Geochemistry and minerals at DSDP Leg 81 Holes

Three phases of volcanism have been recognized in the lower Paleogene sequence of the southwest Rockall Plateau which are related to the onset of seafloor spreading in the NE Atlantic. The earliest, Phase 1, is marked by a sequence of tholeiitic basalts and hyaloclastites which form the dipping reflector sequence in Edoras Basin. Phase 2 is characterized by tuffs and lapilli tuffs of air-fall origin, ranging in composition from basic to intermediate. They were generated by highly explosive igneous activity due to magma-water interaction, and terminate at the level of a major transgression. Subsequently, volcanism reverted to tholeiitic basalt type, producing the thin tuffs and minor basalt flows of Phase 3. Alteration of the volcanic glass and diagenesis of the tuffs and lapilli tuffs has been considerable in many cases, with a large number of diagenetic mineral phases observed, including smectite, celadonite, analcime, phillipsite, clinoptilolite, mordenite, and calcite. Although calcite is the latest observed diagenetic cement, it nevertheless occurred relatively early, in one case totally preserving basaltic glass from alteration.

Elemental abundance and water content at DSDP Leg 86 Holes

X-ray fluorescence analyses of 1143 samples from Site 576 (32°21.4'N, 164°16.5'E) and 539 samples from Site 578 (33°55.6'N, 151°37.7'E) for the elements Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, Ba, and S show consistent trends from Si-rich surficial deposits to dark brown clays rich in Mn, Fe, P, and Ti in early Cenozoic sections. These data sets form the basis for a detailed paleogeochemical stratigraphy of North Pacific "red" clays.

Grain-size distribution and Folk's statistics at DSDP Leg 64 Holes

Grain size of 139 unconsolidated sediment samples from seven DSDP sites in the Guaymas Basin and the southeastern tip of the Baja California Peninsula was determined by sieve and pipette techniques. Shepard (1954) classification and Inman (1952) parameters correlation were used for all samples. Sediment texture ranged from sand to silty clay. On the basis of grain-size parameter, the sediments can be divided into three broad groups: (1) very fine sands and coarse silts; (2) medium- to very fine silts; and (3) clays and coarse silts.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Geochemistry of Lau Backarc Basin sediments

Major and minor (Mn, Sr, Ba, V, Cr, Ni, Co, Zn, Cu, Zr, Y, Sc) elements and mineralogic compositions were determined on bulk sediments collected during Ocean Drilling Program Leg 135. Three classes of sediment samples from holes drilled in the Lau Basin are discriminated by mineralogy and major element data. Samples labeled Class 1 are significantly enriched in biogenic calcite and occur predominantly in the northern part of the basin (Sites 834-835), whereas those of Class 3 are mostly enriched in volcanogenic material and are predominant in the central part of the basin (Sites 836-839). The minor element composition records the effects of the hydrothermal activity on the sediments. In the northern area of the basin (Sites 834-835), sedimentation is characterized by higher accumulation rates of the carbonate and hydrothermal fractions. These sediments are probably reworked predominantly, transported in the water column, and then settled locally. Thus, ponded sediments are probably responsible to this high accumulation rates. Diagenetic processes altered the volcanic material to a grade corresponding to the stability of phillipsite. In the central area of the basin (Sites 836-839), sedimentation is characterized by the action of bottom currents preferentially reworking the carbonate and hydrothermal fractions. Volcanogenic accumulation rates are greater at these sites than in the northern Lau Basin. Alteration of volcanic material is more important deeper in the holes and records authigenesis of clay rich in Fe-Mg, most likely smectite. Locally, clay minerals have apparently incorporated Cr and other ore-forming elements.

Diagenesis of siliceous particles in ODP Hole 114-699A

A number of neogenic opaline structures, not previously reported in the literature, as well as other neogenic phases are described from four Oligocene to Pliocene biosiliceous sediment samples from Hole 699A. The possible influence of microbes on the formation or the morphology of some of them is discussed. The samples, which are early Pliocene, early to middle Miocene, and late Oligocene (two) in age, were histologically fixed aboard ship upon retrieval. Investigations of the samples used SEM (with Edax/Tracor) and XRD methods. Diagenesis has affected all four samples, but the most extensive development of neoformed structures occurs in the Miocene and uppermost Oligocene samples, where microbial filaments (0.05 to 10 ?m long), microbial colonies, and siliceous microhemispheroids (0.2 to 0.7 µm diameter) were observed. The latter encrust filaments, diatoms, and detrital grains to varying degrees. Other neoformed structures include (1) flakes formed by coalesced microhemispheroids, some of which are guided by short, stubby filaments, which occur only in the Miocene and uppermost Oligocene samples, and (2) flakes characterized by smooth or microfissured surfaces, which grow on diatom frustules and in pore spaces and have a more widespread distribution. The XRD data indicate possible cristobalite formation in the Miocene and uppermost Oligocene samples; we believe that the neoformed opaline structures (encrusted filaments and microhemispheroids) may represent an early phase of opal-CT. The timing of neoformation of most of these features appears to have been fairly recent, continuing even at the time of sampling. There appears to be no direct correlation of this incipient, lower Miocene-uppermost Oligocene diagenetic layer and the pore-water chemistry profiles; a massive increase in shear strength in these sediments, however, may indicate some cementation. Smectite was identified by XRD as the most prominent clay mineral in these generally clay-poor sediments. Honeycombed minerals with filamentous edges, which could correspond to smectite, were observed with SEM in the pore spaces.

