Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Chemistry of siliciclastic and volcanoclastic sediments of DSDP Site 47-397

The Lower Cretaceous and Miocene sequences of the NW African passive continental margin consist of siliciclastic, volcaniclastic and hybrid sediments. These sediments contain a variety of diagenetic carbonates associated with zeolites, smectite clays and pyrite, reflecting the detrital mineralogical composition and conditions which prevailed during opening of the North Atlantic. In the Lower Cretaceous siliciclastic sediments, siderite (-6 per mil to +0.7per mil d18O PDB, -19.6 per mil to +0.6 per mil d13C PDB) was precipitated as thin layers and nodules from modified marine porewaters with input of dissolved carbon from the alteration of organic matter. Microcrystalline dolomite layers, lenses, nodules and disseminated crystals (-3.0 per mil to +2.5 per mil d18O PDB, -7.2 per mil to +4.9 per mil d13C PDB) predominate in slump and debris-flow deposits within the Lower Miocene sequence. During the opening of the Atlantic, volcanic activity in the Canary Islands area resulted in input of volcaniclastic sediments to the Middle and Upper Miocene sequences. Calcite is the dominant diagenetic carbonate in the siliciclastic-bioclastic-volcaniclastic hybrid and in the volcaniclastic sediments, which commonly contain pore-rimming smectite. Diagenetic calcite (-22 per mil to +1.6 per mil d18O PDB, -35.7 per mil to +0.8 per mil d13C PDB) was precipitated due to the interaction of volcaniclastic and bioclastic grains with marine porewaters. Phillipsite is confined to the alteration of volcaniclastic sediments, whereas clinoptilolite is widely disseminated, occurring essentially within foraminiferal chambers, and formed due to the dissolution of biogenic silica.

Sedimentology and gas hydrates of IODP Expedition 311 samples

Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8 km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49 mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23 cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63 µm) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245 mbsf.

Sapropels in the Mediterranean Sea

Eastern Mediterranean sediments are characterized by cyclic deposition of organic-rich sediments known as sapropels. Enhanced primary productivity combined with bottom water oxygen depletion are thought to be the main drivers for sapropel deposition. We selected sapropel layers from a suite of ODP-Leg 160 cores, and applied a set of geochemical proxies to determine paleo-productivity variations, redox conditions of the water column during deposition, and provenance of detrital material. High sedimentary Ba/Al and Corg contents indicate enhanced primary production, whereas the sedimentary La/Lu ratio, points to an enhanced contribution from a North African riverine source, during sapropel formation. These features are especially pronounced on Sapropels S5 and S7, deposited during a particularly warm climatic interval. This indicates a more intense North African drainage/weathering and consequently run-off for those sapropels that have the most enhanced expression of productivity too. Correspondingly, the latter has also resulted in bottom water redox conditions that have been more severe during these sapropels than during others. Deepwater formation from Adriatic and Aegean areas, thought to be mainly controlled by sustained cooling of preconditioned surface waters, triggers the onset of bottomwater ventilation, thus sapropel duration. Our data, therefore, suggest that the intensity of sapropel formation is determined by the North African monsoonal system, whereas their duration is directed by northern borderlands climatic conditions.

(Table 1) Heavy fraction minerals in bottom sediments of the Markov Deep, Mid-Atlantic Ridge

An additional ore field in the central part of the MARhas been discovered. Together with previously discovered Logachev (14°45'N) and Ashadze (12°58'N) ore fields, the new ore field constitutes a cluster with preliminarily estimated total ore reserve of >10 Mt, which is comparable with large continental massive sulfide deposits.

Strontium isotope geochemistry of ODP Leg 113 sites

The concentration of dissolved Sr and the distribution of 87Sr/86Sr isotope ratios in Leg 113 interstitial waters may be interpreted in terms of mixing of Sr from four different reservoirs: indigenous seawater, marine carbonate minerals, and basaltic and siliceous detrital material. The input to the pore water from these reservoirs is determined by the reactivity of the reservoir rather than its size. The presence of strontium derived from siliceous detrital material is unequivocally demonstrated in the pore waters of the hemipelagic deposits, and is also significant in the calcareous Maud Rise sediments due to the unusually low degree of carbonate recrystallization. Also, alteration of basic volcanic material is important at several sites.

