Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.

Stable carbon and oxygen isotope ratios of benthic foraminifera from Paleocene to Oligocene sediments

Benthic oxygen and carbon isotopic results from a depth transect on Maud Rise, Antarctica, provide the first evidence for Warm Saline Deep Water (WSDW) in the Paleogene oceans. Distinct reversals occur in the oxygen isotopic gradient between the shallower Hole 689B (Eocene depth ~1400 m; present-day depth 2080 m) and the deeper Hole 690B (Eocene depth ~2250 m; present-day depth 2914 m). The isotopic reversals, well developed by at least 46 Ma (middle middle Eocene), existed for much of the remaining Paleogene. We do not consider these reversals to be artifacts of differential diagenesis between the two sites or to have resulted from other potentially complicating factors. This being so, the results show that deep waters at Hole 690B were significantly warmer than deep waters at the shallower Hole 689B. A progressive decrease and eventual reversal in benthic to planktonic delta18O gradients in Hole 690B, demonstrate that the deeper waters became warmer relative to Antarctic surface waters during the Eocene. The warmer deep waters of the Paleogene are inferred to have been produced at middle to low latitudes, probably in the Tethyan region which contained extensive shallow-water platforms, ideal sites for the formation of high salinity water through evaporative processes. The ocean during the Eocene, and perhaps the Paleocene, is inferred to have been two-layered, consisting of warm, saline deep waters formed at low latitudes and overlain by cooler waters formed at high latitudes. This thermospheric ocean, dominated by halothermal circulation we name Proteus. The Neogene and modern psychrospheric ocean Oceanus is dominated by thermohaline circulation of deep waters largely formed at high latitudes. An intermediate condition existed during the Oligocene, with a three-layered ocean that consisted of cold, dense deep waters formed in the Antarctic (Proto-AABW), overlain by warm, saline deep waters from low latitudes, and in turn overlain by cool waters formed in the polar regions. This we name Proto-oceanus which combined both halothermal and thermohaline processes. The sequence of high latitude, major, climatic change inferred from the oxygen isotopic records is as follows: generally cooler earlier Paleocene; warming during the late Paleocene; climax of Cenozoic warmth during the early Eocene and continuing into the early middle Eocene; cooling mainly in a series of steps during the remainder of the Paleogene. Superimposed upon this Paleogene pattern, the Paleocene/Eocene boundary is marked by a brief but distinct warming that involved deep to surface waters and a reduction in surface to deep carbon and oxygen isotopic gradients. This event coincided with major extinctions among the deep-sea benthic foraminifers as shown by Thomas (1990 doi:10.2973/odp.proc.sr.113.123.1990). Salinity has played a major role in deep ocean circulation, and thus paleotemperatures cannot be inferred directly from the oxygen isotopic composition of Paleogene benthic foraminifers without first accounting for the salinity effect.

(Table 1) Comparison of adjacent Cenomanian black shales with green claystones from DSDP Hole 75-530A

Black shales possessing high concentrations of organic carbon (Foresman, 1978, doi:10.2973/dsdp.proc.40.111.1978) were deposited in many parts of the proto South Atlantic Ocean during the Cretaceous period (Bolli et al., 1978, doi:10.2973/dsdp.proc.40.104.1978). The way such sediments accumulated is not fully understood, but is likely to have occurred through a combination of low oxygen availability and abundant supply of organic matter. Thin, centimetre-thick layers of black shales are commonly interbedded with thicker layers of organic carbon-deficient, green claystones, as found in strata of Aptian to Coniacian age, at Deep Sea Drilling Project (DSDP) Site 530, in the southern Angola Basin (Hay et al., 1982, doi:10.1130/0016-7606(1982)93<1038:SAAOOC>2.0.CO;2) and elsewhere. These differences in carbon content and colour reflect the conditions of deposition, and possibly variations in the supply of organic matter (Summerhayes and Masran, 1983, doi:10.2973/dsdp.proc.76.116.1983; Dean and Gardner, 1982). We have compared, using organic geochemical methods the compositions of organic matter in three pairs of closely-bedded black and green Cenomanian claystones obtained from Site 530. Kerogen analyses and distributions of biological markers show that the organic matter of the black shales is more marine and better preserved than that of the green claystones.