Geochemical and isotopic composition of pore fluids of ODP Hole 131-808C

At the Western Nankai Trough subduction zone at ODP Site 808, chemical concentration and isotopic ratio depth profiles of D, O, Sr, and He do not support fluid flow along the décollement nor at the frontal thrust. They do, however, support continuous or periodic lateral fluid flow: (1) at the base of the Shikoku Basin volcanic-rich sediment member, situated ~140 m above the décollement, and particularly (2) below the décollement. The latter must have been rather vigorous, as it was capable of transporting clay minerals over great distances. The fluid at ~140 m above the décollement is characterized by lower than seawater concentrations of Cl- (>=18% seawater dilution). It is 18O-rich and D-poor and has a non-radiogenic, oceanic, or volcanic arc Sr isotopic signature. It originates from "volcanic" clay diagenesis. The fluid below the décollement has also less Cl- than seawater (>20% dilution), is more enriched in 18O and depleted in D than fluid, but its Sr isotopic signature is radiogenic, continentalterrigenous. The source of this fluid is located arcward, is deep-seated, where illitization of the subducted clay minerals, a mixture of terrigenous and volcanic clays, occurs. The 3He/4He ratio below the décollement points to an ~25% mantle contribution. The nature of the physical and chemical discontinuities across the décollement suggests it is overpressured and is forming a leaky "dynamic seal" for fluid flow. In contrast with the situation at Barbados and Peru, where the major tectonic features are mineralized, here, although the complex is extremely fractured and faulted, mineralized macroscopic veins, fractures, and faults are absent. Instead, mineralized microstructures are widespread, indicating a diffuse mode of dewatering.

Geochemical analyses of chert nodules and beds from deep-sea sediments (Table 1)

Concentrations of Fe, Mg, Ca, Sr, Mn, Zn, and other heavy metals were analyzed by atomic absorption spectrometry in 27 chert samples from the Pacific deep sea, 17 chert samples from land, and 4 associated sediments from the Pacific Ocean. Among the elements, Fe and Mg concentrations are highly correlatable as are the relationships between Ca and Sr, or between Ca and CO2. The correlation between Fe and Mg is particularly high for Pacific deep-sea flints and cherts, and for cherts of deep-sea origin from outcrops on land. Enrichments in heavy metals were recognized in some deep-sea cherts; volcanogenic cherts are enriched in Fe, a chert nodule containing basaltic fragments is enriched in Zn and Cr, and biogenically enclosed carbonates in flint nodules are enriched in Mn. The correlation of Fe and Mg and their constant ratio [Mg(%)/Fe(%)] of around 0.33 might be characteristic features in the pelagic clays contained in deep-sea flints and cherts, and the concentrations of heavy metals in them would be controlled by the concentrations of Fe-Mg correlated clays. Although the mineralogical nature of the Fe-Mg clay in deep-sea cherts was not clarified by dissolution experiments on opaline minerals in chert, the high concentrations of Fe-montmorillonite and fine-grained olivine or other ferromagnesian silicate minerals in the clay may result in the high correlations between Fe and Mg.

Mineralogy and pyrolysis at DSDP Hole 62-463

A 15-meter sequence of early Aptian organic-matter-rich sediments, cored at Deep Sea Drilling Project Site 463 (western Mid-Pacific Mountains) has been submitted for detailed mineralogical studies (XRD, SEM) and organiccarbon characterization. Although intense diagenesis has obscured the sedimentary record of depositional conditions, the history has been tentatively reconstructed. Through sustained volcanic activity and alteration processes on the archipelago, large amounts of silica were released into the sea water, resulting in a "bloom" of radiolarians. Hard parts settled in large amounts, yielding a hypersiliceous sediment; amorphous silica was diagenetically transformed into chalcedony, opal-CT and clinoptilolite through dissolution and recrystallization. Oxidization of part of the radiolarian soft parts (1) depleted the sea water in dissolved oxygen, allowing the burial of organic matter, and (2) generated carbon dioxide which led to dissolution of most of the calcareous tests. Moderate depositional depth and a high sedimentation rate are though to have prevailed during this episode. An immature stage of evolution is assigned to the studied organic matter, which is of two origins: autochthonous marine material, and allochthonous humic compounds and plant debris. Rhythmic sedimentation characterizes the distribution of the organic matter; each sequence shows (1) an upward progressive increase in organic-carbon content, and (2) an upward enrichment in marine organic matter.

