Mineralogy and major-element chemistry of volcanic ash of ODP Site 131-808

Mineralogical and major-element compositions of 72 samples of volcanic ash, recovered from Site 808 at Nankai Trough during Leg 131, were analyzed in relation to the early diagenetic alteration. Alteration products are first observed at the following depths: smectite, 200 mbsf; clinoptilolite, 646 mbsf; and analcite, 810 mbsf. Glass decomposition dominates over authigenic mineral formation between 200 and 550 mbsf in the sediment column, whereas mineral formation becomes dominant below 550 mbsf. Based on the X-ray diffraction patterns, a broad and asymmetric peak of 15A suggests a presence of illite/smectite (I/S) mixed-layered minerals in a sample from 646 mbsf. I/S mixed-layered mineral formation, however, rarely occurs even at the bottom of the sediment column (1290 mbsf) at 120° C. This is possibly because zeolite (especially clinoptilolite) formed in the ash interferes with illite formation in the smectite. The formation of alteration minerals affects the major-element chemistry of the ash and the interstitial waters. H4SiO4 concentrations in interstitial waters increase during glass decomposition and decrease with smectite and clinoptilolite formation. K is removed from interstitial water into smectite and/or clinoptilolite. Mg is fixed into smectite (and/or chlorite).

Composition of ODP Leg 126 sandstones

Early diagenesis in Leg 126 forearc and backarc sands/sandstones is characterized by the dissolution of intermediate to mafic brown glass, the alteration of colorless rhyolitic glass to clay minerals, precipitation of thin clay-mineral rim cements, and minor precipitation of clinoptilolite cements. Later, more intense diagenesis is restricted to Oligocene forearc basin sediments at Sites 787,792, and 793. In these sections, the effects of early diagenesis have been intensified and overprinted by later diagenetic effects including (1) large-scale dissolution of feldspar and pyroxene crystals, (2) further dissolution of vitric components, (3) precipitation of minor carbonate cements, and (4) pervasive, multiple-staged zeolite cementation. Zeolite minerals present include analcite, mordenite, natrolite, heulandite, wairakite, chabazite, erionite, herschelite, and phillipsite. The latest diagenetic events appear to be the minor dissolution of zeolite cements and the precipitation of minor carbonate and potassium feldspar(?) cements. Observed porosity types include primary interparticles; primary intraparticles in vesicular glass and foraminifers; primary interparticles reduced by compaction and cementation; secondary intraparticles produced by dissolution of feldspar, nonopaque heavy minerals, volcanic glass, and foraminifer tests; and secondary interparticles produced by the dissolution of zeolite cements. Within forearc Oligocene sections at Sites 787 and 792, diagenetic effects appear to decrease with depth in the Oligocene section; however, at Site 793 the majority of samples are intensely altered.

Composition of suspended matter and bottom sediments from the North Dvina mouth area

Grain-size, mineral and chemical compositions of suspended particulate matter (SPM) from waters of the Severnaya (North) Dvina River mouth area during the spring flood in May 2004 is studied. Data published on composition of riverine SPM in the White Sea basin are very poor. The spring flood period when more than half of annual runoff is supplied from the river to the sea in during short time is understood more poorly. The paper considers comparison results of the grain size compositions of SPM and bottom sediments. Data of laser and hydraulic techniques of grain size analysis are compared. Short-period variations of SPM concentration and composition representing two diurnal peaks of the tide level are studied. It is found that SPM is mainly transferred during the spring flood as mineral aggregates up to 40 µm diameter. Sandy-silty fraction of riverine SPM settles in delta branches and channels, and bulk of clay-size material is supplied to the sea. Mineral and chemical compositions of SPM from the North Dvina River are determined by supply of material from the drainage basin. This material is subjected to intense mechanic separation during transfer to the sea. Key regularities of formation of mineral composition of SPM during the flood time are revealed. Effect of SPM grain size composition on distribution of minerals and chemical elements in study in the dynamic system of the river mouth area are characterized.