Heavy minerals, grain size distribution, and ice-rafted debris in the Greenland Sea during 44 to 30 Ma

The widely accepted age estimate for the onset of glaciation in the Northern Hemisphere ranges between 2 and 15 million years ago (Ma). However, recent studies indicate the date for glacial onset may be significantly older. We report the presence of ice-rafted debris (IRD) in ~44 to 30 Ma sediments from the Greenland Sea, evidence for glaciation in the North Atlantic during the Middle Eocene to Early Oligocene. Detailed sedimentological evidence indicates that glaciers extended to sea level in the region, allowing icebergs to be produced. IRD may have been sourced from tidewater glaciers, small ice caps, and/or a continental ice sheet.

U-Th dating of marine sediments from the Bahamas slope

In order to understand the driving forces for Pleistocene climate change more fully we need to compare the timing of climate events with their possible forcing. In contrast to the last interglacial (marine isotope stage (MIS) 5) the timing of the penultimate interglacial (MIS 7) is poorly constrained. This study constrains its timing and structure by precise U-Th dating of high-resolution delta18O records from aragonite-rich Bahamian slope sediments of ODP Leg 166 (Sites 1008 and 1009). The major glacial-interglacial cycles in delta18O are distinct within these cores and some MIS 7 substages can be identified. These sediments are well suited for U-Th dating because they have uranium concentrations of up to 12 ppm and very low initial 230Th contributions with most samples showing 230Th/232Th activity ratio of >75. U and Th concentrations and isotope ratios were measured by thermal ionisation mass spectrometry and multiple collector inductively coupled plasma mass spectrometry, with the latter providing dramatically better precision. Twenty-nine of the 41 samples measured have a delta234U value close to modern seawater suggesting that they have experienced little diagenesis. Ages from 27 of the 41 samples were deemed reliable on the basis of both their U and their Th isotope ratios. Ages generally increase with depth, although we see a repeated section of stratigraphy in one core. Extrapolation of constant sedimentation rate through each substage suggests that the peak of MIS 7e lasted from ~237 to 228 ka and that 7c began at 215 ka. This timing is consistent with existing low precision radiometric dates from speleothem deposits. The beginning of both these substages appears to be slightly later than in orbitally tuned timescales. The end of MIS 7 is complex, but also appears to be somewhat later than is suggested by orbitally tuned timescales, although this event is not particularly well defined in these cores.

Dead Sea lake level for the last 140 ka

In this paper we describe the stratigraphy and sediments deposited in Lake Samra that occupied the Dead Sea basin between ~135 and 75 ka. This information is combined with U/Th dating of primary aragonites in order to estimate a relative lake-level curve that serves as a regional paleohydrological monitor. The lake stood at an elevation of ~340 m below mean sea level (MSL) during most of the last interglacial. This level is relatively higher than the average Holocene Dead Sea (~400±30 m below MSL). At ~120 and ~85 ka, Lake Samra rose to ~320 m below MSL while it dropped to levels lower than ?380 m below MSL at ~135 and ~75 ka, reflecting arid conditions in the drainage area. Lowstands are correlated with warm intervals in the Northern Hemisphere, while minor lake rises are probably related to cold episodes during MIS 5b and MIS 5d. Similar climate relationships are documented for the last glacial highstand Lake Lisan and the lowstand Holocene Dead Sea. Yet, the dominance of detrital calcites and precipitation of travertines in the Dead Sea basin during the last interglacial interval suggest intense pluvial conditions and possible contribution of southern sources of wetness to the region.

Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Mineral composition and 40Ar-39Ar data of samples from Garnet Point, Aurora Peak, Correll Nunatak, Penguin Point and Horn Bluffs, East Antarctica

