Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

(Table 1) Stable isotope data of chemoherm carbonates at Hydrate Ridge on the Cascadia continental margin

Two active chemoherm build-ups growing freely up into the oceanic water column, the Pinnacle and the South East-Knoll Chemoherms, have been discovered at Hydrate Ridge on the Cascadia continental margin. These microbially-mediated carbonate formations rise above the seafloor by several tens of meters and display a pinnacle-shaped morphology with steep flanks. The recovered rocks are pure carbonates dominated by aragonite. Based on fabric and mineralogic composition different varieties of authigenic aragonite can be distinguished. Detailed visual and petrographic investigations unambiguously reveal the involvement of microbes during the formation of the carbonates. The fabric of the cryptocrystalline and fibrous aragonite can be described as thrombolitic. Fossilized microbial filaments in the microcrystalline aragonite indicate the intimate relationship between microbes and carbonates. The strongly 13C-depleted carbon isotope values of the samples (as low as -48.1 per mill PDB) are characteristic of methane as the major carbon source for the carbonate formation. The methane-rich fluids from which the carbonates are precipitated originate most probably from a gas reservoir below the bottom-simulating reflector (BSR) and rise through fault systems. The d18O values of the aragonitic chemoherm carbonates are substantially higher (as high as 5.0 per mill PDB) than the expected equilibrium value for an aragonite forming from ambient seawater (3.5 per mill PDB). As a first approximation this indicates formation from glacial ocean water but other factors are considered as well. A conceptual model is presented for the precipitation of these chemoherm carbonates based on in situ observations and the detailed petrographic investigation of the carbonates. This model explains the function of the consortium of archaea and sulfate-reducing bacteria that grows on the carbonates performing anaerobic oxidation of methane (AOM) and enabling the precipitation of the chemoherms above the seafloor surrounded by oxic seawater. Beggiatoa mats growing on the surface of the chemoherms oxidize the sulfide provided by sulfate-dependent anaerobic oxidation of methane within an oxic environment. The contact between Beggiatoa and the underlying microbial consortium represents the interface between the overlying oxic water column and an anoxic micro-environment where carbonate formation takes place.

Isotopic composition of foraminifera from sediments of DSDP Legs 3, 6-9, 17

Oxygen isotopic compositions of the tests of planktonic foraminifera from several Deep Sea Drilling Project sites provide a general picture of low-latitude marine temperatures from Maastrichtian time to the present. Bottom temperatures determined from the isotopic compositions of benthonic foraminifera are interpreted as being indicative of high-latitude surface temperatures. Prior to the beginning of middle Miocene time, high- and low-latitude temperatures changed in parallel fashion. Following an apparently small and short-lived drop in temperature near the Tertiary-Cretaceous boundary, temperatures remained warm and relatively constant through Paleocene and early and middle Eocene time; bottom temperatures then were on the order of 12°C. A sharp temperature drop in late Eocene time was followed by a more gradual lowering of temperature, culminating in a late Oligocene high-latitude temperature minimum of about 4°C. A temperature rise through early Miocene time was followed in middle Miocene time by a sudden divergence of high- and low-latitude temperatures: high-latitude temperatures dropped dramatically, perhaps corresponding to the onset of major glaciation in Antarctica, but low-latitude temperatures remained constant or perhaps increased. This uncoupling of high-and low-latitude temperatures is postulated to be related to the establishment of a circum-Antarctic circulation similar to that of today. A further drop in high-latitude temperatures in late Pliocene time probably signaled the onset of a major increase in polar glaciation, including extensive sea-ice formation. Early Miocene, small-amplitude (1 per mil) sympathetic fluctuations in isotopic compositions of planktonic and benthonic foraminifera have been identified. These have a period of several hundred thousand years. Superimposed upon these are much more rapid and smaller fluctuations (0.2 to 0.5 per mil) with a period of about 80000 to 90000 yr. This is similar to the period observed for Pleistocene isotopic temperature fluctuations. In low latitudes, much smaller vertical temperature gradients seem to have existed during Maastrichtian and Paleogene time than exist at present. The absence of a sharply defined thermocline during early Tertiary time is also suggested.

