Organic geochemistry of ODP Hole 162-985A sediments

Dark, organic-rich sediments were recovered from the lower Miocene section (~16.6 Ma) in Hole 985A in the Norway Basin during Ocean Drilling Program Leg 162. Organic carbon and total sulfur contents of the dark sediments showed a maximum concentration of 5.6 and 26.1 wt%, respectively. Sulfur enrichment in the sediments indicates that these dark layers were formed under anoxic conditions in bottom water. Four dark and eight greenish gray sediment samples, ranging in age from early Miocene to Pleistocene, were analyzed for lipid-class compounds (aliphatic hydrocarbons, fatty alcohols, and sterols) using gas chromatography (GC) and GC/mass spectrometry to better understand the formation processes of the organic-rich dark layers and to reconstruct the paleoenvironmental changes. The molecular distributions of n-alkanes and fatty alcohols indicate that terrigenous organic matter largely contributed to both types of sediments. Significant amounts of hopanoid hydrocarbons, such as diploptene and hop-17(21)-ene, however, were detected characteristically in the dark sediments, which suggests that prokaryotes such as methane-oxidizing bacteria or cyanobacteria may have significantly contributed to the formation of these organic-rich, dark sediments. These results indicate that the bottom waters of the Norway Basin had been subjected to anoxic conditions during the early Miocene.

Revised age model of DSDP Site 95-612

Alkenone-based Cenozoic records of the partial pressure of atmospheric carbon dioxide (pCO2) are founded on the carbon isotope fractionation that occurred during marine photosynthesis (epsilon [p37:2]). However, the magnitude of epsilon [p37:2] is also influenced by phytoplankton cell size - a consideration lacking in previous alkenone-based CO2 estimates. In this study, we reconstruct cell size trends in ancient alkenone-producing coccolithophores (the reticulofenestrids) to test the influence that cell size variability played in determining epsilon [p37:2] trends and pCO2 estimates during the middle Eocene to early Miocene. At the investigated deep-sea sites, the reticulofenestrids experienced high diversity and largest mean cell sizes during the late Eocene, followed by a long-term decrease in maximum cell size since the earliest Oligocene. Decreasing haptophyte cell sizes do not account for the long-term increase in the stable carbon isotopic composition of alkenones and associated decrease in epsilon [p37:2] values during the Paleogene, supporting the conclusion that the secular pattern of epsilon [p37:2] values is primarily controlled by decreasing CO2 concentration since the earliest Oligocene. Further, given the physiology of modern alkenone producers, and considering the timings of coccolithophorid cell size change, extinctions, and changes in reconstructed pCO2 and temperature, we speculate that the selection of smaller reticulofenestrid cells during the Oligocene primarily reflects an adaptive response to increased [CO2(aq)] limitation.

(Table T1) Stable oxygen and carbon isotopic composition of benthic foraminifers in ODP Site 199-1218 sediments

The transition from the late Oligocene warm period into the early Miocene was marked by a series of rapid and brief episodes of cryospheric expansion and global cooling. We analyzed benthic foraminifers from nannofossil oozes recovered at Ocean Drilling Program Site 1218 to construct a stable isotope stratigraphy for the deep Pacific.

Magnetostratigraphy and biostratigraphy of ODP Leg 105 sites and DSDP Hole 12-112

