Rare earth element contents in deposits and minerals of the ocean floor

Current understanding of rare earth element (REE) geochemistry in the ocean is given in the book. Chemical properties determining REE migration ability in natural processes, sources of REE in the ocean, behavior of REE in river-sea mixing zones, fractionation of dissolved and particulate REE in ocean waters under aerobic and anaerobic conditions, distribution of REE in terrigenous, authigenic, hydrothermal and biogenic sediment components (clay, bone detritus, barite, phillipsite, Fe- and Mn-oxyhydroxides, Fe-Ca hydroxophosphate, diatoms and foraminiferas) are under consideration.

Mineralogy and stable isotopic composition of carbonates and sulfide minerals from ODP Leg 164 sites

During Ocean Drilling Program Leg 164, gas hydrates were recovered in the Blake Ridge where the top of the gas hydrate zone lies at about 200 meters below seafloor (mbsf) and the bottom-simulating reflector (BSR) is located at about 450 mbsf. There is no sedimentological discontinuity crossing the BSR. The BSR is disrupted by the salt piercement of the Cape Fear Diapir. The authigenic carbonates (dolomite and siderite) are always present in small amounts (a few weight percent) in the sediments; they are also concentrated in millimeter- to centimeter-sized nodules and layers composed of dolomite above the top of the gas hydrate reservoir, and of siderite below the BSR. In the Blake Ridge, the dolomite/siderite boundary is located near 140 mbsf. The distribution with depth of the d18O values of dolomite and siderite shows a sharp decrease from high values (maximum 7.5 per mil) in the topmost 50 m, to very low values (minimum -2.7 per mil) at 140 mbsf, and at greater depth increase to positive values within the range of 1.8 per mil to 5.0 per mil. The d13C distribution is marked by the rapid increase with greater depth from low values (-31.3 per mil to -11.4 per mil) near 50 mbsf to positive values at 110 mbsf, which remain in the range of 1.7 to 5.4 down to 700 mbsf. Diagenetic carbonates were precipitated in pore waters in which d18O and d13C values were highly modified by strong fractionation effects, both in the water and in the CO2-CH4 systems associated with the formation and dissociation of gas hydrates.

Clay and silica minerals of ODP Site 123-765

Sediments recovered from Site 765 can be divided into seven mineral associations, based on differences in clay mineralogy. These clay mineral associations correlate with the lithologic units and reflect the rift-to-drift history of the passive Australian margin. In general, the Lower to mid-Cretaceous sediments represent altered volcanic material and detrital aluminosilicates that were deposited during the early formation of the Argo Basin. The predominant clay mineral is randomly interstratified illite/smectite (I/S) that contains less than 10% illite layers. The transformation of smectite to illite is suggested by an increase in the percentage of illite layers in the basal sediments (from <10% to 40%) that corresponds to the silica transformation of opal-CT to quartz. This mixed-layered illite/smectite has an average composition of (K0.14 Na0.29 C0.07)(Al0.88 Mg0.43 Fe0.61 Ti0.06)(Si3.88 Al0.12)(O)10(OH)2. The highly smectitic composition of the I/S and its association with bentonite layers and zeolite minerals suggest that much of the I/S was derived from the alteration of volcanic material. The condensed middle to Upper Cretaceous sediments consist of palygorskite and detrital I/S that contains 30% to 60% illite layers. The condensed Paleogene sediments contain no palygorskite and are dominated by detrital clay minerals or by highly smectitic I/S associated with bentonite layers and zeolite minerals. The overlying, rapidly deposited Neogene clayey calcareous turbidites consist of three distinct clay mineral associations. Middle Miocene sediments contain palygorskite, kaolinite, and a tentatively identified mixed-layered illite/smectite/chlorite (I/S/C) or saponite. Upper Miocene sediments contain abundant sepiolite and kaolinite and lesser amounts of detrital I/S. Detrital I/S and kaolinite dominate the clay mineralogy of Pliocene and Pleistocene sediments. The fibrous, magnesium-rich clay minerals sepiolite and palygorskite appear to be authigenic and occur intimately associated with authigenic dolomite. The magnesium required to form these Mg-rich minerals was supplied by diffusion from the overlying seawater, and silica was supplied by the dissolution of associated biogenic silica.

