Bromine and iodine concentrations in sediments and pore fluids of ODP Leg 112

At the Peruvian convergent margin, two distinct pore fluid regimes are recognized from differences in their Cl- concentrations. The slope pore fluids are characterized by low Cl- concentrations, but elevated Br- and I- concentrations due to biogenic production. The shelf pore fluids exhibit elevated Cl- and Br- concentrations due to diffusive mixing with an evaporitic brine. In the slope pore fluids, the Br-, I-, and NH4+ concentrations are elevated following bacterial decomposition of organic matter, but the I- concentrations are in excess of those expected based on mass balance calculations using NH4+ and Br- concentrations. The slope sediment organic matter, which is enriched in iodine from oxidationreduction processes at the oxygenated sediment-water interface, is responsible for this enrichment. The increases in dissolved I- and the I- enrichments relative to NH4+ and Br- correlate well with sedimentation rates because of differential trapping following regeneration. The pore-fluid I-/Br- ratios suggest that membrane ion fiitration is not a major cause of the decreases in Cl- concentrations. Other possible sources for low Cl- water, including meteoric water, clathrate dissociation, and/or mineral dehydration reactions, imply that the diluting component of the slope low-Cl- fluids has flowed at least 1 km through the sediment. The low bottom-water oxygenation in the shelf is responsible for the low (if any) enrichment of iodine in the shelf sediments. Fluctuations in bottom-water oxygen concentrations in the past, however, may be responsible for the observed variations in the sediment I/Br ratios. Comparison of Na+/Cl- and Br-/Cl- molar ratios in the pore fluids shows that the shelf high-Cl- fluid formed from mixing with a brine that formed from seawater concentrated by twelve to nineteen times and probably was modified by halite dissolution. This dense brine, located below the sediment sections drilled, appears to have flowed a distance >500 km through the sediment.

High-resolution isotope stratigraphy of ODP Site 184-1144

Narrow-spaced oxygen and carbon stable isotope records of the planktonic foraminifer Globigerinoides ruber (white) were obtained at Ocean Drilling Program Leg 184 Site 1144 to establish a first record of high-resolution Pleistocene monsoon variability on orbital to centennial timescales in the northern South China Sea. The new records extend from the Holocene back to marine isotope Stage (MIS) 34 (1.1 Ma). Sedimentation rates average 0.56 m/k.y. for the upper Matuyama and Brunhes Chrons and increase to 1.8 m/k.y. over the last 100 k.y. Stable isotope records thus reach an average time resolution of 270-500 yr for the last 375 k.y. and 570 yr further back to 700 ka. On the other hand, major stratigraphic gaps were identified for peak warm Stages 5.5, 7.5 (down to 8.4), 11.3, and 15.5. These gaps probably resulted from short-lasting events of contour current erosion induced by short-term enhanced incursions of Upper Pacific Deep Water near the end of glacial terminations. A further major hiatus extends from MIS 34 to MIS 73(?). The long-term variations in monsoon climate were largely dominated by the 100-k.y. eccentricity cycle. Planktonic delta13C values culminated near 30, 480, and 1035 ka and reflect an overlying 450-k.y. eccentricity cycle of minimum nutrient concentrations in the surface ocean. Superimposed on the orbital variations, millennial-scale cycles were prominent throughout the last 700 k.y., mainly controlled by short-term changes in monsoon-driven precipitation and freshwater input from mainland China. During the last 110 k.y. these short-lasting oscillations closely match the record of 1500-yr Dansgaard-Oeschger climate cycles in the Greenland ice core record.

Age determination and planktonic foraminifera og ODP Site 159-958

Site 958 was drilled to monitor the late Neogene history of both continental aridity in northwestern Africa and the Canary Current distant from nearshore upwelling. Based on magnetostratigraphy, biostratigraphic datums, variations in carbonate, coarse fraction components, and the species composition of planktonic foraminifers, as well as using the d18O records of Globigerinoides ruber (white), we established a splice between Holes 958A and 958B and a stratigraphic age scale deciphering Milankovitch cycles. Over the last 630 k.y., sedimentation rates amount to 2.9 cm/k.y., and to 2.05-2.53 cm/k.y. back to the base of the Pleistocene. Extremely low rates of 0.4 cm/k.y. and a reworking of fossils mark the late Pliocene. The first continuous, long, sea-surface temperature (SST) record from the center of the Canary Current, which is based on foraminifer species census data, depicts a general temperature decrease in the late Pliocene, lower SST and high seasonalities of up to 6°C ~2.0-1.6 Ma, a warmer interval from 1.6 Ma to ~0.85 Ma, again lower SST and higher seasonalities until 0.33 or 0.26 Ma, and a final warmer interval, lasting until at least 50 ka, possibly reflecting the attenuated dynamics of the Canary Current. Especially over the last 400 k.y., since Stage 11, glacial stages are hardly reflected by cold SST cycles, except for various abrupt and extremely short cooling events amounting to D6°C, which possibly result from North Atlantic Heinrich events. Similar, but not necessarily synchronous, events of short-term, extremely high values occur in the paleoproductivity and (d13Cbased) paleonutrient records, which indicate a generally low primary production averaging to 180 g C m**-2 yr**-1 at 50-330 ka and about 300 g C m**-2 yr**-1 back to the base of the Pleistocene. Near 1.2-1.6 Ma, the grain-size and magnetic susceptibility records document a significant increase in the discharge of south Saharan/Sahelian dust, possibly linked to increasing aridity.