During Ocean Drilling Program (ODP) Leg 105, three sites (Sites 645 through 647) were drilled in Baffin Bay and the Labrador Sea to examine the tectonic evolution and the climatic and oceanic histories of this region. Biostratigraphic and magnetostratigraphic results vary at each site, while stratigraphic resolution depends on the limited abundance of marker species and the completeness of the paleomagnetic record. Because of the paucity of planktonic microfossils and the poor paleomagnetic record signatures, stratigraphic determinations at Site 645 often rely on defining minimum temporal constraints on specific samples or stratigraphic intervals. The completed stratigraphy indicates that the sedimentary sequence recovered at Site 645 is early Miocene to Holocene in age. The magnetostratigraphy and biostratigraphies are better defined at Sites 646 and 647 in the Labrador Sea. Site 646 generally contains a well-developed magnetostratigraphy and calcareous microfossil biostratigraphy. This biostratigraphy is based on calcareous nannofossils and planktonic foraminifers typical of the North Atlantic Ocean. Siliceous microfossils are also present at Site 646, but they are restricted to upper Pliocene through Holocene sediments. The stratigraphic sequence recovered at Site 646 is late Miocene to Holocene in age. Based primarily on the calcareous nannofossil stratigraphy, the sequence recovered at Site 647 consists of lower Eocene to lower Oligocene, lower Miocene, upper Miocene, and upper Pliocene through Holocene sediments. Three hiatuses are present in this sequence: the older hiatus separates lower Oligocene sediments from lower Miocene sediments, another hiatus separates lower Miocene sediments from upper Miocene sediments, and the youngest one separates upper Miocene from upper Pliocene sediments. A magnetostratigraphy is defined for the interval from the Gauss/Matuyama boundary through the Brunhes (Clement et al., this volume). Both planktonic foraminifers and siliceous microfossils have restricted occurrences. Planktonic foraminifers occur in Pliocene and younger sediments, and siliceous microfossils are present in lower Miocene and lower Oligocene sediments. The near-continuous Eocene through lower Oligocene sequence recovered at Site 647 allows the calcareous nannofossils and diatom stratigraphies at this site to act as a Paleogene stratigraphic framework. This framework can be compared with the stratigraphy previously completed for DSDP Site 112.

Abundance of ostracoda in sediment cores CRP-1 and CRP-2

Sparse, poorly preserved late Oligocene (3 species) and early Miocene (4 species) ostracod faunas have been recovered from CRP-2A, while relatively more abundant Quaternary faunas occur in CRP-1 (24 species). All taxa are marine. No definitive age assignments can be made on the two older faunas, which are not considered to be in situ, although the taxa identified are not at variance with sediment ages determined on other grounds. The Oligocene ostracods (Lithostratigraphical Unit, LSU 9.4) suggest deposition in cold, relatively shallow, shelf waters with faunal connections to the Antarctic Peninsula and South America, while the Miocene fauna (LSU 5.1) is considered to be a cool-cold, deeper water (?outer shelf) association with faunal connections to both New Zealand and the Antarctic Peninsula. The Quaternary faunas are primarily from LSU 3.1 (carbonate-rich layer), and suggest deposition in very cold, relatively quiet water that was at least 100 m, and possibly 130-200 m deep. None of the taxa are known from pre-Pleistocene sediments, and all occur in modern Antarctic/sub-Antarctic regimes, predominantly from south of 60° S. Specimens in the "carbonate-rich layer" probably have suffered minor penecontemporaneous fractionation, while the fauna in LSU 2.2 has suffered more extensive post-mortem transportation and possible reworking (though not necessarily from pre-Quaternary sources).

