Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Minerals and geochemistry of DSDP Hole 81-552A

The acid insoluble coarse fractions of the glacial-interglacial sequence of Hole 552A in the NE Atlantic are made up of varying amounts of terrigenous detritus, biogenic silica, and pyroclastic material, principally volcanic glass. Volcanic ash content varies significantly over the entire interval, and the three North Atlantic ash horizons of Ruddiman and Glover (1972) can be recognized satisfactorily. The terrigenous detritus is of mixed metamorphic-basaltic type and probably originated on the Greenland landmass

Characteristics and radiocarbon ages of four retrogressive thaw slumps on Herschel Island and King Point

Four retrogressive thaw slumps (RTS) located on Herschel Island and the Yukon coast (King Point) in the western Canadian Arctic were investigated to compare the environmental, sedimentological and geochemical setting and characteristics of zones in active and stabilised slumps and at undisturbed sites. In general, the slope, sedimentology and biogeochemistry of stabilised and undisturbed zones differ, independent of their age or location. Organic carbon contents were lower in slumps than in the surrounding tundra, and the density and compaction of slump sediments were much greater. Radiocarbon dating showed that RTS were likely to have been active around 300 a BP and are undergoing a similar period of increased activity now. This cycle is thought to be controlled more by local geometry, cryostratigraphy and the rate of coastal erosion than by variation in summer temperatures.

Age models and foraminifer isotopes of four ODP Leg 202 sites

We present benthic isotope stratigraphies for Sites 1236, 1237, 1239, and 1241 that span the late Miocene-Pliocene time interval from 6 to 2.4 Ma. Orbitally tuned timescales were generated for Sites 1237 and 1241 by correlating the high-frequency variations in gamma ray attenuation density, percent sand of the carbonate fraction, and benthic d13C to variations in Earth's orbital parameters. The astronomical timescales for Sites 1237 and 1241 are in agreement with the one from Atlantic Site 925/926 (Ocean Drilling Program Leg 154). The comparison of benthic d18O and d13C records from the east Pacific sites and Atlantic Site 925/926 revealed a surprising clarity of the "41-k.y. signal" in d13C records and a remarkably good correlation between their d13C records. This suggests that the late Miocene-Pliocene amplitudes of obliquity-related d13C cycles reflect a magnitude of global response often larger than that provided by obliquity-related d18O cycles. At Site 1237, the orbitally derived ages of Pliocene magnetic reversal boundaries between the base of Réunion and the top of Thvera confirm astronomical datings of the generally accepted ATNTS2004 timescale, except for the top of Kaena and the base of Sidufjall. Our astronomical age for the top of Kaena is about one obliquity cycle older. The base of Sidufjall appears to be about one precession cycle younger. The age models of Sites 1236 and 1239 were established by correlating their benthic d18O and d13C records directly to the orbitally tuned isotope record of Site 1241.

Geochemistry and isotopic ratios of samples obtained during R/V Akademik Nikolaj Strakhov cruise ANS24

New petrological and geochemical data were obtained for basalts recovered during cruise 24 of the R/V "Akademik Nikolay Strakhov" in 2006. These results significantly contributed to the understanding of the formation of tholeiitic magmatism at the northern end of the Knipovich Ridge of the Polar Atlantic. Dredging was performed for the first time both in the rift valley and on the flanks of the ridge. It showed that the conditions of magmatism have not changed since at least 10 Ma. The basalts correspond to slightly enriched tholeiites, whose primary melts were derived at the shallowest levels and were enriched in Na and depleted in Fe (Na-TOR type). The most enriched basalts are typical of the earlier stages of the opening and were found on the flanks of the ridge in its northernmost part. Variations in the ratios of Sr, Nd, and Pb isotopes and lithophile elements allowed us to conclude that the primary melts generated beneath the spreading zone of the Knipovich Ridge were modified by the addition of the enriched component that was present both in the Neogene and Quaternary basalts of Spitsbergen Island. Compared with the primitive mantle, the extruding magmas were characterized by positive Nb and Zr anomalies and a negative Th anomaly. The formation of primary melts involved melting of the metasomatized depleted mantle reservoir that appeared during the early stages of opening of the Norwegian-Greenland Basin and transformation of the paleo-Spitsbergen Fault into the Knipovich spreading ridge, which was accompanied by magmatism in western Spitsbergen during its separation from the northern part of Greenland.

(Appendix B) Carbonate fraction geochemistry at DSDP Hole 72-516F

This paper presents data on trace elements (Sr, Mg, Na, K, Mn, Fe, Ni, Cr) and isotopes (13C, 18O) on the carbonate fraction of bulk sediments from the Coniacian to Paleocene samples of Hole 516F. Relationships of trace elements to mineralogy and stratigraphic position are discussed at length, with special emphasis on 1) the differences between Hole 516F and other oceanic sites, and 2) the transitions observed at the Cretaceous/Tertiary boundary. Isotope data are compared to those obtained in other localities of the same age. The sections show the same major 13C variations at the Cretaceous/Tertiary boundary, indicating that this event is a planetary phenomenon.

