Compositions of Ni-rich magnesiowüstite and coexisting magnesioferrite spinel from sediments of DSDP Holes 86-577 and 91-596

We have found trace inclusions of Ni-rich magnesiowüstite within grains of magnesioferrite spinel recovered from Cretaceous/Tertiary boundary sediments from DSDP Site 596, South Pacific (23°51.20'S, 169°39.27'W) and DSDP Site 577, North Pacific (3°6.51'N, 157°43.40'E). Measured compositions of these inclusions range from (Mg_0.85Ni_0.74Fe_0.17)O to (Mg_0.74Ni_0.09Fe_0.17)O. Coexisting magnesioferrite and magnesiowüstite can only crystallize from ultramafic, refractory, Mg-rich liquids with Mg/Si > 2 (atom ratio). Such liquid compositions cannot form as a result of fractional crystallization and are unknown to occur as a result of terrestrial igneous processes or meteoroid ablation. We infer that these minerals crystallized from liquid droplets that equilibrated with silicate vapor at high temperatures (probably >2300°C), resulting in fractionation of volatile SiO2 from more refractory MgO. The most plausible source of this high-temperature vapor is in the fireball of the major impact event that terminated the Cretaceous.

Chemical composition of bottom sediments along the Transpacific section

Distribution of Fe, Mn, Ti, Cu, Ni, Co, V, Cr, Mo, As in bottom sediments of a section from the Hawaiian Islands to the coast of Mexico. In the surface layer and isochronic layers of sediments from biogenic-terrigenous sediments of the Mexico coast to pelagic red clays of the Northeast Basin contents of all studied elements increase, and more sharply for mobile ones - Mn, Mo, Cu, Ni, Co, As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basalt composition enriched in Ti, Fe, Cr, V, P contents of these elements in surface sediments and in sediment mass increase and contents of Mn, Mo, Ni, Co, Cu, As (for the same reason) decrease compared to red clays. An area of hemipelagic and transition sediments is identified; these sediments have much higher contents of Mn, Fe, Cu, Ni, Mo, As, (Ba) than red clays and similar sediments of the Northwest Pacific Ocean. This is due to hydrothermal activity in the tectonically active zone at the northern extension of the East Pacific Rise. Similar character of distribution of the elements in the surface layer and in the isochrone layers of bottom sediments along the most part of the section is shown. Similarity between distribution of the elements in sediments of the western and the eastern parts of the Transpacific section is established.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

Seagrass biofilm communities at a naturally CO2-rich vent at Papua New Guinea

Seagrass meadows are a crucial component of tropical marine reef ecosystems. The seagrass plants are colonized by a multitude of epiphytic organisms that contribute to determining the ecological role of seagrasses. To better understand how environmental changes like ocean acidification might affect epiphytic assemblages, the microbial community composition of the epiphytic biofilm of Enhalus acroides was investigated at a natural CO2 vent in Papua New Guinea using molecular fingerprinting and next generation sequencing of 16S and 18S rRNA genes. Both bacterial and eukaryotic epiphytes formed distinct communities at the CO2-impacted site compared to the control site. This site-related CO2 effect was also visible in the succession pattern of microbial epiphytes. We further found an increased abundance of bacterial types associated with coral diseases at the CO2-impacted site (Fusobacteria, Thalassomonas) whereas eukaryotes such as certain crustose coralline algae commonly related to healthy reefs were less diverse. These trends in the epiphytic community of E. acroides suggest a potential role of seagrasses as vectors of coral pathogens and may support previous predictions of a decrease in reef health and prevalence of diseases under future ocean acidification scenarios.

(Table 1) Chemical composition of Fe-rich layered silicates from the East Korean Rise, Japan Sea

Mineral and chemical compositions of highly ferruginous layered silicates (HLS) of glauconite sands occurred on the East Korean Rise outside volcanic structures and on an unnamed volcano and the Chentsov Volcano have been studied. The use of cluster and discriminant analyses has resulted to more objectively distinguished groups among HLS, and the use of factor analysis - to illustrate correlations between chemical elements in different groups. It has been found that green mineral assemblages of the East Korean Rise are heterogeneous in terms of morphology, composition and origin, and their formation is a complex multistage process including both neoformation and degradation.