U/Th systematics of authigenic carbonates and d18O records from Hydrate Ridge, off the coast of Oregon, USA

Uranium (U) concentrations and activity ratios (d234U) of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon-rich fluids ("cold seeps") at Hydrate Ridge, off the coast of Oregon, USA. The low U concentrations (mean: 1.3 ± 0.4 µg/g) and high 234U values (165-317 per mil) of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor. Their 230Th/234U ages span a time interval from 0.8 to 6.4 ka and cluster around 1.2 and 4.7 ka. In contrast, chemoherm carbonates precipitate from marine bottom water marked by relatively high U concentrations (mean: 5.2 ± 0.8 µg/g) and a mean d234U ratio of 166 ± 3 per mil. Their U isotopes reflect the d234U ratios of the bottom water being enriched in 234U relative to normal seawater. Simple mass balance calculations based on U concentrations and their corresponding d234U ratios reveal a contribution of about 11% of sedimentary pore water to the bottom water. From the U pore water flux and the reconstructed U pore water concentration a mean flow rate of about 147 ± 68 cm/a can be estimated. 230Th/234U ages of chemoherm carbonates range from 7.3 to 267.6 ka. 230Th/234U ages of two chemoherms (Alvin and SE-Knoll chemoherm) correspond to time intervals of low sealevel stands in marine isotope stages (MIS) 2, 4, 5, 6, 7 and 8. This observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments. The d18OPDB ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times. Deviations of the chemoherm d18O values from the marine d18O record can be interpreted as to reflect temporally and spatially varying bottom water and/or vent fluid temperatures during carbonate precipitation between 2.6 and 8.6°C.

Carbon and oxygen isotope data for carbonates and benthic foraminifers from ODP Hole 113-689B

At Ocean Drilling Program Site 689 (Maud Rise, Southern Ocean), d18O records of fine-fraction bulk carbonate and benthic foraminifers indicate that accelerated climate cooling took place following at least two closely spaced early late Eocene extraterrestrial impact events. A simultaneous surface-water productivity increase, as interpreted from d13C data, is explained by enhanced water-column mixing due to increased latitudinal temperature gradients. These isotope data appear to be in concert with organic-walled dinoflagellate-cyst records across the same microkrystite-bearing impact-ejecta layer in the mid-latitude Massignano section (central Italy). In particular, the strong abundance increase of Thalassiphora pelagica is interpreted to indicate cooling or increased productivity at Massignano. Because impact-induced cooling processes are active on time scales of a few years at most, the estimated 100 k.y. duration of the cooling event appears to be too long to be explained by impact scenarios alone. This implies that a feedback mechanism, such as a global albedo increase due to extended snow and ice cover, may have sustained impact-induced cooling for a longer time after the impacts.

Stable carbon and oxygen isotope ratios of bulk sediment from the Weddell Sea

Carbon isotope measurements were made on bulk sediments from the well preserved calcareous sequences recovered at ODP Sites 689 and 690 on the Maud Rise, Weddell Sea, Antarctica. The very positive delta13C values that characterize the late Paleocene and the rapid trend toward lighter values in the early Eocene established in other sites are clearly recorded here and may be of value for long-distance stratigraphic correlation. However, values in the late Eocene are significantly more positive than have been reported from other areas. The general pattern of the records from Sites 689 and 690 is sufficiently unlike those previously reported from lower latitudes that we suggest that carbon isotope data should be used only with considerable caution for correlating sequences from such high latitudes with lower latitude records.

Stable-isotope records from Dronning Maud Land, Antarctica

The European Project for Ice Coring in Antarctica (EPICA) includes a comprehensive pre-site survey on the inland ice plateau of Dronning Maud Land. This paper focuses on the investigation of the 18O content of shallow firn and ice cores. These cores were dated by profiles derived from dielectric-profiling and continuous flow analysis measurements. The individual records were stacked in order to obtain composite chronologies of 18O contents and accumulation rates with enhanced signal-to-noise variance ratios.These chronologies document variations in the last 200 and 1000 years.The 18O contents and accumulation rates decreased in the 19th century and increased during the 20th century.Using the empirical relationships between stable isotopes, accumulation rates and the 10m firn temperature, the variation of both parameters can be explained by the same temperature history.But other causes for these variations, such as the build-up of the snow cover, cannot be excluded. A marked feature of the 1000 year chronology occurs during the period AD 1180-1530 when the 18O contents remains below the long-term mean. Cross-correlation analyses between five cores from the Weddell Sea region and Dronning Maud Land show that 18O records can in some periods be positively correlated and in others negatively correlated, indicating a complex climatic history in time and space.