(Tabls S1) Bulk geochemistry for sediment samples collected from the Cenomanian-Turonian boundary section at Pont d'Issole

Oceanic Anoxic Event 2 (OAE2), spanning the Cenomanian-Turonian boundary (CTB), represents one of the largest perturbations in the global carbon cycle in the last 100 Myr. The d13Ccarb, d13Corg, and d18O chemostratigraphy of a black shale-bearing CTB succession in the Vocontian Basin of France is described and correlated at high resolution to the European CTB reference section at Eastbourne, England, and to successions in Germany, the equatorial and midlatitude proto-North Atlantic, and the U.S. Western Interior Seaway (WIS). Delta13C (offset between d13Ccarb and d13Corg) is shown to be a good pCO2 proxy that is consistent with pCO2 records obtained using biomarker d13C data from Atlantic black shales and leaf stomata data from WIS sections. Boreal chalk d18O records show sea surface temperature (SST) changes that closely follow the Delta13C pCO2 proxy and confirm TEX86 results from deep ocean sites. Rising pCO2 and SST during the Late Cenomanian is attributed to volcanic degassing; pCO2 and SST maxima occurred at the onset of black shale deposition, followed by falling pCO2 and cooling due to carbon sequestration by marine organic productivity and preservation, and increased silicate weathering. A marked pCO2 minimum (~25% fall) occurred with a SST minimum (Plenus Cold Event) showing >4°C of cooling in ~40 kyr. Renewed increases in pCO2, SST, and d13C during latest Cenomanian black shale deposition suggest that a continuing volcanogenic CO2 flux overrode further drawdown effects. Maximum pCO2 and SST followed the end of OAE2, associated with a falling nutrient supply during the Early Turonian eustatic highstand.

Geochemistry of ODP Hole 135-839B lavas

Four petrographic lava types occur, ranging from aphyric to moderately phyric clinopyroxene-olivine tholeiitic basalts (Unit 1); olivine-clinopyroxene picritic basalts, sparsely to strongly olivine-phyric (Unit 3-type); olivine-clinopyroxene basalts (clinopyroxene dominant) (Unit 4); and moderately to strongly phyric two-pyroxene-plagioclase basaltic andesites (Unit 9-type). The olivine phyric lavas contain forsteritic olivines (extending to Fo92), and very magnesian Cr-rich spinels similar to those occurring in boninitic lavas. The basaltic andesites are mineralogically and petrographically indistinguishable from the modern Tofua Arc basaltic andesites, one notable feature being the highly calcic cores in plagioclase phenocrysts (up to An95). The forsteritic olivines, the Cr-spinels, and the calcic plagioclases are unlikely to have been precipitated in the lava compositions in which they occur, and are thought to have been incorporated from highly primitive melts by way of mixing processes (as advocated by Allan, this volume). Notwithstanding the evidence for mixing, the major element chemistries of the Unit 1- and Unit 9-type lavas are shown to be consistent with the derivation of the Unit 9-type basaltic andesites by means of fractional crystallization, through magmas of similar chemistry to Unit 1. Some trace element discrepancies in the modeling, and the relative volcanic stratigraphy of Site 839, however, preclude a direct liquid line of descent between the actual recovered units. Trace element data as well as TiO2 and Na2O data clearly illustrate the arc-like affinities of the magmas, with strong highfield-strength element depletion and large-ion-lithophile element enrichment. The abundance patterns are very close to those of the Tofua and Kermadec arc magmas, and also Valu Fa. Pb-, Sr-, and Nd-isotopic compositions indicate closest affinities with a "Pacific" MORB source, apparently characteristic of the western, older part of the Lau Basin. A subduction-related isotopic contribution is, however, inferred. The sources of the Site 839 magmas are thus inferred to be similar to, but less depleted geochemically, than those of the modern Tofua Arc magmas. The Site 839 sequence is interpreted as an older remnant of a volcanic construct of the "proto-Tofua arc", originally developed adjacent to the Tonga Ridge. Opening of the eastern Lau Basin, because of southward migrating propagators, has split and isolated the sequence, leaving it stranded within the modern Lau Basin.

(Table 2) Concentrations of particulate chemical elements in waters of the Pechora Sea

Mineralogy of suspended matter from surface and bottom waters has been studied at two sites in the Barents Sea. Along with terrigenous minerals, particulate matter samples contain authigenic mineral phases of iron and manganese oxyhydroxides. Mn-feroxyhite, Fe-vernadite, goethite, and proto-ferrihydrite have been identified in samples from the surface waters, whereas birnessite and non-ferruginous vernadite have been found in samples from the bottom waters. Formation of suspended manganese minerals in the bottom waters is explained by an additional Mn supply from underlying reduced sediments during their early diagenesis and oxygen depletion in the near-bottom nepheloid layer. Bacteria are supposed to take part in the authigenic mineral formation.