Geochemistry at DSDP Holes 80-550 amd 80-548

At Sites 548 and 550 of DSDP Leg 80 several condensed sedimentary sections contain various types of polymetallic crusts. The relationships between mineralogic and geochemical data in the sections have been studied in the context of the biostratigraphic and sedimentologic results. The diagenetic evolution during periods of low accumulation rate varies according to depth and sedimentary environment. At Site 548 on the continental margin, the phosphatic and manganiferous crusts are similar to those related to upwelling influences before Late Cretaceous deposition. At Site 550 the upper Paleocene cherts, deposited directly on oceanic crust, are overlain by pelagic brown clays containing diagenetic manganiferous concretions characterized by very high Sr and Ba contents. The origin of these small nodules is probably related to the authigenesis of fecal pellets. The upper Eocene indurated section is made up of authigenic zeolites, clays, and Fe-Mn phases and is similar to the volcanic-sedimentary deposits described in deep basins and seamounts of the Pacific. These crusts and a polynucleated nodule within the overlying sediments have geochemical characteristics (high Ni, Co, and Cu contents) similar to those formed in the deep ocean under volcanic influences during periods of low sedimentation rates or sedimentary hiatuses. Volcaniclastic material is ubiquitous and peculiarly abundant in Eocene sections and can be related to the volcanic formation of Iceland in the North Atlantic.

Magnetic stratigraphy of ODP Leg 133 sites

This study is a synthesis of paleomagnetic and mineral magnetic results for Sites 819 through 823 of Ocean Drilling Program (ODP) Leg 133, which lie on a transect from the outer edge of the Great Barrier Reef (GBR) down the continental slope to the bottom of the Queensland Trough. Because of viscous remagnetization and pervasive overprinting, few reversal boundaries can be identified in these extremely high-resolution Quaternary sequences. Some of the magnetic instability, and the differences in the quality of the paleomagnetic signal among sites, can be explained in terms of the dissolution of primary iron oxides in the high near-surface geochemical gradients. Well-defined changes in magnetic properties, notably susceptibility, reflect responses to glacio-eustatic sea-level fluctuations and changes in slope sedimentation processes resulting from formation of the GBR. Susceptibility can be used to correlate between adjacent holes at a given site to an accuracy of about 20 cm. Among-site correlation of susceptibility is also possible for certain parts of the sequences and permits (tentative) extension of the reversal chronology. The reversal boundaries that can be identified are generally compatible with the calcareous nannofossil biostratigraphy and demonstrate a high level of biostratigraphic consistency among sites. A revised chronology based on an optimum match with the susceptibility stratigraphy is presented. Throughout most of the sequences there is a strong inverse correlation both between magnetic susceptibility and calcium carbonate content, and between susceptibility and d18O. In the upper, post-GBR, sections a more complicated type of magnetic response occurs during glacial maxima and subsequent transgressions, resulting in a positive correlation between susceptibility and d18O. Prior to and during formation of the outer-reef barrier, the sediments have relatively uniform magnetic properties showing multidomain behavior and displaying cyclic variations in susceptibility related to sea-level change. The susceptibility oscillations are controlled more by carbonate dilution than by variation in terrigenous influx. Establishment of the outer reef between 1.01 and 0.76 Ma restricted the supply of sediment to the slope, causing a four-fold reduction in sedimentation rates and a transition from prograding to aggrading seismic geometries (see other chapters in this volume). The Brunhes/Matuyama boundary and the end of the transition period mark a change to lower and more subdued susceptibility oscillations with higher carbonate contents. The major change in magnetic properties comes at about 0.4 Ma in the aggrading sequence, which contains prominent sharp susceptibility peaks associated with glacial cycles, with distinctive single-domain magnetite and mixed single-domain/superparamagnetic characteristics. Bacterial magnetite has been found in the sediments, particularly where there are high susceptibility peaks, but its importance has not yet been assessed. A possible explanation for the characteristic pattern of magnetic properties in the post-GBR glacial cycles can be found in terms of fluvio-deltaic processes and inter-reefal lagoonal reservoirs that develop when the shelf becomes exposed at low sea-level.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.

