Geochemical traces across the Paleocene-Eocene thermal maximum on Walvis Ridge

An understanding of sediment redox conditions across the Paleocene-Eocene thermal maximum (PETM) (?55 Ma) is essential for evaluating changes in processes that control deep-sea oxygenation, as well as identifying the mechanisms responsible for driving the benthic foraminifera extinction. Sites cored on the flanks of Walvis Ridge (Ocean Drilling Program Leg 208, Sites 1262, 1266, and 1263) allow us to examine changes in bottom and pore water redox conditions across a ~2 km depth transect of deep-sea sediments of PETM age recovered from the South Atlantic. Here we present measurements of the concentrations of redox-sensitive trace metals manganese (Mn) and uranium (U) in bulk sediment as proxies for redox chemistry at the sediment-water interface and below. All three Walvis Ridge sites exhibit bulk Mn enrichment factors (EF) ranging between 4 and 12 prior to the warming, values at crustal averages (Mn EF = 1) during the warming interval, and a return to pre-event values during the recovery period. U enrichment factors across the PETM remains at crustal averages (U EF = 1) at Site 1262 (deep) and Site 1266 (intermediate depth). U enrichment factors at Site 1263 (shallow) peaked at 5 immediately prior to the PETM and dropped to values near crustal averages during and after the event. All sites were lower in dissolved oxygen content during the PETM. Before and after the PETM, the deep and intermediate sites were oxygenated, while the shallow site was suboxic. Our geochemical results indicate that oxygen concentrations did indeed drop during the PETM but not sufficiently to cause massive extinction of benthic foraminifera.

Nd and Pb isotope data for DSDP and ODP sediments from the Bengal Fan

Correlation of new multichannel seismic profiles across the upper Indus Fan and Murray Ridge with a dated industrial well on the Pakistan shelf demonstrates that ~40% of the Indus Fan predates the middle Miocene, and ~35% predates uplift of the Murray Ridge (early Miocene, ~22 Ma). The Arabian Sea, in addition to the Makran accretionary complex, was therefore an important repository of sediment from the Indus River system during the Paleogene. Channel and levee complexes are most pronounced after the early Miocene, coincident with an increase in sedimentation rates. Middle Eocene sandstones from Deep Sea Drilling Project Site 224 on the Owen Ridge yield K-feldspars whose Pb isotopic composition, measured by in situ ion microprobe methods, indicates an origin in, or north of, the Indus suture zone. This observation requires that India-Asia collision had occurred by this time and that an Indus River system, feeding material from the suture zone into the basin, was active soon after collision. Pleistocene provenance was similar to that during the Eocene, albeit with greater contribution from the Karakoram. A mass balance of the erosional record on land with deposition in the fan and associated basins suggests that only ~40% of the Neogene sediment in the fan is derived from the Indian plate.

Geochemistry of the sheeted dike complex at Pito Deep

Alteration of sheeted dikes exposed along submarine escarpments at the Pito Deep Rift (NE edge of the Easter microplate) provides constraints on the crustal component of axial hydrothermal systems at fast spreading mid-ocean ridges. Samples from vertical transects through the upper crust constrain the temporal and spatial scales of hydrothermal fluid flow and fluid-rock reaction. The dikes are relatively fresh (average extent of alteration is 27%), with the extent of alteration ranging from 0 to >80%. Alteration is heterogeneous on scales of tens to hundreds of meters and displays few systematic spatial trends. Background alteration is amphibole-dominated, with chlorite-rich dikes sporadically distributed throughout the dike complex, indicating that peak temperatures ranged from <300°C to >450°C and did not vary systematically with depth. Dikes locally show substantial metal mobility, with Zn and Cu depletion and Mn enrichment. Amphibole and chlorite fill fractures throughout the dike complex, whereas quartz-filled fractures and faults are only locally present. Regional variability in alteration characteristics is found on a scale of <1-2 km, illustrating the diversity of fluid-rock interaction that can be expected in fast spreading crust. We propose that much of the alteration in sheeted dike complexes develops within broad, hot upwelling zones, as the inferred conditions of alteration cannot be achieved in downwelling zones, particularly in the shallow dikes. Migration of circulating cells along rides axes and local evolution of fluid compositions produce sections of the upper crust with a distinctive character of alteration, on a scale of <1-2 km and <5-20 ka.