Rb-Sr systematics of volcanic rocks and alteration minerals of ODP Hole 104-642E

Subaerially erupted tholeiites at Hole 642E were never exposed to the high-temperature seawater circulation and alteration conditions that are found at subaqueous ridges. Alteration of Site 642 rocks is therefore the product of the interaction of rocks and fluids at low temperatures. The alteration mineralogy can thus be used to provide information on the geochemical effects of low temperature circulation of seawater. Rubidium-strontium systematics of leached and unleached tholeiites and underlying, continentally-derived dacites reflect interactions with seawater in fractures and vesicular flow tops. The secondary mineral assemblage in the tholeiites consists mainly of smectite, accompanied in a few flows by the assemblage celadonite + calcite (+/- native Cu). Textural relationships suggest that smectites formed early and that celadonite + calcite, which are at least in part cogenetic, formed later than and partially at the expense of smectite. Smectite precipitation occurred under variable, but generally low, water/rock conditions. The smectites contain much lower concentrations of alkali elements than has been reported in seafloor basalts, and sequentially leached fractions of smectite contain Sr that has not achieved isotopic equilibrium. 87Sr/86Sr results of the leaching experiments suggest that Sr was mostly derived from seawater during early periods of smectite precipitation. The basalt-like 87Sr/86Sr of the most readily exchangeable fraction seems to suggest a late period of exposure to very low water /rock. Smectite formation may have primarily occurred in the interval between the nearly 58-Ma age given by the lower series dacites and the 54.5 +/- 0.2 Ma model age given by a celadonite from the top of the tholeiitic section. The 54.5 +/- 0.2 Ma Rb-Sr model age may be recording the timing of foundering of the Voring Plateau. Celadonites precipitated in flows below the top of the tholeiitic section define a Rb-Sr isochron with a slope corresponding to an age of 24.3 +/- 0.4 Ma. This isochron may be reflecting mixing effects due to long-term chemical interaction between seawater and basalts, in which case the age provides only a minimum for the timing of late alteration. Alternatively, inferrential arguments can be made that the 24.3 +/- 0.4 isochron age reflects the timing of the late Oligocene-early Miocene erosional event that affected the Norwegian-Greenland Sea. Correlation of 87Sr/86Sr and 1/Sr in calcites results in a two-component mixing model for late alteration products. One end-member of the mixing trend is Eocene or younger seawater. Strontium from the nonradiogenic endmember can not, however, have been derived directly from the basalts. Rather, the data suggest that Sr in the calcites is a mixture of Sr derived from seawater and from pre-existing smectites. For Site 642, the reaction involved can be generalized as smectite + seawater ++ celadonite + calcite. The geochemical effects of this reaction include net gains of K and CO2 by the secondary mineral assemblage. The gross similarity of the reactions involved in late, low-temperature alteration at Site 642 to those observed in other sea floor basalts suggests that the transfer of K and C02 to the crust during low-temperature seawater-ocean crust interactions may be significant in calculations of global fluxes.

Stable isotope composition of Neogene planktonic foraminifera from ODP Leg 130 sites

We produced a preliminary record for shallow-dwelling planktonic foraminifer d18O at Site 807 for the late Pleistocene, early Pliocene, and early Miocene. Site 807 d18O values between 4 and 5 Ma average 0.75 per mil more than Holocene values and show an average variation of 0.5 per mil. For the early Pliocene, peak maximum d18O at Site 807 attain values equivalent with the last glacial maximum whereas peak minimum d18O were never less than Holocene d18O. Shallow-dwelling planktonic d18O at Site 807 between 16 and 24 Ma average more than 1.0 per mil more positive than Holocene d18O and exhibit 0.5 per mil average amplitude. Assuming that the global ice budget for the early Pliocene and early Miocene was restricted to Antarctica, it is difficult to attribute the very positive Site 807 d18O for these intervals to ice on Antarctica. Site 807 d18O for these intervals more likely reflect sea-surface temperatures cooler than at present, sea-surface salinity greater than at present, increased dissolution, or some combination of these changes.

(Table 2) Stratigraphic marker taxa in ODP Hole 162-985A sediments

The rich and diverse dinocyst assemblages in Cores 162-985A-32X through 62X confirm the importance of these microfossils in unraveling the evolution of the Norwegian Sea. Cosmopolitan taxa, with well-documented stratigraphic ranges in northwest Europe, indicate the following ages: Sections 162-985A-62X-1 through 51X-2, Rupelian (early Oligocene); 50X-5, Oligocene, possibly Chattian; 48X-6, Aquitanian? (early Miocene); 48X-4 through 37X-5, Aquitanian (early Miocene); and 36X-5 through 32X-1, Burdigalian (early Miocene). This stratigraphic interpretation suggests that a major hiatus, which can be correlated with an apparently coeval hiatus at Site 643, occurs within the Chattian at Site 985. Several endemic dinocyst taxa with unusual morphology and restricted stratigraphic occurrences are present in Hole 985A and other Norwegian Sea sites, especially Site 643. By using Hole 985A data for control, the Oligocene-Miocene sediments can be correlated with some degree of confidence in the Norwegian Basin.