40Ar-39Ar dating and isotopic composition of groundmass and felspar samples from core AND-2A

The AND-2A drillcore (Antarctic Drilling Program-ANDRILL) was successfully completed in late 2007 on the Antarctic continental margin (Southern McMurdo Sound, Ross Sea) with the aim of tracking ice proximal to shallow marine environmental fluctuations and to document the 20-Ma evolution of the Erebus Volcanic Province. Lava clasts and tephra layers from the AND-2A drillcore were investigated from a petrographic and stratigraphic point of view and analyzed by the 40Ar-39Ar laser technique in order to constrain the age model of the core and to gain information on the style and nature of sediment deposition in the Victoria Land Basin since Early Miocene. Ten out of 17 samples yielded statistically robust 40Ar-39Ar ages, indicating that the AND-2A drillcore recovered <230 m of Middle Miocene (~128-358 m below sea floor, ~11.5-16.0 Ma) and >780 m of Early Miocene (~358-1093 m below sea floor, ~16.0-20.1 Ma). Results also highlight a nearly continuous stratigraphic record from at least 358 m below sea floor down hole, characterized by a mean sedimentation rate of ~19 cm/ka, possible oscillations of no more than a few hundreds of ka and a break within ~17.5-18.1 Ma. Comparison with available data from volcanic deposits on land, suggests that volcanic rocks within the AND-2A core were supplied from the south, possibly with source areas closer to the drill site for the upper core levels, and from 358 m below sea floor down hole, with the 'proto-Mount Morning' as the main source.

Miocene planktonic foraminifera of ODP Hole 130-806B

We document the waxing and waning of a "proto-warm pool" in the western equatorial Pacific (WEP) based on a study of multi-species planktic foraminiferal isotope ratios and census data spanning the 13.2-5.8 Ma interval at ODP Site 806. We hypothesize that the presence or absence of a proto-warm pool in the WEP, caused by the progressive tectonic constriction of the Indonesian Seaway and modulated by sea level fluctuations, created El Niño/La Niña-like alternations of hydrographic conditions across the equatorial Pacific during the late Miocene. This hypothesis is supported by the general antithetical relationship observed between carbonate productivity and preservation in the western and eastern equatorial Pacific, which we propose is caused by these alternating ocean-climate states. Warming of thermocline and surface waters, as well as a major change in planktic foraminferal assemblages record a two-step phase of proto-warm pool development ~11.6-10 Ma, which coincides with Miocene isotope events Mi5 and Mi6, and sea-level low stands. We suggest that these changes in the biota and structure of the upper water column in the WEP mark the initiation of a more modern equatorial current system, including the development of the Equatorial Undercurrent (EUC), as La Niña-like conditions became established across the tropical Pacific. This situation sustained carbonate and silica productivity in the eastern equatorial Pacific (EEP) at a time when carbonate preservation sharply declined in the Caribbean. Proto-warm pool weakening after ~10 Ma may have contributed to the nadir of a similar "carbonate crash" in the EEP. Cooling of the thermocline and increased abundances of thermocline taxa herald the decay of the proto-warm pool and higher productivity in the WEP, particularly ~ 9.0-8.8 Ma coincident with a major perturbation in tropical nannofossil assemblages. We suggest that this interval of increased productivity records El Niño-like conditions across the tropical Pacific and the initial phase of the widespread "biogenic bloom". Resurgence of a later proto-warm pool in the WEP ~6.5-6.1 Ma may have spurred renewed La Niña-like conditions, which contributed to a strong late phase of the "biogenic bloom" in the EEP.

Stratigraphic occurrence of selected marine palynomorph species recorder in the Paleogene of ODP Hole 105-647A (Table 3)

Dinoflagellate cysts were recovered throughout the Paleogene succession of Hole 647A, which contains an almost complete deep-water record of early Eocene through early late Oligocene sedimentation in the Labrador Sea. Dinoflagellate cyst biostratigraphy is in general accord with that provided by other microfossil groups and is consistent with a lower Eocene age, as determined by nannofossils, for basal sediments in Hole 647A. These sediments overlie oceanic crust of Chron 24 age. Dinocyst assemblages indicate outer neritic to oceanic conditions throughout, although the persistent occurrence of Wetzeliellaceae specimens in the lower Eocene suggests a greater influence from shelf environments during this time. Lower Eocene dinocyst assemblages are similar to coeval assemblages from the Rockall Plateau, but those from the middle to upper Eocene have mixed affinities and may be related to the intensification of the proto-Gulf Stream from middle Eocene time. Oligocene dinocyst assemblages suggest the influence of both arctic and North Atlantic wate rmasses at this site. The presence of protoperidineacean species in the upper Eocene and Oligocene may indicate increased availability of nutrients, perhaps related to increased upwelling or the effects of water-mass mixing. Productive samples are dominated by dinocysts and acritarchs, while sporomorphs are represented mainly by bisaccate pollen. Preservational differences within samples may reflect mixing of penecontemporaneous dinocyst populations during the Eocene, and all samples examined may have a considerable allochthonous component. Variability in relative abundance of many species during the Eocene may be related to fluctuating water-mass properties. A total 175 dinocyst and acritarch taxa were recorded from 53 productive samples from the Paleogene. Only one Paleogene sample was barren of palynomorphs. Of three Miocene samples processed, all were barren.