(Table 1) Oxygen and carbon isotope compositions of altered carbonates from DSDP Hole 6-53 from the western Pacific Ocean

In the lower part of DSDP core 53.0, partly recrystallized carbonate sediments and well recrystallized limestone breccias of Oligo-Miocene age are associated with altered volcanic flows, lithified tuffs, and tuff breccias, suggesting that carbonate alteration was the result of thermal metamorphism. However, the oxygen isotope compositions of these carbonates (-3.4 to +0.6 per mil rel. PDB) are not compatible with recrystallization and isotope exchange with sea water at high temperatures. Evaluating the effects of the composition of the water which exchanged with the carbonates and of carbonate-water isotope exchange in closed systems yields the following approximate maximum temperature of recrystallization: limestone breccias, 100°C; calcite veins rimming breccia clasts, 30°C; and unconsolidated sediments overlying the breccias, 20°C. Therefore, the volcanics at site 53.0 must have been emplaced into the primary carbonate sediments at relatively low temperatures. Subsequent carbonate alteration was probably a consequence of chemical changes in ambient pore waters resulting from the submarine weathering of volcanic material.

Core alignment and composite depth scale of DSDP Site 86-577

Deep Sea Drilling Project Site 577 on Shatsky Rise (North Pacific Ocean) recovered a series of cores at three holes that contain calcareous nannofossil ooze of latest Cretaceous (late Maastrichtian) through early Eocene age. Several important records have been generated using samples from these cores, but the stratigraphy has remained outdated and confusing. Here we revise the stratigraphy at Site 577. This includes refining several age datums, realigning cores in the depth domain, and placing all stratigraphic markers on a current time scale. The work provides a template for appropriately bringing latest Cretaceous and Paleogene data sets at old drill sites into current paleoceanographic literature for this time interval. While the Paleocene Eocene Thermal Maximum (PETM) lies within core gaps at Holes 577* and 577A, the sedimentary record at the site holds other important events and remains crucially relevant to understanding changes in oceanographic conditions from the latest Cretaceous through early Paleogene.

Total number of benthic foraminifera in sediments below the K/T boundary in the Atlantic and Pacific Ocean

Most species of Late Cretaceous deep-sea benthic foraminifera are believed to be cosmopolitan and therefore to exhibit only minor biogeographical differences. In this preliminary report, six Deep Sea Drilling Project (DSDP) sites from different oceans, paleolatitudes, and paleodepths were analyzed for terminal Cretaceous abyssal-bathyal benthic foraminifera in order to investigate their assumed cosmopolitan distribution and the question of whether different faunal compositions are related to time, different paleolatitudes, and/or different paleodepths. The material studied was obtained from the low-latitude Site 465 (Pacific Ocean), and the intermediate-latitude Sites 384 (North Atlantic) and 356, 516, 525, and 527 (South Atlantic). The material analyzed represents a time slice encompassing the last 20-50 k.y. of the Cretaceous. The faunas contain numerous "Velasco-type" species, such as Gavelinella beccariiformis (White), Cibicidoides velascoensis (Cushman), Nuttallides truempyi (Nuttall), Gaudryina pyramidata Cushman, and various gyroidinoids and buliminids. The results contradict the general assumption of the cosmopolitan nature of Late Cretaceous deep-sea benthic foraminifera advocated in the literature. Only about 9% of the taxa identified were found to be truly "cosmopolitan" through their occurrence at all the sites analyzed. On the basis of correspondence analysis and relative abundance data, three assemblages and three subassemblages were recognized: (1) a bathyal-abyssal assemblage [Nuttallinella sp. A, Cibicidoides hyphalus (Fisher), Valvalabamina sp. evolute form, and Gyroidinoides spp.] at the South Atlantic Sites 356, 516, 525, and 527, divided into three subassemblages, namely (a) a middle bathyal subassemblage [Eouvigerina subsculptura McNeil and Caldwell, Truaxia aspera (Cushman), and G. pyramidata] at Sites 516 and 525, (b) a lower bathyal subassemblage [Osangularia? sp., Pyramidina rudita (Cushman and Parker), and Quadrimorphina camerata (Brotzen)] at Site 356, and (c) an abyssal subassemblage [Gyroidinoides sp. C, Hyperammina-Bathysiphon, Gyroidinoides beisseli (White), and Globorotalites sp. B] at Site 527; (2) an abyssal assemblage [Buliminella cf. plana (Cushman and Parker) and Bulimina incisa Cushman] at the North Atlantic Site 384; and (3) a middle bathyal assemblage [Vulvulina sp. A, Osangularia navarroana (Cushman), Alabamina? sp., Bulimina velascoensis (Cushman), Spiroplectammina spp. calcareous forms, and Bulimina trinitatensis Cushman and Jarvis] at the Pacific Site 465.

