events in their early burial history, meaning that the degree of exchange between sediments and pore fluids during the early postburial phase holds the key to determining the palaeotemperature significance of diagenetic alteration of benthic foraminifera. Postburial sedimentation rate and lithology are likely to be important determinants of the paleoceanographic significance of this sediment-pore fluid interaction. Here we report an investigation of the impact of extreme change in sedimentation rate (a prolonged and widespread Upper Cretaceous hiatus in the North Atlantic Ocean) on the preservation and d18O of benthic foraminifera of Middle Cretaceous age (nannofossil zone NC10, uppermost Albian/lowermost Cenomanian, ~99 Ma ago) from multiple drill sites. At sites where this hiatus immediately overlies NC10, benthic foraminifera appear to display at least moderate preservation of the whole test. However, on closer inspection, these tests are shown to be extremely poorly preserved internally and yield d18O values substantially higher than those from contemporaneous better preserved benthic foraminifera at sites without an immediately overlying hiatus. These high d18O values are interpreted to indicate alteration close to the seafloor in cooler waters during the Late Cretaceous hiatus. Intersite differences in lithology modulate the diagenetic impact of this extreme change in sedimentation rate. Our results highlight the importance of thorough examination of benthic foraminiferal wall structures and lend support to the view that sedimentation rate and lithology are key factors controlling the paleoceanographic significance of diagenetic alteration of biogenic carbonates.

Dissolved Iron, Aluminium, and Dissolved Inorganic Phosphorus in the (Sub-)Tropical Atlantic Surface Ocean

Inorganic nitrogen depletion restricts productivity in much of the low-latitude oceans, generating a selective advantage for diazotrophic organisms capable of fixing atmospheric dinitrogen (N2). However, the abundance and activity of diazotrophs can in turn be controlled by the availability of other potentially limiting nutrients, including phosphorus (P) and iron (Fe). Here we present high-resolution data (~0.3°) for dissolved iron, aluminum, and inorganic phosphorus that confirm the existence of a sharp north-south biogeochemical boundary in the surface nutrient concentrations of the (sub)tropical Atlantic Ocean. Combining satellite-based precipitation data with results from a previous study, we here demonstrate that wet deposition in the region of the intertropical convergence zone acts as the major dissolved iron source to surface waters. Moreover, corresponding observations of N2 fixation and the distribution of diazotrophic Trichodesmium spp. indicate that movement in the region of elevated dissolved iron as a result of the seasonal migration of the intertropical convergence zone drives a shift in the latitudinal distribution of diazotrophy and corresponding dissolved inorganic phosphorus depletion. These conclusions are consistent with the results of an idealized numerical model of the system. The boundary between the distinct biogeochemical systems of the (sub)tropical Atlantic thus appears to be defined by the diazotrophic response to spatial-temporal variability in external Fe inputs. Consequently, in addition to demonstrating a unique seasonal cycle forced by atmospheric nutrient inputs, we suggest that the underlying biogeochemical mechanisms would likely characterize the response of oligotrophic systems to altered environmental forcing over longer timescales.

(Table S1) Qualitative and semi-quantitative abundance of magnetic particles in Paleocene-Eocene sediments

On the mid-Atlantic Coastal Plain of the United States, Paleocene sands and silts are replaced during the Paleocene-Eocene Thermal Maximum (PETM) by the kaolinite-rich Marlboro Clay. The clay preserves abundant magnetite produced by magnetotactic bacteria and novel, presumptively eukaryotic, iron-biomineralizing microorganisms. Using ferromagnetic resonance spectroscopy and electron microscopy, we map the magnetofossil distribution in the context of stratigraphy and carbon isotope data and identify three magnetic facies in the clay: one characterized by a mix of detrital particles and magnetofossils, a second with a higher magnetofossil-to-detrital ratio, and a third with only transient magnetofossils. The distribution of these facies suggests that suboxic conditions promoting magnetofossil production and preservation occurred throughout inner middle neritic sediments of the Salisbury Embayment but extended only transiently to outer neritic sediments and the flanks of the embayment. Such a distribution is consistent with the development of a system resembling a modern tropical river-dominated shelf.

Biogeochemical properties of sinking particles intercepted at three depths on the NW Atlantic margin

Three conical sediment were deployed at three depths 968 m (top trap), 1976 m (middletrap), and 2938 m (50mabove the bottom, bottom trap) - from June 27, 2004 to April 27, 2005 on the NW Atlantic margin at a water depth of 2988 m. The sediment trap carousels were programmed to open each collection cup for 23.4 days for the top trap and 14.5 days for the other two traps, resulting in total 13 samples from the top trap and 21 samples each from the middle and bottom traps. The samples were analyzed for the biogeochemical properties with various methods. Frequent occurrences of higher fluxes in deep relative to shallower sediment traps and low delta 14C values of sinking POC together provide strong evidence for significant lateral transport of aged organic matter over the margin. Comparison of biogeochemical properties such as aluminum concentration and flux, and iron concentration between samples intercepted at different depths shows that particles collected by the deepest trap had more complex sources than the shallower ones. These data also suggest that at least two modes of lateral transport exist over the New England margin. Based on radio carbon mass balance, about 30% (± 10%) of sinking POC in all sediment traps is estimated to be derived from lateral transport of re-suspended sediment. A strong correlation between delta 14C values and aluminum concentrations suggests that the aged organic matter is associated with lithogenic particles.