Composition of palygorskite-rich and montmorillonite-rich zeolite-containing sediments from DSDP Sites 164 and 196

Cretaceous, Tertiary, and Quaternary sediments from Deep Sea Drilling Project Sites 164 and 196 (13°12' N, 161°31' W and 30°07' N, 148°34' E, respectively) were analyzed for major chemical elements and mineralogy. Sediments from these sites contain large proportions of authigenic minerals: mainly palygorskite, clinoptilolite and chert in the Cretaceous, and montmorillonite, phillipsite and chert in the Tertiary. The montmorillonite-phillipsite assemblage is thought to be derived from volcanic ash or glass, and the palygorskite-clinoptilolite assemblage is thought to be derived by reaction of biogenic silica with volcanic ash or glass or with montmorillonite and phillipsite. Both assemblages have generally moderate Ti/Al ratios, ranging from 0.026 to 0.047, so most of the palygorskite, clinoptilolite, montmorillonite and phillipsite could not be derived in situ from alteration of basaltic material. Plagioclase compositions suggest that the volcanic precursors were silicic or intermediate, but it is also possible that the sediments have been extensively fractionated by redistribution from nearby seamounts. Available data on other Late Cretaceous sediments in the Pacific were analyzed. Clinoptilolite and chert are present nearly everywhere where palygorskite is abundant; phillipsite is rare where palygorskite is abundant. It is suggested that increased water temperatures during the Cretaceous increased reaction rates and determined the alteration products.

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.

Sediment facies of the Indian-Pakistan continental margin, Indian Ocean Expedition