Radiocarbon ages and clay minerals in sediment cores obtained during a 2009 Jan Mayen cruise to the Norwegian Sea

The origin of two acoustic sediment units has been studied based on lithological facies, chronology and benthic stable isotope values as well as on foraminifera and clay mineral assemblages in six marine sediment cores from Kveithola, a small trough west of Spitsbergenbanken on the western Barents Sea margin. We have identified four time slices with characteristic sedimentary environments. Before c. 14.2 cal. ka, rhythmically laminated muds indicate extensive sea ice cover in the area. From c. 13.9 to 14.2 cal. ka, muds rich in ice-rafted debris were deposited during the disintegration of grounded ice on Spitsbergenbanken. From c. 10.3 to 13.1 cal. ka, sediments with heterogeneous lithologies suggest a shifting influence of suspension settling and iceberg rafting, probably derived from a decaying Barents Sea Ice Sheet in the inner-fjord and land areas to the north of Kveithola. Holocene deposition was episodic and characterized by the deposition of calcareous sands and shell debris, indicative of strong bottom currents. We speculate that a marked erosional boundary at c. 8.2 cal. ka may have been caused by the Storegga tsunami. Whilst deposition was sparse during the Holocene, Kveithola acted as a sediment trap during the preceding deglaciation. Investigation of the deglacial sediments provides unprecedented details on the dynamics and timing of glacial retreat from Spitsbergenbanken.

Geochemistry of Neogene volcanic ashs in ODP Leg 124 holes

Mineralogical and geochemical analyses were performed on 40 ash layers of Pleistocene to late Miocene age, recovered during Leg 124 in the Celebes and Sulu Seas (Sites 767, 768, and 769). They provide information on alteration processes related to burial diagenesis. The zonal distribution of secondary volcanic products emphasizes a major diagenetic change, characterized by the complete replacement of volcanic glass by an authigenic smectite-phillipsite assemblage, in tephra layers dated at 3.5-4 Ma. This diagenetic "event" occurs simultaneously in the two basins, and, on the basis of isotopic data, under low-temperature conditions. It is independent of distinct sedimentation rates and related to a relative quiescence of on-land volcanic activity. This period suggests a more uniform paleooceanographic situation having tectonic significance, and probably reflects a kinetic and environmental control of diagenetic reactions.

Biogenic and mineral composition and foraminiferal stratigraphy of sediment cores obtained in northern Germany

The Ratekau boring ended in clays of the so-called Asterigerina-Zone; these clays have shallow-water features in the uppermost samples. The clays are overlain by deep-water clays with pteropods; this formation is split into two parts by a shallow-water deposit. The fossiliferous series ends upward in sandy deposits with shallow-water fossils. The question is raised whether the two deep-water deposits might correspond to the Lower Doberg Beds (Eochattian) and the Upper Doberg Beds (Neochattian) at the Doberg hill, closer to the rim of the basin. All fossiliferous samples from this boring are thought to be of Late Oligocene age; the boundary towards the Middle Oligocene, however, could not be ascertained. The Vaale boring ended in rather typical Septaria clay of the Middle Oligocene. This clay is capped by some metres of unfossiliferous glauconite clays, which in turn are overlain by silts and silty clays with planktonic fossils identical to those found at Dingden locality. These deposits are tentatively dated as Early Miocene. The next higher series of samples consists of sands and clays deposited in shallower waters. They contain a rich fauna of benthic molluscs, which, according to the current notion in stratigraphy, would have a Reinbek Age. In addition, they contain a set of planktonic fossils which differs from the 'Lower Miocene' assemblages. These sands and clays are overlain by a thick series of marine sands very poor in fossils. Finally, four metres of clay with foraminifera, having Younger Miocene affinities, form the top of the fossiliferous sequence. The borings at Wulksfelde and Langenhorn were not far apart and their sediments are easily correlated. Both wells start below in continental 'Lignite Sands' and contain overlying shallow water sands and clays. These yielded Hemmoor benthic mollusca, supposed to indicate Lower Miocene in the relevant literature; however, we encountered their planktonic foraminifera in the uppermost Miocene as well. The same planktonic species were found in all samples of both borings. These deposits under discussion furthermore contain a particular pteropod species. They are overlain by a thick series of gypsiferous clays, with scarce fossils. The uppermost fossiliferous clays (probably Langenfelde Age) contain another pteropod species, not met with in other samples. The discrepancies between the plankton zonation and the traditional subdivision according to benthic molluscs in the borings of Vaale, Wulksfelde and Langenhorn (and in samples from Twistringen, Dingden and Antwerp localities as well) renders the time-stratigraphic value of the denominations Reinbek and Hemmoor rather doubtful. The samples of the Westerland boring can be placed in the Gram and Sylt stages of local chronostratigraphy on the strength of the Astarte series established by HINSCH. The Gram samples contain a typical pteropod species; both groups of samples contain the same planktonic foraminifera as the borings Wulksfelde and Langenhorn. Our material did not bring the problem of the Miocene-Pliocene boundary in this region any closer to a solution. In conclusion, it can be claimed that this investigation provides strong arguments that the usual recognition of Hemmoor and Reinbek does not correspond to well-defined chronostratigraphical units. A better chronostratigraphic subdivision has to be based on the examination of many more samples, and on a better understanding of the paleoecology of the fossils involved.