Results of bulk sediment X-ray diffraction analysis and quantification of mineral phases based on the RockJock and on the QUAX quantitative analysis

We have performed quantitative X-ray diffraction (qXRD) analysis of 157 grab or core-top samples from the western Nordic Seas between (WNS) ~57°-75°N and 5° to 45° W. The RockJock Vs6 analysis includes non-clay (20) and clay (10) mineral species in the <2 mm size fraction that sum to 100 weight %. The data matrix was reduced to 9 and 6 variables respectively by excluding minerals with low weight% and by grouping into larger groups, such as the alkali and plagioclase feldspars. Because of its potential dual origins calcite was placed outside of the sum. We initially hypothesized that a combination of regional bedrock outcrops and transport associated with drift-ice, meltwater plumes, and bottom currents would result in 6 clusters defined by "similar" mineral compositions. The hypothesis was tested by use of a fuzzy k-mean clustering algorithm and key minerals were identified by step-wise Discriminant Function Analysis. Key minerals in defining the clusters include quartz, pyroxene, muscovite, and amphibole. With 5 clusters, 87.5% of the observations are correctly classified. The geographic distributions of the five k-mean clusters compares reasonably well with the original hypothesis. The close spatial relationship between bedrock geology and discrete cluster membership stresses the importance of this variable at both the WNS-scale and at a more local scale in NE Greenland.

Quantitative component analysis of the coarse fraction of surface sediments from the Persian Gulf

In the Persian Gulf and the Gulf of Oman marl forms the primary sediment cover, particularly on the Iranian side. A detailed quantitative description of the sediment components > 63 µ has been attempted in order to establish the regional distribution of the most important constituents as well as the criteria governing marl sedimentation in general. During the course of the analysis, the sand fraction from about 160 bottom-surface samples was split into 5 phi° fractions and 500 to 800 grains were counted in each individual fraction. The grains were cataloged in up to 40 grain type catagories. The gravel fraction was counted separately and the values calculated as weight percent. Basic for understanding the mode of formation of the marl sediment is the "rule" of independent availability of component groups. It states that the sedimentation of different component groups takes place independently, and that variation in the quantity of one component is independent of the presence or absence of other components. This means, for example, that different grain size spectrums are not necessarily developed through transport sorting. In the Persian Gulf they are more likely the result of differences in the amount of clay-rich fine sediment brought in to the restricted mouth areas of the Iranian rivers. These local increases in clayey sediment dilute the autochthonous, for the most part carbonate, coarse fraction. This also explains the frequent facies changes from carbonate to clayey marl. The main constituent groups of the coarse fraction are faecal pellets and lumps, the non carbonate mineral components, the Pleistocene relict sediment, the benthonic biogene components and the plankton. Faecal pellets and lumps are formed through grain size transformation of fine sediment. Higher percentages of these components can be correlated to large amounts of fine sediment and organic C. No discernable change takes place in carbonate minerals as a result of digestion and faecal pellet formation. The non-carbonate sand components originate from several unrelated sources and can be distinguished by their different grain size spectrum; as well as by other characteristics. The Iranian rivers supply the greatest amounts (well sorted fine sand). Their quantitative variations can be used to trace fine sediment transport directions. Similar mineral maxima in the sediment of the Gulf of Oman mark the path of the Persian Gulf outflow water. Far out from the coast, the basin bottoms in places contain abundant relict minerals (poorly sorted medium sand) and localized areas of reworked salt dome material (medium sand to gravel). Wind transport produces only a minimal "background value" of mineral components (very fine sand). Biogenic and non-biogenic relict sediments can be placed in separate component groups with the help of several petrographic criteria. Part of the relict sediment (well sorted fine sand) is allochthonous and was derived from the terrigenous sediment of river mouths. The main part (coarse, poorly sorted sediment), however, was derived from the late Pleistocene and forms a quasi-autochthonous cover over wide areas which receive little recent sedimentation. Bioturbation results in a mixing of the relict sediment with the overlying younger sediment. Resulting vertical sediment displacement of more than 2.5 m has been observed. This vertical mixing of relict sediment is also partially responsible for the present day grain size anomalies (coarse sediment in deep water) found in the Persian Gulf. The mainly aragonitic components forming the relict sediment show a finely subdivided facies pattern reflecting the paleogeography of carbonate tidal flats dating from the post Pleistocene transgression. Standstill periods are reflected at 110 -125m (shelf break), 64-61 m and 53-41 m (e.g. coare grained quartz and oolite concentrations), and at 25-30m. Comparing these depths to similar occurrences on other shelf regions (e. g. Timor Sea) leads to the conclusion that at this time minimal tectonic activity was taking place in the Persian Gulf. The Pleistocene climate, as evidenced by the absence of Iranian river sediment, was probably drier than the present day Persian Gulf climate. Foremost among the benthonic biogene components are the foraminifera and mollusks. When a ratio is set up between the two, it can be seen that each group is very sensitive to bottom type, i.e., the production of benthonic mollusca increases when a stable (hard) bottom is present whereas the foraminifera favour a soft bottom. In this way, regardless of the grain size, areas with high and low rates of recent sedimentation can be sharply defined. The almost complete absence of mollusks in water deeper than 200 to 300 m gives a rough sedimentologic water depth indicator. The sum of the benthonic foraminifera and mollusca was used as a relative constant reference value for the investigation of many other sediment components. The ratio between arenaceous foraminifera and those with carbonate shells shows a direct relationship to the amount of coarse grained material in the sediment as the frequence of arenaceous foraminifera depends heavily on the availability of sand grains. The nearness of "open" coasts (Iranian river mouths) is directly reflected in the high percentage of plant remains, and indirectly by the increased numbers of ostracods and vertebrates. Plant fragments do not reach their ultimate point of deposition in a free swimming state, but are transported along with the remainder of the terrigenous fine sediment. The echinoderms (mainly echinoids in the West Basin and ophiuroids in the Central Basin) attain their maximum development at the greatest depth reached by the action of the largest waves. This depth varies, depending on the exposure of the slope to the waves, between 12 to 14 and 30 to 35 m. Corals and bryozoans have proved to be good indicators of stable unchanging bottom conditions. Although bryozoans and alcyonarian spiculae are independent of water depth, scleractinians thrive only above 25 to 30 m. The beginning of recent reef growth (restricted by low winter temperatures) was seen only in one single area - on a shoal under 16 m of water. The coarse plankton fraction was studied primarily through the use of a plankton-benthos ratio. The increase in planktonic foraminifera with increasing water depth is here heavily masked by the "Adjacent sea effect" of the Persian Gulf: for the most part the foraminifera have drifted in from the Gulf of Oman. In contrast, the planktonic mollusks are able to colonize the entire Persian Gulf water body. Their amount in the plankton-benthos ratio always increases with water depth and thereby gives a reliable picture of local water depth variations. This holds true to a depth of around 400 m (corresponding to 80-90 % plankton). This water depth effect can be removed by graphical analysis, allowing the percentage of planktonic mollusks per total sample to be used as a reference base for relative sedimentation rate (sedimentation index). These values vary between 1 and > 1000 and thereby agree well with all the other lines of evidence. The "pteropod ooze" facies is then markedly dependent on the sedimentation rate and can theoretically develop at any depth greater than 65 m (proven at 80 m). It should certainly no longer be thought of as "deep sea" sediment. Based on the component distribution diagrams, grain size and carbonate content, the sediments of the Persian Gulf and the Gulf of Oman can be grouped into 5 provisional facies divisions (Chapt.19). Particularly noteworthy among these are first, the fine grained clayey marl facies occupying the 9 narrow outflow areas of rivers, and second, the coarse grained, high-carbonate marl facies rich in relict sediment which covers wide sediment-poor areas of the basin bottoms. Sediment transport is for the most part restricted to grain sizes < 150 µ and in shallow water is largely coast-parallel due to wave action at times supplemented by tidal currents. Below the wave base gravity transport prevails. The only current capable of moving sediment is the Persian Gulf outflow water in the Gulf of Oman.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Hydrate, ice and quartz content of eight holes of Leg 204