George V Land (Antarctica) includes the boundary between Late Archean-Paleoproterozoic metamorphic terrains of the East Antarctic craton and the intrusive and metasedimentary rocks of the Early Paleozoic Ross-Delamerian Orogen. This therefore represents a key region for understanding the tectono-metamorphic evolution of the East Antarctic Craton and the Ross Orogen and for defining their structural relationship in East Antarctica, with potential implications for Gondwana reconstructions. In the East Antarctic Craton the outcrops closest to the Ross orogenic belt form the Mertz Shear Zone, a prominent ductile shear zone up to 5 km wide. Its deformation fabric includes a series of progressive, overprinting shear structures developed under different metamorphic conditions: from an early medium-P granulite-facies metamorphism, through amphibolite-facies to late greenschist-facies conditions. 40Ar-39Ar laserprobe data on biotite in mylonitic rocks from the Mertz Shear Zone indicate that the minimum age for ductile deformation under greenschist-facies conditions is 1502 ± 9 Ma and reveal no evidence of reactivation processes linked to the Ross Orogeny. 40Ar-39Ar laserprobe data on amphibole, although plagued by excess argon, suggest the presence of a ~1.7 Ga old phase of regional-scale retrogression under amphibolite-facies conditions. Results support the correlation between the East Antarctic Craton in the Mertz Glacier area and the Sleaford Complex of the Gawler Craton in southern Australia, and suggest that the Mertz Shear Zone may be considered a correlative of the Kalinjala Shear Zone. An erratic immature metasandstone collected east of Ninnis Glacier (~180 km east of the Mertz Glacier) and petrographically similar to metasedimentary rocks enclosed as xenoliths in Cambro-Ordovician granites cropping out along the western side of Ninnis Glacier, yielded detrital white-mica 40Ar-39Ar ages from ~530 to 640 Ma and a minimum age of 518 ± 5 Ma. This pattern compares remarkably well with those previously obtained for the Kanmantoo Group from the Adelaide Rift Complex of southern Australia, thereby suggesting that the segment of the Ross Orogen exposed east of the Mertz Glacier may represent a continuation of the eastern part of the Delamerian Orogen.

Strontium isotopes, ages and carbonate content of sediments from the Agulhas Current

The Agulhas Leakage represents a significant portion of the warm, surface return flow of the global overturning circulation and thus may be an important feedback in the ocean climate system. Models indicate that reduced leakage could be caused by a stronger Agulhas Current and/or a more upstream (eastward) Agulhas Retroflection, while a weaker Agulhas Current would result in a more westward retroflection and increased leakage. However, data for the Last Glacial Maximum support both a weaker Agulhas Current and less leakage, implying a possible displacement of the retroflection. We present new 87Sr/86Sr results for modern sediments within this region, confirming that the modern pathway of the Agulhas Current, Retroflection, and Leakage can be traced by terrigenous sediment provenance using Sr isotopes. New 87Sr/86Sr data from sediments deposited during the Last Glacial Maximum suggest that the glacial Agulhas Current and Retroflection followed nearly their modern trajectory. The provenance data appear to rule out both a stronger Agulhas Current and a more upstream Agulhas Retroflection. We conclude that the reduced glacial leakage was caused by the weakened Agulhas Current, with no significant change in the retroflection position. This is inconsistent with the model predictions and thus emphasizes the need for further work in this region.

(Table 1) Mineral composition at DSDP Leg 64 Holes

Mineral composition and compounds of sediments from the Guaymas Basin.

Age determination, carbon geochemistry and palynology of section AC003

Sedimentary records from California's Northern Channel Islands and the adjacent Santa Barbara Basin (SBB) indicate intense regional biomass burning (wildfire) at the Ållerød-Younger Dryas boundary (~13.0-12.9 ka) (All age ranges in this paper are expressed in thousands of calendar years before present [ka]. Radiocarbon ages will be identified and clearly marked "14C years".). Multiproxy records in SBB Ocean Drilling Project (ODP) Site 893 indicate that these wildfires coincided with the onset of regional cooling and an abrupt vegetational shift from closed montane forest to more open habitats. Abrupt ecosystem disruption is evident on the Northern Channel Islands at the Ållerød-Younger Dryas boundary with the onset of biomass burning and resulting mass sediment wasting of the landscape. These wildfires coincide with the extinction of Mammuthus exilis [pygmy mammoth]. The earliest evidence for human presence on these islands at 13.1-12.9 ka (~11,000-10,900 14C years) is followed by an apparent 600-800 year gap in the archaeological record, which is followed by indications of a larger-scale colonization after 12.2 ka. Although a number of processes could have contributed to a post 18 ka decline in M. exilis populations (e.g., reduction of habitat due to sea-level rise and human exploitation of limited insular populations), we argue that the ultimate demise of M. exilis was more likely a result of continental scale ecosystem disruption that registered across North America at the onset of the Younger Dryas cooling episode, contemporaneous with the extinction of other megafaunal taxa. Evidence for ecosystem disruption at 13-12.9 ka on these offshore islands is consistent with the Younger Dryas boundary cosmic impact hypothesis [Firestone et al., 2007, doi:10.1073/pnas.0706977104].