Dating analysis from DSDP Hole 90-594

Date-32 is a fast and easily used computer program developed to date Quaternary deep-sea cores by associating variations in the earth's orbit with recurring oscillations in core properties, such as carbonate content or isotope composition. Starting with known top and bottom dates, distortions in the periodicities of the core properties due to varying sedimentation rates are realigned by fast Fourier analysis so as to maximise the spectral energy density at the orbital frequencies. This allows age interpolation to all parts of the core to an accuracy of 10 kyrs, or about 1.5% of the record duration for a typical Brunhes sequence. The influence of astronomical forcing is examined and the method is applied to provide preliminary dates in a high-resolution Brunhes record from DSDP Site 594 off southeastern New Zealand.

(Table 1) Redox potential and chemical element contents in CaCO3 and amorphous silica free matter in surface layer bottom sediments of the Pacific Ocean from Hawaiian Islands to Mexico coast

Distribution of Fe, Mn, P, Ti, Cu, Ni, Co, V, Cr, W, Mo, and As in the surface sediment layer on the section from the Hawaiian Islands to the coast of Mexico (Mexico section) is studied. Contents of all studied elements increase from biogenic-terrigenous sediments off the coast of Mexico to pelagic red clays of the Northeast Basin, and more sharply for mobile elements - Mn, Mo, Cu, Ni, Co, and As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basaltic composition with high contents of Ti, Fe, V, Cr, W, and P, contents of these elements increase sharply, and contents of Mn, Mo, Ni, Co, and Cu for the same reason decrease sharply in comparison with red clay. Abnormally high contents of Mn, Mo, Cu, Ni, Co, and As in the upper layer of hemipelagic and transition sediments of the Mexico section result from diagenetic redistribution and their accumulation on the surface. Processes of diagenetic redistribution in hemipelagic and transition sediment mass of the Mexico section are more rapid than in similar sediments of the Japan section due lower sedimentation rates and higher initial concentrations of Mn. Basic similarity of element distribution regularities in sediments of Japan and Mexico sections is shown.

Thorium and uranium isotopes in upper Pleistocene sediments of the Baffin Bay

Concentrations and activity ratios of uranium and thorium isotopes (234U/238U, 230Th/232Th) were determined at about 5-m intervals through the composite top 22-m sequence of Ocean Drilling Program (ODP) Hole 645 in Baffin Bay and, in the Labrador Sea, at 1-m intervals through the top 11 m of Core 84-030-003 (TWC and P) collected by the Hudson during a preliminary survey of Site 647, and also at about 2-m intervals through the composite top 22-m sequence of Hole 646. In the Labrador Sea, surficial sediments show unsupported 230Th having a 230Th/234U activity ratio of about 3. At Site 647, a regular decrease in the 230Th/232Th activity ratio was observed downcore from about 1.2 (at 1 mbsf) to about 0.4 (at ~8 mbsf), through a sequence spanning over 18O stages 2 through 8. The correlative thorium/uranium chronology and 18O stratigraphy indicate relatively constant sedimentation rates throughout the sequence. At Site 646, down Greenland slope, and at Site 645, in Baffin Bay, highly variable uranium and thorium concentrations and isotopic ratios were observed in relation to highly variable sedimentation rates. As a whole, the lower-excess observed in Baffin Bay records is indicative of very high absolute sedimentation rates in comparison with those of the Labrador Sea. These rates are confirmed by the 18O-stratigraphy and a few AMS 14C controls on handpicked foraminifers. At both Labrador Sea sites, a clear indication of an initial 230Th-excess (over the 230Th-rain from the water column) was found.