Age determination on rock samples from Svalbard

A linear, N-S-trending belt of elliptical, positive magnetic anomalies occurs in central Nordaustlandet, northeast Svalbard. They extend from the Caledonian and older complexes in the vicinity of Duvefjorden, southwards beneath the western margin of Austfonna and the offshore areas covered by Carboniferous and younger strata, to the vicinity of Edge¯ya. One of the strongest anomalies occurs in inner Duvefjorden where it coincides with a highly magnetic quartz monzonite-granite pluton at Djupkilsodden. U-Pb and Pb-Pb zircon dating of this post-tectonic pluton defines an age of c. 415 Ma, this being based on the Pb-Pb analyses of three specimens (Pb-Pb ages of 414±10 Ma, 411±10 Ma and 408±10 Ma) and a U-Pb discordia with an upper intercept at 417+18/-7 Ma. Neighbouring felsic plutons in central Nordaustlandet, including the Rijpfjorden and Winsnesbreen granites, lack magnetic signatures in their exposed parts, but have a similar Caledonian age. The central Nordaustlandet magnetic anomalies appear to be part of a circa 300 km long linear belt of late Silurian or early Devonian post-tectonic plutonism that characterizes the Caledonian basement of eastern Svalbard. Felsic intrusions of similar age further west in Spitsbergen are likewise both highly magnetic (Hornemantoppen batholith) and largely non-magnetic (Newtontoppen batholiths / Chydeniusbreen granitoid suite). They all appear to have been intruded at the end of the main period of Caledonian terrane assembly of the northwestern Barents Shelf.

Geochemistry of lavas and dikes from the upper oceanic crust of Hess Deep Rift, eastern Pacific Ocean

Strontium isotopes are useful tracers of fluid-rock interaction in marine hydrothermal systems and provide a potential way to quantify the amount of seawater that passes through these systems. We have determined the whole-rock Sr-isotopic compositions of a section of upper oceanic crust that formed at the fast-spreading East Pacific Rise, now exposed at Hess Deep. This dataset provides the first detailed comparison for the much-studied Ocean Drilling Program (ODP) drill core from Site 504B. Whole-rock and mineral Sr concentrations indicate that Sr-exchange between hydrothermal fluids and the oceanic crust is complex, being dependent on the mineralogical reactions occurring; in particular, epidote formation takes up Sr from the fluid increasing the 87Sr/86Sr of the bulk-rock. Calculating the fluid-flux required to shift the Sr-isotopic composition of the Hess Deep sheeted-dike complex, using the approach of Bickle and Teagle (1992, doi:10.1016/0012-821X(92)90221-G) gives a fluid-flux similar to that determined for ODP Hole 504B. This suggests that the level of isotopic exchange observed in these two regions is probably typical for modern oceanic crust. Unfortunately, uncertainties in the modeling approach do not allow us to determine a fluid-flux that is directly comparable to fluxes calculated by other methods.

Mineralogy and inorganic geochemistry of sediments at DSDP Leg 65 Holes

During Leg 65, 15 holes were drilled at four sites located on young crust in the mouth of the Gulf of California. Quaternary to upper Pliocene hemipelagic sediments above and interlayered within the young basaltic basement were cored. The influence of hot lava, high temperature gradients, and hydrothermal activity on the mineralogy and geochemistry of the terrigenous sediments near contacts with basalts might therefore be expected. The purpose of the present study was to determine the mineralogy and inorganic geochemistry of these sediments and to analyze the nature and extent of low temperature alteration. To this end we studied the mineralogy and inorganic geochemistry of 75 sediment samples, including those immediately overlying uppermost basalts and those from layers alternating with basalts within the basement. We separated three size fractions - <2 µm (clay), 2-20 µm (intermediate), and >20 µm (coarse) - and applied the following mineralogical determinations: x-ray diffraction (XRD), infrared spectroscopy, transmission and scanning electron microscopy, and optical microscopy (for coarse fractions, using thin sections and smear slides). We calculated the percentages of clay minerals using Biscaye's (1964) method, and used routine wet chemical analyses to determine bulk composition and quantitative spectral analyses for trace elements.

Chemical and isotopic compositions of volcanics from ODP Hole 210-1276

Site 1276, Leg 210 of the Ocean Drilling Program, was located on the Newfoundland margin in a seismically-defined ~128 Ma "transitional" crust just west of the presumed oceanic crust, and the M3 magnetic anomaly. The goal of drilling on this non-volcanic margin was to study the rifting, nature of basement, and post-rift sedimentation in the Newfoundland-Iberia rift. Drilling of this 1739 m hole was terminated 90-160 m above basement, in the lower of a doublet of alkaline diabase sills. We have carried out geochemical studies of the sill complex, in the hopes that they will provide proxy information regarding the nature of the underlying basement. Excellent 40Ar/39Ar plateau ages were obtained for the two sills: upper sill ~105.3 Ma; lower sill ~97.8 Ma. Thus the sills are substantially younger than the presumed age of the seafloor at site 1276 (~128 Ma), and were intruded beneath substantial sediment overburden (250 m for the upper, older sill, and 575 m for the lower younger sill). While some of the geochemistry of the sills has been compromised by alteration, the "immobile" trace elements show these sills to be hawaiites, differentiated from an enriched alkaline or basanitic parentage. Sr, Nd and Pb isotopes are suggestive of an enriched hotspot/plume mantle source, with a possible "added" component of continental material. These sills unequivocally were not derived from typical MORB (asthenospheric) upper mantle.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Geochemistry of ODP Leg 115 basalts