Composition and stable isotope record of bulk sediment and belemnite rostra from ODP Hole 122-761C

A sedimentary sequence documenting the early history of the proto-Indian Ocean was drilled at Site 761 on the Wombat Plateau, northwest Australia. Directly above the post-rift unconformity, two lithologic units were recovered which reflect deposition in incipient oceanic environments. The lower unit, composed of sandstone, contains abundant belemnites and a few lenses composed of low-diversity coccolith assemblages. The second unit, composed of chalk, contains abundant calcispheres, thoracospheres, low-diversity coccolith assemblages, and a few radiolarians. Belemnites and organisms that produced calcispheres and thoracospheres are thought to be opportunistic. Their abundance, and the absence of a normal marine fauna and flora, reflects an unstable early ocean environment. Stable oxygen and carbon isotopic data for the two units fall into almost separate fields. Heavy delta18O values for the belemnites indicate that they have not been affected by recrystallization. Instead, these isotopic values are thought to indicate either the deep, cool habitat of the belemnites or strong vital effects. A bulk chalk delta18O value from the belemnite sand is 3 to 4 parts per mil lighter than the belemnite delta18O values, possibly because it is largely composed of coccoliths which inhabited warmer surface waters. Light delta13C values for bulk calcisphere-bearing nannofossil chalk samples are thought to be a direct result of upwelling or of vital effects. Heavy delta18O values for the chalk unit are interpreted as resulting from upwelling of cool waters. Assemblage and isotopic data are consistent with this incipient ocean basin being highly productive, either as a result of upwelling or runoff of nutrient-rich waters from nearby land areas. However, it is not possible to rule out the control of vital effects on the isotopic signature of any of the fossil groups.

Upper Triassic nannofossils from Wombat Plateau, Northwest Australia

A taxonomic and biostratigraphic investigation has been carried out on Upper Triassic (Carnian-Rhaetian) nannofossils from Sites 759, 760, 761 and 764 drilled on the Wombat Plateau during ODP Leg 122. The recovery of continuous sequences containing well preserved nannofossils has enabled us to refine the previous taxonomy and biostratigraphy of this interval. Fossil assemblages are of two major types: (1) previously described calcareous taxa were recovered at Sites 761 and 764; and (2) sideritic forms, which may represent diagenetic replacement of calcareous nannofossils, were observed in material from Sites 759 and 760. The sideritic forms proved difficult to study taxonomically due to inadequate optical properties. Calcareous nannofossil assemblages in the Upper Triassic are dominated by Prinsiosphaera triassica. We show that the multitude of identities of this species in the light microscope are the result of selective etching on a layered structure. We propose an evolutionary lineage for the earliest known coccoliths, with Crucirhabdus primulus as the ancestor. This species gave rise to C. minutus and Archaeozygodiscus koessenensis. The Upper Triassic can be subdivided based on the sequential first occurrences of C. primulus and Eoconusphaera zlambachensis in the upper Norian. The late Norian and Rhaetian were times of slow evolution of calcareous nannofossils. However, we noted three morphometric changes in this time-interval which possess biostratigraphic utility: (1) P. triassica increases in diameter from an average of 6 µm to over 9 µm; (2) E. zlambachensis evolves from a stubby to an elongated shape; and (3) C. primulus increases in size. Upper Triassic assemblages from the Wombat Plateau are similar in composition and diversity to those which have been described in detail from the Alps. In both areas, nannofossiliferous sediments interfinger with massive limestones deposited in reef and peri-platform environments. Stable isotopic analyses of Wombat Plateau nannofossil assemblages indicate that they thrived in open ocean conditions. Biostratigraphy allows sequence chronostratigraphic interpretation of ODP Site 761 and supports the chronostratigraphic cycle charts of Haq et al. (1987).

Carbon and oxygen stable isotope composition of bulk sediment and abundance of Braarudospahaera in ODP Site 122-762 (Table 1)

Nannofossil assemblages enriched in Braarudosphaera occur in lower Oligocene to lower Miocene sediments at Ocean Drilling Program Sites 762 and 763 on the central Exmouth Plateau. Braarudosphaerids appear here rather abruptly in the lower Oligocene (in Zone NP21). They reach their greatest numbers in the lower Oligocene (in Zones NP22 and NP23), where they comprise up to 10% of some samples. Braarudosphaera bigelowii is the overwhelmingly dominant species, occurring together with rare specimens of B. discula and Micrantholithus pinguis. The holococcoliths Peritrachelina joidesa and Lantemithus minutus are also associated with the Braarudosphaera enrichment. There are two populations of B. bigelowii: one of normal size (10-14 µm) and one of large specimens (20-22 µm). The larger braarudosphaerids are more common than the smaller forms. Braarudosphaera-rich sediments are absent at Wombat Plateau sites during the same time interval. We attribute this to latitudinal control, because the Wombat sites are about 4° north of the central Exmouth Plateau sites. We believe that the occurrence of braarudosphaerids is related to an Oligocene to early Miocene oceanographic event on the Exmouth Plateau. We suspect that mid-ocean up welling of cool, low-salinity, nutrient-rich water along a divergent zone created the Braarudosphaera-nch sediments in the South Atlantic and Indian oceans.