Magnetic susceptibility of deep-sea cores from the Scotia Sea

We studied two deep-sea cores from the Scotia Sea to reconstruct past atmospheric circulation in the southern hemisphere and to resolve a long-standing debate on the interpretation of magnetic susceptibility (MS) records in Southern Ocean (SO) sediment. High-sedimentation sites MD07-3134 (0.2 - 1.2 m/kyr) and MD07-3133 (0.3 - 2 m/kyr) cover the last 92.5 kyr and 36 kyr, respectively. Both exhibit a one-to-one coupling of the MS and Ca2+ signal to the non-sea salt (nss) Ca2+ signal of the EDML ice core, clearly identifying atmospheric circulation as means of distribution. Comparison of additional proxies also excludes major influence by volcanic sources, sea-ice, icebergs, or oceanic current transport. The close resemblance of the dust proxies over the last glacial cycle, in turn, allows for the establishment of an age model of unprecedented resolution and precision for SO deep-sea sediment because atmospheric transport involves no major leads or lags. This is of particular importance because MS is routinely measured on deep-sea cores in the SO but the sediments usually lack biogenic carbonate and therefore had only limited stratigraphic control so far. Southern South America (SSA) is the likely source of eolian material because Site MD07-3133, located closer to the continent, has slightly higher MS values than Site MD07-3134, and also the MS record of Patagonian Site SALSA shows comparable variability. Patagonia was the dust source for both the Scotia Sea and East Antarctica. Dust fluxes were several times higher during glacial times, when atmospheric circulation was either stronger or shifted in latitude, sea level was lowered, shelf surfaces were exposed, and environmental conditions in SSA were dominated by glaciers and extended outwash plains. Hence, MS records of SO deep-sea sediment are reliable tracers of atmospheric circulation, allowing for chronologically-constrained reconstructions of the circum Antarctic paleoclimate history.

40Ar/39Ar ages of boulders drilled at DSDP Hole 57-439

The 40Ar/39Ar stepheating dating method was applied to parts of three boulders recovered at Site 439, DSDP Leg 57. All the samples gave a well-defined isochron. The isochron ages agree with each other within the experimental uncertainties and give a mean value of 21.4 ± 1.0 Ma.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