Magnetic susceptibility and documentation of sediment cores from the Antarctic Peninsula Pacific margin

The effects of glaciation on sediment drifts is recognised from marked sedimentary facies variation in deep sea cores taken from the continental rise of the Antarctic Peninsula Pacific margin. Nineteen sediment cores were visually described, logged for magnetic susceptibility, and X-radiographed. About 1000 analyses were performed for grain size, clay minerals and biostratigraphy (foraminifera, nannofossils and diatoms). Four sediment types associated with distinct sedimentary processes are recognised based on textural/compositional analysis. (1) Hemipelagic mud forms the bulk of the interglacial sediment, and accumulated from the pelagic settling of bioclasts and ice-rafted/windtransported detritus. (2) Terrigenous mud forms the bulk of the glacial sediment, and accumulated from a combination of sedimentary processes including turbidity currents, turbid plumes, and bottom current reworking of nepheloid layers. (3) Silty deposits occurring as laminated layers and lenses, represent the lateral spillout of lowdensity turbidity currents. (4) Lastly, glacial/interglacial gravelly mud layers derive from settling of ice-rafted detritus. Five depositional settings are interpreted within sediment Drift 7, each characterised by the dominance/interaction of one or several depositional processes. The repetitive succession of typical sedimentary facies is inferred to reflect a sequence of four climatic stages (glaciation, glacial, deglaciation, and interglacial), each one characterised by a distinctive clay mineral assemblage and bioclastic content. Variations in clay mineral assemblage within interglacial stage 5 (core SED-06) suggest minor colder climatic fluctuations, possibly correlatable with substages 5a to 5e.

Climatic records of the late Holocene from sediment core GeoB9504-3 off Senegal

High-resolution climatic records of the late Holocene along the north-west African continental margin are scarce. Here we combine sediment grain size, elemental distribution and mineral assemblage data to trace dust and riverine sources at a shallow-marine sediment depocentre in the vicinity of the Senegal River mouth. The aim is to understand how these terrigenous components reflect climate variability during the late Holocene. Major element contents were measured and mineral identification was performed on three sub-fractions of our sediment core: (i) fluvial material <2 µm, (ii) aeolian material of 18-63 µm and (iii) a sub-fraction of dual-origin material of 2-18 µm. Results show that more than 80% of the total Al and Fe terrigenous bulk content is present in the fluviogenic fraction. In contrast, Ti, K and Si cannot be considered as proxies for one specific source off Senegal. The Al/Ca ratio, recording the continental river runoff, reveals two dry periods from 3010 to 2750 cal a BP and from 1900 to 1000 cal a BP, and two main humid periods from 2750 to 1900 cal a BP and from 1000 to 700 cal a BP. The match between (i) intervals of low river runoff inferred by low Al/Ca values, (ii) reduced river discharge inferred by integrated palynological data from offshore Senegal and (iii) periods of enhanced dune reactivation in Mali confirms this interpretation.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Chemical composition of <0.001 mm grain size fraction from sedimentary rocks and bottom sediments of the Philippine Sea

Distriburtion and formation of clay minerals in different types of bottom sediments from the West Pacific are under consideration.

Geochemistry on sapropel deposition in the eastern Mediterranean from cores TTR-GL94 and M25/4-KL11

The geochemistry of the youngest Mediterranean sapropel layer suggests changes in productivity and water column oxygen conditions during sapropel deposition. The Ba-enriched interval is broader than the organic-carbon-rich interval of this sapropel. We suggest that the Ba-enriched horizon records the original thickness of the sapropel prior to subsequent partial oxidation. The main carrier of Ba is barite, as microcrystals (0.5-5 µm ) having a morphology characteristic of marine barite, particularly abundant beneath high productivity regions. Ba concentrations do not change at the sapropel layer oxidation front and diagenetic barite crystals are absent, thus the Ba-enriched layer reflects original oceanic conditions of increased biological productivity during sapropel deposition and not diagenetic Ba remobilization. Paleoredox indicators point to restricted oxygenated bottom water but not to fully anoxic conditions. Detrital elements within this layer indicate a lower eolian terrigenous input, enhanced humidity, and increased precipitation/runoff, thus likely higher nutrient supply.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Petrology and geochemistry of altered ocenaic crust of ODP Hole 140-504B

Altered basalt dikes from Hole 504B were partially melted at 1150°C and 1180°C to determine the composition of the first melts as oceanic Layer 2C is assimilated by a magma chamber. The partial melts are chemically similar to actinolite, the most abundant secondary mineral, but the melts are not simply melted actinolite. High TiO2, P2O5, and K2O abundances of the melts indicate that minor secondary minerals that are enriched in these elements also contribute to the melt. The incorporation of partial melts into a ridge-crest magma chamber may explain the local variability that is sometimes found in ocean ridge basalts that are not readily explained fractional crystallization or partial melting.

