Sedimentology and stable carbon and oxygen isotope record of the Central Arctic

Stable oxygen and carbon isotope and sedimentological-paleontological investigations supported by accelerator mass spectrometry 14C datings were carried out on cores from north of 85°N in the eastern central Arctic Ocean. Significant changes in accumulation rates, provenance of ice-rafted debris (IRD), and planktic productivity over the past 80,000 years are documented. During peak glacials, i.e., oxygen isotope stages 4 and 2, the Arctic Ocean was covered by sea ice with decreased seasonal variation, limiting planktic productivity and bulk sedimentation rates. In early stage 3 and during Termination I, major deglaciations of the circum-Arctic regions caused lowered salinities and poor oxygenation of central Arctic surface waters. A meltwater spike and an associated IRD peak dated to ~14-12 14C ka can be traced over the southern Eurasian Basin of the Arctic Ocean. This event was associated with the early and rapid deglaciation of the marine-based Barents Sea Ice Sheet. A separate Termination Ib meltwater event is most conspicuous in the central Arctic and is associated with characteristic dolomitic carbonate IRD. This lithology suggests an origin of glacial ice from northern Canada and northern Greenland where lower Paleozoic platform carbonates crop extensively out.

(Table S1) FMR and rock magnetic parameters for upper Paleocene to lower Eocene strata, Site Ancora

Previous workers identified a magnetically anomalous clay layer deposited on the northern United States Atlantic Coastal Plain during the Paleocene-Eocene thermal maximum (PETM). The finding inspired the highly controversial hypothesis that a cometary impact triggered the PETM. Here we present ferromagnetic resonance (FMR), isothermal and anhysteretic remanent magnetization, first-order reversal curve, and transmission electron microscopy analyses of late Paleocene and early Eocene sediments in drill core from Ancora, New Jersey. A novel paleogeographic analysis applying a recent paleomagnetic pole from the Faeroe Islands indicates that New Jersey during the initial Eocene had a ~6°-9° lower paleolatitude (~27.3° for Ancora) and a more zonal shoreline trace than in conventional reconstructions. Our investigations of the PETM clay from Ancora reveal abundant magnetite nanoparticles bearing signature traits of crystals produced by magnetotactic bacteria. This result, the first identification of ancient biogenic magnetite using FMR, argues that the anomalous magnetic properties of the PETM sediments are not produced by an impact. They instead reflect environmental changes along the eastern margin of North America during the PETM that led to enhanced production and/or preservation of magnetofossils.

(Fig. 9) Pollen analysis of sediment core GIK16017-2

The improved understanding of the pollen signal in the marine sediments offshore of northwest Africa is applied to deep-sea core M 16017-2 at 21°N. Downcore fluctuations in the percentage, concentration and influx diagrams record latitudinal shifts of the main northwest African vegetation zones and characteristics of the trade winds and the African Easterly Jet. Time control is provided by 14C ages and 180 records. During the period 19,000-14,000 yr B.P. a compressed savanna belt extended between about 12 ° and 14-15°N. The Sahara had maximally expanded northward and southward under hyperarid climatic conditions. The belt with trade winds and dominant African Easterly Jet transport had not shifted latitudinally. The trade winds were strong as compared to the modern situation but around 13,000 yr B.P. the trade winds weakened. After 14,000 yr B.P. the climate became less arid south of the Sahara and a first spike of fluvial runoff is registered around 13,000 yr B.P. Fluvial runoff increased strongly around 11,000 yr B.P. and maximum runoff is recorded from about 9000-7800 yr B.P. Around 12,500 yr B.P. the savanna belt started to shift northward and became richer in woody species: it shifted about 6° of latitude, reached its northernmost position during the period of 9200-7800 yr B.P. and extended between about 16° and 24°N at that time. Tropical forest had reached its maximum expansion and the Guinea zone reached as far north as about 15°N, reflecting very humid climatic conditions south of the Sahara. North of the Sahara the climate also became more humid and Mediterranean vegetation developed rapidly. The Sahara had maximally contracted and the trade winds were weak and comparable with the present day intensity. After about 7800 yr B.P. the southern fringe of the Sahara and accordingly the savanna belt, shifted rapidly southward again.