The studies described here base mainly on sedimentary material collected during the "Indian Ocean Expedition" of the German research vessel "Meteor" in the region of the Indian-Pakistan continental margin in February and March 1965. Moreover,samples from the mouth of the Indus-River were available, which were collected by the Pakistan fishing vessel "Machhera" in March 1965. Altogether, the following quantities of sedimentary material were collected: 59.73 m piston cores. 54.52 m gravity cores. 33 box grab samples. 68 bottom grab samples Component analyses of the coarse fraction were made of these samples and the sedimentary fabric was examined. Moreover, the CaCO3 and Corg contents were discussed. From these investigations the following history of sedimentation can be derived: Recent sedimentation on the shelf is mainly characterized by hydrodynamic processes and terrigenous supply of material. In the shallow water wave action and currents running parallel to the coast, imply a repeated reworking which induces a sorting of the grains and layering of the sediments as well as a lack of bioturbation. The sedimentation rate is very high here. From the coast-line down to appr. 50 m the sediment becomes progressively finer, the conditions of deposition become less turbulent. On the outer shelf the sediment is again considerably coarser. It contains many relicts of planktonic organisms and it shows traces of burrowing. Indications for redeposition are nearly missing, a considerable part of the fine fraction of the sediments is, however, whirled up and carried away. In wide areas of the outer shelf this stirring has gained such a degree that recent deposits are nearly completely missing. Here, coarse relict sands rich in ooids are exposed, which were formed in very shallow stirred water during the time when the sea reached its lowest level, i.e. at the turn of the Pleistocene to the Holocene. Below the relict sand white, very fine-grained aragonite mud was found at one location (core 228). This aragonite mud was obviously deposited in very calm water of some greater depth, possibly behind a reef barrier. Biochemic carbonate precipitation played an important part in the formation of relict sands and aragonite muds. In postglacial times the relict sands were exposed for long periods to violent wave action and to areal erosion. In the present days they are gradually covered by recent sediments proceeding from the sides. On the continental margin beyond the shelf edge the distribution of the sediments is to a considerable extent determined by the morphology of the sea bottom. The material originating from the continent and/or the shelf, is less transported by action of the water than by the force of gravity. Within the range of the uppermost part of the continental slope recent sedimentation reaches its maximum. Here the fine material is deposited which has been whirled up in the zone of the relict sands. A laminated fine-grained sediment is formed here due to the very high sedimentation rate as well as to the extremely low O2-content in the bottom water, which prevents life on the bottom of the sea and impedes thus also bioturbation. The lamination probaly reflects annual variation in deposition and can be attributed to the rhythm of the monsoon with its effects on the water and the weather conditions. In the lower part of the upper continental slope sediments are to be found which show in varying intensity, intercalations of fine material (silt) from the shelf, in large sections of the core. These fine intercalations of allochthonous material are closely related to the autochthonous normal sediment, so that a great number of small individual depositional processes can be inferred. In general the intercalations are missing in the uppermost part of the cores; in the lower part they can be met in different quantities, and they reach their maximum frequency in the upper part of the lower core section. The depositions described here were designated as turbid layer sediments, since they get their material from turbid layers, which transport components to the continental slope which have been whirled up from the shelf. Turbidites are missing in this zone. Since the whole upper continental slope shows a low oxygen-content of the bottom water the structure of the turbid layer sediments is more or less preserved. The lenticular-phacoidal fine structure does, however, not reflect annual rhythms, but sporadic individual events, as e.g. tsunamis. At the lower part of the continental slope and on the continental rise the majority of turbidites was deposited, which, during glacial times and particularly at the beginning of the post-glacial period, transported material from the zone of relict sands. The Laccadive Ridge represented a natural obstacle for the transport of suspended sediments into the deep sea. Core SIC-181 from the Arabian Basin shows some intercalations of turbidites; their material, however, does not originate from the Indian Shelf, but from the Laccadive Ridge. Within the range of the Indus Cone it is surprising that distinct turbidites are nearly completely missing; on the other hand, turbid layer sediments are to be found. The bottom of the sea is showing still a slight slope here, so that the turbidites funneled through the Canyon of the Swatch probably rush down to greater water depths. Due to the particularly large supply of suspended material by theIndus River the turbid layer sediments show farther extension than in other regions. In general the terrigenous components are concentrated on the Indus Cone. It is within the range of the lower continental slope that the only discovery of a sliding mass (core 186) has been located. It can be assumed that this was set in motion during the Holocene. During the period of time discussed here the following development of kind and intensity of the deposition of allochthonous material can be observed on the Indian-Pakistan continental margin: At the time of the lowest sea level the shelf was only very narrow, and the zone in which bottom currents were able to stir up material by oscillating motion, was considerably confined. The rivers flowed into the sea near to the edge of the shelf. For this reason the percentage of terrigenous material, quartz and mica is higher in the lower part of many cores (e.g. cores 210 and 219) than in the upper part. The transition from glacial to postglacial times caused a series of environmental changes. Among them the rise of the sea level (in the area of investigation appr. 150 m) had the most important influence on the sedimentation process. In connection with this event many river valleys became canyons, which sucked sedimentary material away from the shelf and transported it in form of turbidites into the deep sea. During the rise of the sea level a situation can be expected with a maximum area of the comparatively plane shelf being exposed to wave action. During this time the process of stirring up of sediments and formation of turbid layers will reach a maximum. Accordingly, the formation of turbidites and turbid layer sediments are most frequent at the same time. This happened in general in the older polstglacial period. The present day high water level results in a reduced supply of sediments into the canyons. The stirring up of sediments from the shelf by wave action is restricted to the finest material. The missing of shelf material in the uppermost core sections can thus be explained. The laminated muds reflect these calm sedimentation conditions as well. In the southwestern part of the area of investigation fine volcanic glass was blown in during the Pleistocene, probably from the southeast. It has thus become possible to correlate the cores 181, 182, 202. Eolian dust from the Indian subcontinent represents probably an important component of the deep sea sediments. The chemism of the bottom as well as of the pore water has a considerable influence on the development of the sediments. Of particular importance in this connection is a layer with a minimum content of oxygen in the sea water (200-1500 m), which today touches the upper part of the continental slope. Above and beyond this oxygen minimum layer somewhat higher O2-values are to be observed at the sea bottom. During the Pleistocene the oxygen minimum layer has obviously been locatedin greater depth as is indicated by the facies of laminated mud occuring in the lower part of core 219. The type of bioturbation is mainly determined by the chemism. Moreover, the chemism is responsible for a considerable selective dissolution, either complete or partial, of the sedimentary components. Within the range of the oxygen minimum layer an alkaline milieu is developed at the bottom. This causes a complete or partial dissolution of the siliceous organisms. Here, bioturbation is in general completely missing; sometimes small pyrite-filled burrowing racks are found. In the areas rich in O2 high pH-values result in a partial dissolution of the calcareous shells. Large, non-pyritized burrowing tracks characterize the type of bioturbation in this environment. A study of the "lebensspuren" in the cores supports the assumption that, particularly within the region of the Laccadive Basin, the oxygen content in the bottom sediments was lower than during the Holocene. This may be attributed to a high sedimentation rate and to a lower O2-content of the bottom water. The composition of the allochthonous sedimentary components, detritus and/or volcanic glass may locally change the chemism to a considerable extent for a certain time; under such special circumstances the type of bioturbation and the state of preservation of the components may be different from those of the normal sediment.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Vertical variations in basic salt composition of interstitial waters from Pacific sediments

Basic chemical composition of interstitial water in sediments of the Northwestern Pacific along a profile from the continental shelf of the Japan Trench to the ocean bed is discussed. Transformation of interstitial water in sediments rich in organic matter on the continental shelf and at the bottom of the Japan Trench is indicated. Variation in the vertical direction of elementary constituents of interstitial salt solution and variations in certain biogenic elements permit to make conclusions concerning processes taking place in sediments during sedimentation and diagenesis. These processes cause both metamorphism of water and transformation of organic and mineral content of sediments.