Grain counts and XRD mineralogy of turbidite sand and hemipelagic mud from ODP Leg 168 sites

Sequences of late Pliocene to Holocene sediment lap onto juvenile igneous crust within 20 km of the Juan de Fuca Ridge in northwestern Cascadia Basin, Pacific Ocean. The detrital modes of turbidite sands do not vary significantly within or among sites drilled during Leg 168 of the Ocean Drilling Program. Average values of total quartz, total feldspar, and unstable lithic fragments are Q = 35, F = 35, and L = 30. Average values of monocrystalline quartz, plagioclase, and K-feldspar are Qm = 46, P = 49, and K = 5, and the average detrital modes of polycrystalline quartz, volcanic-rock fragments, and sedimentary-rock plus metamorphic-rock fragments are Qp = 16, Lv = 43, and Lsm = 41. Likely source areas include the Olympic Peninsula and Vancouver Island; sediment transport was focused primarily through the Strait of Juan de Fuca, Juan de Fuca Channel, Vancouver Valley, and Nitinat Valley. Relative abundance of clay minerals (<2-µm-size fraction) fluctuate erratically with depth, stratigraphic age, and sediment type (mud vs. turbidite matrix). Mineral abundance in mud samples are 0%-35% smectite (mean = 8%), 18%-59% illite (mean = 40%), and 29%-78% chlorite + kaolinite (mean = 52%). We attribute the relatively low content of smectite to rapid mechanical weathering of polymictic source terrains, with little or no input of volcanic detritus from the Columbia River. The scatter in clay mineralogy probably was caused by converging of surface currents, turbidity currents, and near-bottom nepheloid clouds from several directions, as well as subtle changes in glacial vs. interglacial weathering products.

Geochemistry of pore fluids from ODP Leg 134 sites

Depending on the temperature and the extent of diagenetic alteration of fluid chemistry, fluid flow at convergent margins may transfer important quantities of heat and mass between the crust and seawater, thereby influencing global mass, isotopic and heat budgets. In the North Aoba Basin, an intra-arc basin located at the New Hebrides Island Arc, alteration of volcanic ash to clay minerals and zeolites forms a CaCl2 brine, perhaps in less than 1 to 3 m.y. The brine results from an exchange of Ca for Na, K, and Mg, and an increase in Cl concentrations to a maximum of 1241 mM. The Cl increase is partly due to the transfer of H2O from the pore fluid into authigenic minerals, but water mass balances, d18O-Cl correlations, and Br/Cl ratios suggest that there is a source of Cl in the sediments. Concentration profiles indicate that Li is transferred from the fluid to solid phase at depths <300 meters below seafloor (mbsf), but at greater depths it is transferred from the solid to fluid phase, at temperatures possibly as low as 25°C. In the accretionary wedge extensive fluid flow appears to be confined to highly faulted regions. Although Cl concentrations less than seawater value are common at convergent margins, the New Hebrides margin contains little low-Cl fluid. Br/Cl ratios suggest the low-Cl fluid is from dilution, and d18O values indicate the water may be derived from mineral dehydration and mixing with meteoric water. The New Hebrides margin exhibits few surface manifestations of venting (e.g., sulfide-oxidizing benthic biological communities, carbonate crusts, mud volcanoes) and thus fluid fluxes may be smaller than at many other margins.

Sediment composition in NE Greenland Fjords, Shelf, and Slope

In order to document changes in Holocene glacier extent and activity in NE Greenland (~73° N) we study marine sediment records that extend from the fjords (PS2631 and PS2640), across the shelf (PS2623 and PS2641), to the Greenland Sea (JM07-174GC). The primary bedrock geology of the source areas is the Caledonian sediment outcrop, including Devonian red beds, plus early Neoproterozoic gneisses and early Tertiary volcanics. We examine the variations in colour (CIE*), grain size, and bulk mineralogy (from X-ray diffraction of the <2 mm sediment fraction). Fjord core PS2640 in Sofia Sund, with a marked red hue, is distinct in grain size, colour and mineralogy from the other fjord and shelf cores. Five distinct grain-size modes are distinguished of which only one is associated with a coarse ice-rafting signal - this mode is rare in the mid- and late Holocene. A sediment unmixing program (SedUnMixMC) is used to characterize down-core changes in sediment composition based on the upper late Holocene sediments from cores PS2640 (Sofia Sund), PS2631 (Kaiser Franz Joseph Fjord) and PS2623 (south of Shannon Is), and surface samples from the Kara Sea (as an indicator of transport from the Russian Arctic shelves). Major changes in mineral composition are noted in all cores with possible coeval shifts centred c. 2.5, 4.5 and 7.5 cal. ka BP (±0.5 ka) but are rarely linked with changes in the grain-size spectra. Coarse IRD (>2 mm) and IRD-grain-size spectra are rare in the last 9-10 cal. ka BP and, in contrast with areas farther south (~68° N), there is no distinct IRD signal at the onset of neoglaciation. Our paper demonstrates the importance of the quantitative analysis of sediment properties in clarifying source to sink changes in glacial marine environments.