Rare earth element fractionation in authigenic illite–smectite from Late Permian clastic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization

REE analyses were performed on authigenic illitic clay. minerals from Late Permian mudrocks, sandstones and bentonites from the Bowen Basin (Australia). The mixed-layer illite-smectite exhibit REE patterns with an obvious fractionation of the HREE from the LREE and MREE, which is an apparent function of degree of illitization reaction. The highly illitic (R greater than or equal to 3) illite-smectite from the northern Bowen Basin show a depletion of LREE relative to the less illitic (R=0 and 1) clays. In contrast, an enrichment of HREE for the illite-rich clays relative to less. illitic clays is evident for the southern Bowen Basin samples. The North American Shale Composite-normalized (La/Lu)(sn) ratios show negative correlations with the illite content in illite-smectite and positive correlations with the delta(18)O values of the clays for both the northern and southern Bowen Basin samples. These correlations indicate that the increasing depletion of LREE in hydrothermal fluids is a function of increasing water/rock ratios in the northern Bowen Basin. Good negative correlations between (La/Lu)(sn) ratios and illite content in illite-smectite from the southern Bowen Basin suggest the involvement of fluids with higher alkalinity and higher pH in low water/ rock ratio conditions. Increasing HREE enrichment with delta(18)O decrease indicates the effect of increasing temperature at low water/rock ratios in the southern Bowen Basin. Results of the present study confirm the conclusions of some earlier studies suggesting that REE in illitic clay minerals are mobile and fractionated during illitization and that this fact should be considered in studies of sedimentary processes and in identifying provenance. Moreover, our results show that REE systematic of illitic clay minerals can be applied as an useful technique to gain information about physico-chemical conditions during thermal and fluid flow events in certain sedimentary basins. (C) 2003 Elsevier Science B.V. All rights reserved.

(Table 2) Terrigenous, authigenic and biogenic composition of sediments at DSDP Hole 93-603B

Pelagic sedimentation during the Early Cretaceous at Site 603 produced alternations of laminated marly limestone and bioturbated limestone-a facies typical of the "Blake-Bahama Formation" of the western Atlantic. This limestone is a nannofossil micrite, rich in calcified radiolarians, with variable amounts of organic matter, pyritized radiolarian tests, fish debris, and micaceous silt. The laminated marly limestone layers are enriched in organic matter when compared with the intervals of bioturbated limestone. The organic carbon is predominantly terrestrial plant debris; where the organic-carbon content is in excess of 1%, there is also a significant marine-derived component. Laminations can result either from bands of alternately enriched and depleted opaque material and clay, or from bands of elongate lenses (microflasers) of micrite, which could be plastically deformed pellets or diagenetic features. The alternating intervals of laminated and bioturbated structures may have resulted from combined changes in surface productivity, in the influx of terrigenous organic matter, and in the intensity of bottom circulation, which led to episodic oxygen depletion in the bottom water and sediments. Variations in the relative proportions of laminated clay-rich and bioturbated lime-rich limestone and in the development of cycles between these structures make it possible to subdivide the Lower Cretaceous pelagic facies into several subunits which appear to be regional in extent. Bioturbated limestone is dominant in the Berriasian, laminated marly limestone in the Valanginian and Barremian-lower Aptian, and well-developed alternations between these end members in the Hauterivian. The Hauterivian to lower Aptian sediments contain abundant terrigenous clastic turbidites associated with a submarine fan complex. These changes in the general characteristics of the pelagic sediment component of the Blake-Bahama Formation at Site 603 are synchronous with those in the Blake-Bahama Basin (Sites 534 and 391) to the south. Carbonate sedimentation ended in the early Aptian, probably because of a regional shoaling of the carbonate compensation depth.

(Table 1) Peak intensity of minerals in ODP Hole 126-793B

Sediments and rocks recovered during Ocean Drilling Program Leg 126 at Sites 792 and 793 in the Izu-Bonin forearc basin are described with a primary focus on clay mineralogy. Evidence for diagenetic hydrothermal alteration processes is present in the upper Oligocene to lower Miocene sediments at these sites. The vitric and pumiceous sand/sandstone and pumiceous gravel contain high concentrations of smectites, zeolites, and gypsum. Microscopic observations show that the volcanic glass and feldspars have been altered to smectites and zeolites. The authigenic mineral assemblages indicate that these minerals resulted from precipitation from circulating fluids, as well as from the alteration of glass and feldspar under temperature conditions that may have reached 200°-300°C. Mineral assemblages in microfractures display thermal gradients that possibly reflect cooling effects.

Raman spectroscopy of the molybdate minerals chillagite (tungsteinian wulfenite-I4), stolzite, scheelite, wolframite and wulfenite

Raman spectra of chillagite, wulfenite, stolzite, scheelite and wolframite were obtained at 298 and 77 K using a Raman microprobe in combination with a thermal stage. Chillagite is a solid solution of wulfenite and stolzite. The spectra of these molybdate minerals are orientation dependent. The band at 695 cm-1 is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The bands at 790 and 881 cm-1 are associated with the antisymmetric and symmetric Ag modes of terminal WO2 whereas the origin of the 806 cm-1 band remains unclear. The 4(Eg) band was absent for scheelite. The bands at 353 and 401 cm-1 are assigned as either deformation modes or as r(Bg) and (Ag) modes of terminal WO2. The band at 462 cm-1 has an equivalent band in the infrared at 455 cm-1 assigned as as(Au) of the (W2O4)n chain. The band at 508 cm-1 is assigned as sym(Bg) of the (W2O4)n chain.