Strontium isotope ratios of planktonic foraminifera from ODP Site 119-744 on the Kerguelen Plateau, Indian Ocean (Table 1)

87Sr/86Sr ratios of well-preserved early Miocene-Oligocene planktonic foraminifers from Site 744 in the southern Indian Ocean provide the highest southern latitude Sr isotope record of this age. The isotopic data have been calibrated with the site magnetostratigraphy. 87Sr/86Sr ages were also determined using the Sr isotope-age equations of Miller et al. (1988, doi:10.1029/PA003i002p00223) and Hess et al. (1989, doi:10.1029/PA004i006p00655). There is good agreement between the calculated ages from 87Sr/86Sr measurements using these equations and those derived from magnetobiostratigraphy. In addition, these equations were useful for inference of sediment ages in intervals where the paleomagnetic record is not well resolved and the biostratigraphy is inconclusive. The Site 744 87Sr/86Sr record can be used for correlation of Antarctic and low-latitude sequences and biostratigraphical zonation of foraminifers, radiolarians, diatoms, and calcareous nannofossils. This record will assist in the development of the high southern latitude biochronology.

(Table T1) Abundance of silicoflagellates in sediments of ODP Hole 199-1219A

Silicoflagellates ranging from middle Eocene to middle Miocene in age are present in Ocean Drilling Program Hole 1219A. The hole was drilled 250.8 meters below seafloor of which an ~120 m section primarily composed of nannofossil ooze with variable radiolarian and clay content is early Miocene and Oligocene in age, and a 95-m section is Eocene radiolarian and zeolithic clays, radiolarian and diatom oozes, and nannofossil oozes and chalks. A total of 150 samples were studied at a sample interval of one per section. Diversity of silicoflagellates is moderate, and the preservation is good. Abundance is generally low, with many samples barren of silicoflagellates, but 31 species and subspecies were identified. One new species, Naviculopsis trigeminus, is described.

Pacific Neogene carbonate accumulation rates

I have compiled CaCO3 mass accumulation rates (MARs) for the period 0-25 Ma for 144 Deep Sea Drilling Project and Ocean Drilling Program drill sites in the Pacific in order to investigate the history of CaCO3 burial in the world's largest ocean basin. This is the first synthesis of data since the beginning of the Ocean Drilling Program. Sedimentation rates, CaCO3 contents, and bulk density were estimated for 0.5 Myr time intervals from 0 to 14 Ma and for 1 Myr time intervals from 14 to 25 Ma using mostly data from Initial Reports volumes. There is surprisingly little coherence between CaCO3 MAR time series from different Pacific regions, although regional patterns exist. A transition from high to low CaCO3 MAR from 23-20 Ma is the only event common to the entire Pacific Ocean. This event is found worldwide. The most likely cause of lowered pelagic carbonate burial is a rising sea-level trend in the early Miocene. The central and eastern equatorial Pacific is the only region with adequate drill site coverage to study carbonate compensation depth (CCD) changes in detail for the entire Neogene. The latitude-dependent decrease in CaCO3 production away from the equator is an important defining factor of the regional CCD, which shallows away from the equatorial region. Examination of latitudinal transects across the equatorial region is a useful way to separate the effects of changes in carbonate production ('productivity') from changes in bottom water chemistry ('dissolution') upon carbonate burial.