Diatom biostratigraphy, Argon ages and chronology of ODP Hole 183-1138A

A thick Neogene section was recovered in the upper ~300 m of Ocean Drilling Program Hole 1138A, drilled on the Central Kerguelen Plateau in the Indian sector of the Southern Ocean. Sediment lithologies consist primarily of mixed carbonate and biosiliceous clays and oozes, with several thin (1-3 cm) tephra horizons. The tephras are glass rich, well sorted, and dominantly trachytic to rhyolitic in composition. Volcaniclastic material in these horizons is interpreted to have originated from Heard Island, 180 km northwest of Site 1138, and was likely emplaced through both primary ash fall and turbiditic, submarine flows. A Neogene age-depth model for Hole 1138A is constructed primarily from 36 diatom biostratigraphic datums. Nannofossil and planktonic foraminifer biostratigraphy provides supporting age information. Additionally, four high-precision 40Ar-39Ar ages are derived from ash and tephra horizons, and these radiometric ages are in close agreement with the biostratigraphic ages. The integrated age-depth model reveals a reasonably complete lower Miocene to upper Pleistocene section in Hole 1138A, with the exception of a ~1-m.y. hiatus at the Miocene/Pliocene boundary. Another possible hiatus is also identified at the Oligocene/Miocene boundary. High Neogene sedimentation rates and the presence of both calcareous and siliceous microfossils, combined with datable tephra horizons, establish Site 1138 as a suitable target for future drilling legs with paleoceanographic objectives. This report also proposes two new diatom species, Fragilariopsis heardensis and Azpeitia harwoodii, from Pliocene strata of Hole 1138A.

Consolidation tests, elastic properties and grain size measurements at the consolidations samples from different Holes of IODP Expedition 302

The Integrated OceanDrilling Program's Expedition 302, the Arctic Coring Expedition (ACEX), recovered the first Cenozoic sedimentary sequence from the central Arctic Ocean. ACEX provided ground truth for basin scale geophysical interpretations and for guiding future exploration targets in this largely unexplored ocean basin. Here, we present results from a series of consolidation tests used to characterize sediment compressibility and permeability and integrate these with high-resolution measurements of bulk density, porosity and shear strength to investigate the stress history and the nature of prominent lithostratigraphic and seismostratigraphic boundaries in the ACEX record. Despite moderate sedimentation rates (10-30 m/Myr) and high permeability values (10**-15 -10**-18 m**2), consolidation and shear strength measurements both suggest an overall state of underconsolidation or overpressure. One-dimensional compaction modelling shows that to maintain such excess pore pressures, an in situ fluid source is required that exceeds the rate of fluid expulsion generated by mechanical compaction alone. Geochemical and sedimentological evidence is presented that identifes the Opal A-C/T transformation of biosiliceous rich sediments as a potential additional in situ fluid source.However, the combined rat of chemical and mechanical compaction remain too low to fully account for the observed pore pressure gradients, implying an additional diagenetic fluid source from within or below the recovered Cenozoic sediments from ACEX. Recognition of the Opal A-C/T reaction front in the ACEX record has broad reaching regional implications on slope stability and subsurface pressure evolution, and provides an important consideration for interpreting and correlating the spatially limited seismic data from the Arctic Ocean.

Pliocene-Pleistocene calcareous nannofossils from the Iberian Abyssal Plain

During Ocean Drilling Program Leg 149, five sites were drilled on the Iberia Abyssal Plain, west of the Iberian Peninsula. Five holes (Holes 897A, 897C, 898A, 899A, and 900A) yielded Pliocene-Pleistocene sediments, which consist mainly of turbidites. Among these, Holes 897C and 898A yielded significant Pliocene-Pleistocene sediments that provided a high-resolution nannofossil biostratigraphy essential for locating paleomagnetic polarity events and for interpreting the age and frequency of turbidite sedimentation in the Iberia Abyssal Plain. Pliocene-Pleistocene nannofossils recovered during Leg 149 are generally abundant and well to moderately preserved. Although reworking is evident in most samples, the Pliocene-Pleistocene nannofossils proved quite reliable for dating the sediments. Most Pleistocene zonal boundaries proposed by S. Gartner in 1977 and the Pliocene standard zonal boundaries proposed by E. Martini in 1971 were easily recognized. In addition, several other nannofossil events proposed by D. Rio et al. in 1990 and by T. Sato and T. Takayama in 1992 were recognized and proved valuable for improving the resolution of Pliocene-Pleistocene nannofossil biostratigraphy. The Pliocene-Pleistocene nannofossil biostratigraphic results of Holes 897C and 900A coincide rather well with the discerned paleomagnetic polarity events. As a result, the combination of nannofossil biostratigraphic and paleomagnetic studies provides important information for fulfilling the second objective of this leg: to determine the history of turbidite sedimentation in the Iberia Abyssal Plain. The general trend of sedimentation rates inferred by nannofossil biostratigraphy indicates that sedimentation rates increase from the continental margin to the deep sea along with increasing water depth.