Melting-phase relations at high pressures and Sr-Nd isotopic compositions are reported for basalts collected from the western Indian Ocean during Ocean Drilling Program Leg 115. Based on the concentrations of high-field-strength elements, we have subdivided the basalts into eight groups. A tholeiitic primary magma estimated using an olivine maximum fractionation model is representative of depleted lavas. This melt is in equilibrium with lherzolite minerals at 1.3 GPa and 1330°C under dry conditions. Also, an alkaline primary magma, representative of enriched lavas, is not saturated with orthopyroxene under dry conditions, but it is saturated with lherzolite minerals under CO2-saturated conditions at 1.7 GPa and 1350°C. These results imply that the tholeiitic magmas were segregated from mantle diapirs at shallower levels than the alkaline magmas. The highest 143Nd/144Nd value is obtained for the most depleted tholeiitic basalts, and the lowest value corresponds to the enriched alkaline basalt. The Sr isotopes of the basalts range from 0.70378 to 0.70449 and are inversely correlated with the Nd isotopic values. The present experimental and geochemical data suggest that depleted mantle material is underlain by the enriched material in the upper mantle beneath the region.

Chert petrology and geochemistry at DSDP Leg 62 Holes

Sixty-five chert, porcellanite, and siliceous-chalk samples from Deep Sea Drilling Project Leg 62 were analyzed by petrography, scanning electron microscopy, analysis by energy-dispersive X-rays, X-ray diffraction, X-ray spectroscopy, and semiquantitative emission spectroscopy. Siliceous rocks occur mainly in chalks, but also in pelagic clay and marlstone at Site 464. Overall, chert probably constitutes less than 5% of the sections and occurs in deposits of Eocene to Barremian ages at sub-bottom depths of 10 to 820 meters. Chert nodules and beds are commonly rimmed by quartz porcellanite; opal-CT-rich rocks are minor in Leg 62 sediments 65 to 108 m.y. old and at sub-bottom depths of 65 to 520 meters. Chert ranges from white to black, shades of gray and brown being most common; yellow-brown and red-brown jaspers occur at Site 464. Seventy-eight percent of the studied cherts contain easily recognizable burrow structures. The youngest chert at Site 463 is a quartz cast of a burrow. Burrow silica maturation is always one step ahead of host-rock silicification. Burrows are commonly loci for initial silicification of the host carbonate. Silicification takes place by volume-f or-volume replacement of carbonate sediment, and more-clay-rich sediment at Site 464. Nannofossils are commonly pseudomorphically replaced by quartz near the edges of chert beds and nodules. Other microfossils, mostly radiolarians and foraminifers, whether in chalk or chert, can be either filled with or replaced by calcite, opal-CT, and (or) quartz. Chemical micro-environments ultimately control the removal, transport, and precipitation of calcite and silica. Two cherts from Site 465 contain sulfate minerals replaced by quartz. Site 465 was never subaerially exposed after sedimentation began, and the formation of the sulfate minerals and their subsequent replacement probably occurred in the marine environment. Several other cherts with odd textures are described in this paper, including (1) a chert breccia cemented by colloform opal-CT and chalcedony, (2) a transition zone between white porcellanite containing opal-CT and quartz and a burrowed brown chert, consisting of radial aggregates of opal-CT with hollow centers, and (3) a chert that consists of silica-replaced calcite pseudospherules interspersed with streaks and circular masses of dense quartz. X-ray-diffraction analyses show that when data from all sites are considered there are poorly defined trends indicating that older cherts have better quartz crystallinity than younger ones, and that opal-CT crystallite size increases and opal-CT cf-spacings decrease with depth of occurrence in the sections. In a general way, depth of burial and the presence of calcite promote the ordering in the opal-CT crystal structure which allows its eventual conversion to quartz. Opal-CT in porcellanites converts to quartz after reaching a minimum d-spacing of 4.07 Å. Quartz/opal-CT ratios and quartz crystallinity vary randomly on a fine scale across four chert beds, but quartz crystallinity increases from the edge to the center of a fifth chert bed; this may indicate maturation of the silica. Twenty-four rocks were analyzed for their major- and minor-element compositions. Many elements in cherts are closely related to major mineral components. The carbonate component is distinguished by high values of CaO, MgO, Mn, Ba, Sr, and (for unknown reasons) Zr. Tuffaceous cherts have high values of K and Al, and commonly Zn, Mo, and Cr. Pure cherts are characterized by high SiO2 and B. High B may be a good indicator of formation of chert in an open marine environment, isolated from volcanic and terrigenous materials.