Calcareous nannofossil biostratigraphy of ODP Hole 108-667A and DSDP Site 85-574

Detailed quantitative analyses of selected calcareous nannofossil species were used to determine the placement of zonal boundaries. In Hole 667A in the equatorial Atlantic Ocean, Zones CP19 through CN5 were recognized, whereas at Site 574 in the equatorial Pacific Ocean, only the CN4/CN5 boundary could be determined. Boundaries were identified by sharp rises and declines in abundance at the beginnings and ends, respectively, of index fossil ranges. The sharp rise in abundance at the beginning of the range of Triquetrorhabdulus rugosus provided a good datum level in both regions; the same is true for the sharp decline in abundance at the end of the range of Cyclicargolithus floridanus. The last occurrence of Helicosphaera ampliaperta was used to mark the CN3/CN4 boundary in Hole 667A, while at Site 574, H. ampliaperta was absent. The abundance pattern of Triquetrorhabdulus carinatus obtained from Hole 667A makes it impossible to observe a distinct disappearance level. Age/depth plots reveal uniform sedimentation rates at both sites during early Miocene times. At Site 667 in the Atlantic the mean sedimentation rate was 14.90 m/m.y., and at Site 574 in the Pacific it was 16.17 m/m.y. during this same period. One new nannofossil species, Triquetrorhabdulus rioensis, is described; and one species, Triquetrorhabdulus serratus, is recombined.

Feldspar size measurements of tephra layers from ODP Leg 165 sites

Crystal size measurements have been carried out on tephra fall layers of Miocene to recent age from Sites 998, 999, and 1000 in the western Caribbean Sea. Maximum crystal size is used as a proxy for the grain size characteristics of the layers and an index of atmospheric dispersal from source eruptions. Crystal sizes range from 50 to 650 µm with the majority falling between 200 and 300 µm. All three sites exhibit a coarsening in the grain size of tephra layers with increasing age to the early Miocene that broadly correlates with an increase in the frequency of layers. Analysis of the present lower and upper level atmospheric circulation in the western Caribbean suggests that the layers were derived from source eruptions to the west of the sites somewhere in the Central American region. Minimum distances to these sources are of the order of 700 km. Crystal sizes in tephra layers at these distances are consistent with their derivation from energetic pyroclastic flow-forming eruptions that injected tephra to stratospheric levels by large-scale co-ignimbrite and plinian-style plumes. Coarsening of the layers during the Miocene peak of explosive volcanism cannot be attributed to any major change in paleowind intensity and is taken to represent the occurrence of more energetic eruptions that were able to disperse tephra over larger areas.

Grain size analysis on core plugs of sediment core CRP-1 (Table 1, 2)

Twenty four core samples from CRP-1, seven from Quaternary strata (20-43.55 meters below sea floor or mbsf) and seventeen from early Miocene strata (43.55 to 147.69 mbsf), have been analysed for their grain-size distribution using standard sieve and Sedigraph techniques. The results are in good agreement with estimates of texture made as part of the visual core description for the 1 :20 core logs for CRP-1 (Cape Roberts Science Team, 1998). Interpretation of the analyses presented here takes into account the likely setting of the site in Quaternary times as it is today, with CRP-1 high on the landward flank of a well-defined submarine ridge rising several hundred metres above basins on either side. In contrast, seismic geometries for strata deposited in early Miocene times indicate a generally planar sea floor dipping gently seaward. Fossils from these strata indicate shallow water depths (< 100 m), indicating the possibility that waves and tidal currents may have influenced sea floor sediments. The sediments analysed here are considered in terms of 3 textural facies: diamict, mud (silt and clay) and sand. Most of the Quaternary section but only 30% of the early Miocene section is diamict, a poorly sorted mixture of sand and mud with scattered clasts, indicating little wave or current influence on its texture. Although not definitive, diamict textures and other features suggest that the sediment originated as basal glacial debris but has been subsequently modified by minor winnowing, consistent with the field interpretation of this facies as ice-proximal and distal glaciomarine sediment. Sediments deposited directly from glacier ice appear to be lacking. Mud facies sediments, which comprise only 10% of the Quaternary section but a third of the early Miocene section, were deposited below wave base and largely from suspension, and show features (described elsewhere in this volume) indicative of the influence of both glacial and sediment gravity flow processes. Sand facies sediments have a considerable proportion of mud, normally more than 20%, but a well-sorted fine-very fine sand fraction. In the context of the early Miocene coastal setting we interpret these sediments as shoreface sands close to wave base.