Geochemistry of samples from Valtournenche, Western Italian Alps

Slices of polycyclic metasediments (marbles and meta-cherts) are tectonically amalgamated with the polydeformed basement of the Dent Blanche tectonic system along a major Alpine shear zone in the Western Alps (Becca di Salé area, Valtournenche Valley). A combination of techniques (structural analysis at various scales, metamorphic petrology, geochronology and trace element geochemistry) was applied to determine the age and composition of accessory phases (titanite, allanite and zircon) and their relation to major minerals. The results are used to reconstruct the polyphase structural and metamorphic history, comprising both pre-Alpine and Alpine cycles. The pre-Alpine evolution is associated with low-pressure high-temperature metamorphism related to Permo-Triassic lithospheric thinning. In meta-cherts, microtextural relations indicate coeval growth of allanite and garnet during this stage, at ~ 300 Ma. Textures of zircon also indicate crystallization at HT conditions; ages scatter from 263-294 Ma, with a major cluster of data at ~ 276 Ma. In impure marble, U-Pb analyses of titanite domains (with variable Al and F contents) yield apparent 206Pb/238U dates range from Permian to Jurassic. Chemical and isotopic data suggest that titanite formed at Permian times and was then affected by (extension-related?) fluid circulation during the Triassic and Jurassic, which redistributed major elements (Al and F) and partially opened the U-Pb system. The Alpine cycle lead to early blueschist facies assemblages, which were partly overprinted under greenschist facies conditions. The strong Alpine compressional overprint disrupted the pre-Alpine structural imprint and/or reactivated earlier structures. The pre-Alpine metamorphic record, preserved in these slices of metasediments, reflects the onset of the Permo-Triassic lithospheric extension to Jurassic rifting.

Cation exchange capacity and water content of ODP sites from Nankai

Pore fluid chlorinity lower than seawater is often observed in accretionary wedges and one of the possible causes of pore water freshening is the smectite to illite reaction. This reaction occurs during diagenesis in the 80-150°C temperature range. Low chlorinity anomalies observed at the toe of accretionary wedges have thus been interpreted as evidence for lateral fluid migration from inner parts of the wedge and the seismogenic zone. However, temperature conditions in Nankai Trough are locally high enough for the smectite to illite transition to occur in situ. Cation exchange capacity is here used as a proxy for smectite content in the sediment and the amount of interlayer water released during the smectite to illite reaction represents in average 12 water molecules per cation charge. Water and chloride budget calculations show that there is enough smectite to explain the chlorinity anomalies by in situ reactions. The shape of the pore fluid chlorinity profiles can be explained if compaction is also taken into account in the model. Lateral flow is not needed. This argument, based solely on chloride concentration, does not imply that lateral flow is absent. However, previous estimations of lateral fluid fluxes, and of the duration of transient flow events along the de.collement, should be reconsidered.

U-series ages from calcitic cold-water corals from the Amundsen Sea

Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) and which to date have not been investigated geochemically. The geochronological results are set in context with solution and laser ablation-based element/Ca ratios (Li, B, Mg, Mn, Sr, Ba, U, Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water D14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial d234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral d234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uranium mobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water D14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.

Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.

Mineral and organic geochemistry from Lake Anterne sediments (North French Alps)

A high-resolution sedimentological and geochemical study was performed on a 20 m long core from the alpine Lake Anterne (2063 m a.s.l., NW French Alps) spanning the last 10 ka. Sedimentation is mainly of minerogenic origin. The organic matter quantity (TOC%) as well as its quality (hydrogen (HI) and oxygen (OI) indices) both indicate the progressive onset and subsequent stabilization of vegetation cover in the catchment from 9950 to 5550 cal. BP. During this phase, the pedogenic process of carbonate dissolution is marked by a decrease in the calcium content in the sediment record. Between 7850 and 5550 cal. BP, very low manganese concentrations suggest anoxic conditions in the bottom-water of Lake Anterne. These are caused by a relatively high organic matter (terrestrial and lacustrine) content, a low flood frequency and longer summer stratification triggered by warmer conditions. From 5550 cal. BP, a decrease in TOC, stabilization of HI and higher sedimentation rates together reflect increased erosion rates of leptosols and developed soils, probably due to a colder and wetter climate. Then, three periods of important soil destabilization are marked by an increased frequency and thickness of flood deposits during the Bronze Age and by increases in topsoil erosion relative to leptosols (HI increases) during the late Iron Age/Roman period and the Medieval periods. These periods are also characterized by higher sedimentation rates. According to palynological data, human impact (deforestation and/or pasturing activity) probably triggered these periods of increased soil erosion.