The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis ("Rietveld method") of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Porosity contributions of radiolarians in ODP Site 110-671 and Hole 110-672A sediments

This study quantitatively addresses the significance of porosity within radiolarian tests in the décollement zone at the toe of the northern Barbados accretionary prism. Quantification was accomplished using scanning electron microscope images of core samples taken from Ocean Drilling Program (ODP) Sites 671 and 672, representing the décollement and proto-décollement, respectively. The décollement is localized to a radiolarian claystone, and its depth correlates with a low-density anomaly that has been attributed to high porosity at all relevant ODP drilling sites in the area (Moore, Klaus, et al., 1998, doi:10.2973/odp.proc.ir.171A.1998; Shipley, Ogawa, Blum, et al., 1995, doi:10.2973/odp.proc.ir.153.1995; Mascle, Moore, et al., 1988, doi:10.2973/odp.proc.ir.110.1988). Porosity in the décollement zone is presumably lost between Sites 672 and 671 because of shear enhanced consolidation (Moore et al., 1998, doi:10.1130/0091-7613(1998)026<0811:CPDIAE>2.3.CO;2).

AMS and EBSD maps of rock salt - lamprophyre dyke contact zone, Loule diapir, Algarve basin, Portugal

A rock salt-lamprophyre dyke contact zone (sub-vertical, NE-SW strike) was investigated for its petrographic, mechanic and physical properties by means of anisotropy of magnetic susceptibility (AMS) and rock magnetic properties, coupled with quantitative microstructural analysis and thermal mathematical modelling. The quantitative microstructural analysis of halite texture and solid inclusions revealed good spatial correlation with AMS and halite fabrics. The fabrics of both lamprophyre and rock salt record the magmatic intrusion, "plastic" flow and regional deformation (characterized by a NW-SE trending steep foliation). AMS and microstructural analysis revealed two deformation fabrics in the rock salt: (1) the deformation fabrics in rock salt on the NW side of the dyke are associated with high temperature and high fluid activity attributed to the dyke emplacement; (2) On the opposite side of the dyke, the emplacement-related fabric is reworked by localized tectonic deformation. The paleomagnetic results suggest significant rotation of the whole dyke, probably during the diapir ascent and/or the regional Tertiary to Quaternary deformation.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.