CaCO3 deposits in the eastern tropical Pacific

We constructed biogenic mass accumulation rate (MAR) time series for eastern Pacific core transects across the equator at ~105° and ~85°W and along the equator from 80° to 140°W. We used empirical orthogonal function (EOF) analysis to extract spatially coherent patterns of CaCO3 deposition for the last 150 kyr. EOF mode 1 (51% variance) is a CaCO3 MAR spike centered in marine oxygen isotope stage 2 (MIS 2) found under the South Equatorial Current. EOF mode 2 (19% of variance) is high north of the equator. EOF mode 3 (9% of variance) is an east-west mode centered along the North Equatorial Counter Current. The MIS 2 CaCO3 spike is the largest event in the eastern Pacific for the last 150 kyr: CaCO3 MARs are 2-3 times higher at 18 ka than elsewhere in the record, including MIS 6. It is caused by high CaCO3 production rather than minimal dissolution. EOF 2, while it resembles deep water flow patterns, nevertheless, shows coherence to Corg deposition and is probably also driven by CaCO3 production.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

Absolute abundances of dinoflagellate cysts in surface sediment samples from four sites: Lycopodium marker-grain method

Absolute abundances (concentrations) of dinoflagellate cysts are often determined through the addition of Lycopodium clavatum marker-grains as a spike to a sample before palynological processing. An inter-laboratory calibration exercise was set up in order to test the comparability of results obtained in different laboratories, each using its own preparation method. Each of the 23 laboratories received the same amount of homogenized splits of four Quaternary sediment samples. The samples originate from different localities and consisted of a variety of lithologies. Dinoflagellate cysts were extracted and counted, and relative and absolute abundances were calculated. The relative abundances proved to be fairly reproducible, notwithstanding a need for taxonomic calibration. By contrast, excessive loss of Lycopodium spores during sample preparation resulted in non-reproducibility of absolute abundances. Use of oxidation, KOH, warm acids, acetolysis, mesh sizes larger than 15 µm and long ultrasonication (> 1 min) must be avoided to determine reproducible absolute abundances. The results of this work therefore indicate that the dinoflagellate cyst worker should make a choice between using the proposed standard method which circumvents critical steps, adding Lycopodium tablets at the end of the preparation and using an alternative method.

Seawater carbonate chemistry and biological processes during experiments with coral Oculina arbuscula, 2010

Anthropogenic elevation of atmospheric pCO2 is predicted to cause the pH of surface seawater to decline by 0.3-0.4 units by 2100 AD, causing a 50% reduction in seawater [CO3] and undersaturation with respect to aragonite in high-latitude surface waters. We investigated the impact of CO2-induced ocean acidification on the temperate scleractinian coral Oculina arbuscula by rearing colonies for 60 days in experimental seawaters bubbled with air-CO2 gas mixtures of 409, 606, 903, and 2,856 ppm pCO2, yielding average aragonite saturation states (Omega aragonite) of 2.6, 2.3, 1.6, and 0.8. Measurement of calcification (via buoyant weighing) and linear extension (relative to a 137Ba/138Ba spike) revealed that skeletal accretion was only minimally impaired by reductions in Omega aragonite from 2.6 to 1.6, although major reductions were observed at 0.8 (undersaturation). Notably, the corals continued accreting new skeletal material even in undersaturated conditions, although at reduced rates. Correlation between rates of linear extension and calcification suggests that reduced calcification under Omega aragonite = 0.8 resulted from reduced aragonite accretion, rather than from localized dissolution. Accretion of pure aragonite under each Omega aragonite discounts the possibility that these corals will begin producing calcite, a less soluble form of CaCO3, as the oceans acidify. The corals' nonlinear response to reduced Omega aragonite and their ability to accrete new skeletal material in undersaturated conditions suggest that they strongly control the biomineralization process. However, our data suggest that a threshold seawater [CO3] exists, below which calcification within this species (and possibly others) becomes impaired. Indeed, the strong negative response of O. arbuscula to Omega aragonite= 0.8 indicates that their response to future pCO2-induced ocean acidification could be both abrupt and severe once the critical Omega aragoniteis reached.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

(Figure 2, page 940) K-T boundary enrichment for cerium and iridium chemical composition of layers inside the ZETES-3D manganese nodule in the Pacific Ocean

Hydrogenous manganese nodules form on the ocean floor by slow authigenic precipitation (1-6 mm/Ma) of the oxyhydroxides of manganese and iron that continuously scavenge trace elements from the marine environment. Consequently, these nodules represent independent marine deposits useful for the study of the chemical signatures of the paleomarine environments. The results presented are a continuation of a study of the Zetes-3D nodule from the Pacific Ocean. It is a large (24x17x10 cm) hydrogenous nodule whose slow growth rate of 1.3 mm/Ma was detremined using 10Be techniques. A positive cerium anomaly is observed throughout the nodule and its Ir content indicates a sharp spike at 54-62 Ma in fair agreement with the K-T event.

Seawater carbonate chemistry, Mg/Ca, Sr/Ca, oxygen production and calcification rate during experiments with coral Pocillopora damicornis, 2011

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca2+ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by 42Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr2+ and Ca2+ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca2+ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.