Microfossil cyclicity in Late Albian sediments of Kirchrode I borehole

We studied the biological response to orbital forcing in marine Upper Albian sediments recovered from the 245 m-long Kirchrode I borehole in the Lower Saxony basin in northwestern Germany. Results from quantitative analysis of planktonic and benthic foraminifera, of calcareous nannofossils, and radiolaria were used for this study. Spectral analysis in the depth domain indicates for the high sedimentation rate part of the Upper Albian dominant periods with wavelengths of 10±13 m, 5±6 m, and 2±3 m, which we interpret to represent the biological response to orbital forcing in the Milankovitch frequency bands eccentricity, obliquity, and precession, respectively. In addition, a low amplitude 40±50 m cycle was found, which would represent the long-term eccentricity variation of roughly 400 ka. Microfossil cyclicity does not change significantly within the whole core indicating sedimentation rates of 11±12 cm/ka on an average, with variations between 3.5 and 13 ka. Microfossils show greater variability in their abundance changes than the physical and chemical parameters and also greater power in the higher-frequency bands (obliquity and precession). While most of the planktonic foraminifer species studied are dominated by variations in the obliquity, most benthic foraminifer species show an additional strong influence of precession. These differences in the cyclicity of the abundance changes are interpreted as reflecting a stronger influence of low latitude water in the deep waters of the Late Albian Lower Saxony basin than in the shallow waters. This basin was part of a wide, 'Boreal' epicontinental sea, which was connected to the Tethys to the south via the Polish strait and via the Paris basin, and which was connected with the North Atlantic and Arctic to the north. In analogy to results from analysis of data from the Late Neogene, strong effects of precession interpreted as being more characteristic for changes/influences triggered in the low latitudes and those of obliquity to be more characteristic for influences from the high latitudes. The presence of a relatively strong eccentricity cycle, not only in the compound parameters, but also in the abundance changes of single species during the Late Albian means that there must have been a non-linear response to orbital forcing and internal feedbacks.

Stable carbon and oxygen isotope compositions of bulk rock samples analyzed from the Zumaia section

Astronomical tuning of sedimentary records to precise orbital solutions has led to unprecedented resolution in the geological time scale. However, the construction of a consistent astronomical time scale for the Paleocene is controversial due to uncertainties in the recognition of the exact number of 405-kyr eccentricity cycles and accurate correlation between key records. Here, we present a new Danian integrated stratigraphic framework using the land-based Zumaia and Sopelana hemipelagic sections from the Basque Basin and deep-sea records drilled during Ocean Drilling Program (ODP) Legs 198 (Shatsky Rise, North Pacific) and 208 (Walvis Ridge, South Atlantic) that solves previous discrepancies. The new coherent stratigraphy utilises composite images from ODP cores, a new whole-rock d13C isotope record at Zumaia and new magnetostratigraphic data from Sopelana. We consistently observe 11 405-kyr eccentricity cycles in all studied Danian successions. We achieve a robust correlation of bioevents and stable isotope events between all studied sections at the ~100-kyr short-eccentricity level, a prerequisite for paleoclimatic interpretations. Comparison with and subsequent tuning of the records to the latest orbital solution La2011 provides astronomically calibrated ages of 66.022 ± 0.040 Ma and 61.607 ± 0.040 Ma for the Cretaceous-Paleogene (K-Pg) and Danian-Selandian 105 (D-S) boundaries respectively. Low sedimentation rates appear common in all records in the mid-Danian interval, including conspicuous condensed intervals in the oceanic records that in the past have hampered the proper identification of cycles. The comprehensive interbasinal approach applied here reveals pitfalls in time scale construction, filtering techniques in particular, and indicates that some caution and scrutiny has to be applied when building orbital chronologies. Finally, the Zumaia section, already hosting the Selandian Global Boundary Stratotype Section and Point (GSSP), could serve as the global Danian unit stratotype in the future.

Sediment and stable carbon isotope record of the Helgoland mud area

The Helgoland mud area in the German Bight is one of the very few sediment depocenters in the North Sea. Despite the shallowness of the setting (<30 m water depth), its topmost sediments provide a continuous and high-resolution record allowing the reconstruction of regional paleoenvironmental conditions for the time since ~400 a.d. The record reveals a marked shift in sedimentation around 1250 a.d., when average sedimentation rates drop from >13 to ~1.6 mm/year. Among a number of major environmental changes in this region during the Middle Ages, the disintegration of the island of Helgoland appears to be the most likely factor which caused the very high sedimentation rates prior to 1250 a.d. According to historical maps, Helgoland used to be substantially bigger at around 800 a.d. than today. After the shift in sedimentation, a continuous and highly resolved paleoenvironmental record reflects natural events, such as regional storm-flood activity, as well as human impacts at work at local to global scales, on sedimentation in the Helgoland mud area.