Geochemistry of the oceanic crust from ocean drilling samples

This book presents new data on chemical and mineral compositions and on density of altered and fresh igneous rocks from key DSDP and ODP holes drilled on the following main tectonomagmatic structures of the ocean floor: 1. Mid-ocean ridges and abyssal plains and basins (DSDP Legs 37, 61, 63, 64, 65, 69, 70, 83, and 91 and ODP Legs 106, 111, 123, 129, 137, 139, 140, 148, and 169); 2. Seamounts and guyots (DSDP Legs 19, 55, and 62 and ODP Legs 143 and 144); 3. Intraplate rises (DSDP Legs 26, 33, 51, 52, 53, 72, and 74 and ODP Legs 104, 115, 120, 121, and 183); and 4. Marginal seas (DSDP Legs 19, 59, and 60 and ODP Legs 124, 125, 126, 127, 128, and 135). Study results of altered gabbro from the Southwest Indian Ridge (ODP Leg 118) and serpentinized ultramafic rocks from the Galicia margin (ODP Leg 103) are also presented. Samples were collected by the authors from the DSDP/ODP repositories, as well as during some Glomar Challenger and JOIDES Resolution legs. The book also includes descriptions of thin sections, geochemical diagrams, data on secondary mineral assemblages, and recalculated results of chemical analyses with corrections for rock density. Atomic content of each element can be quantified in grams per standard volume (g/1000 cm**3). The suite of results can be used to estimate mass balance, but parts of the data need additional work, which depends on locating fresh analogs of altered rocks studied here. Results of quantitative estimation of element mobility in recovered sections of the upper oceanic crust as a whole are shown for certain cases: Hole 504B (Costa Rica Rift) and Holes 856H, 857C, and 857D (Middle Valley, Juan de Fuca Ridge).

Insoluble residues of the fine-grained sediments from DSDP Leg 67 Holes

Insoluble residues of Late Cretaceous to Quaternary deep-sea samples from slope, trench, and oceanic plate sites south of Guatemala were examined, specifically for the distribution of clay minerals in the <2-µm fraction and of silt grains in the 20-63-µm fraction. Widespread "oceanic" particles (biogenic opal, rhyolitic glass) and their diagenetic products (smectite, clinoptilolite, heulandite) were distinguished from terrigenous material - illite, kaolinite, chlorite, plagioclase, quartz, and heavy minerals. The main results of this investigation are: (1) At Site 494 on the slope immediately adjacent to the trench, terrigenous supplies testify to a slope position of the whole sequence back to the Late Cretaceous. (2) At Site 495 on the Pacific Cocos Plate, "oceanic" and terrigenous sedimentation are clearly separated. Whereas the pelagic sedimentation prevailed in the early Miocene, terrigenous minerals appeared in the middle Miocene in the clay fraction, and in the early Pliocene in the coarse silt fraction. These terrigenous supplies are interpreted as having been transported by suspension clouds crossing the slope and even the trench. The alternative, however, an eolian transport, cannot be excluded.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Mineralogy and geochemistry of weathered serpentinites in DSDP Leg 84 sediments

At Sites 566, 567, and 570 of Leg 84, ophiolitic serpentinite basement was covered by a sequence of serpentinitic mud that was formed by weathering of the serpentinites under sea- or pore-water conditions. Several mineralogical processes were observed: (1) The serpentinitic mud that consists mainly of chrysotile was formed from the lizardite component of the serpentinites by alteration. (2) Slightly trioctahedral smectites containing nonexpandable mica layers, trioctahedral smectites containing nonexpandable chlorite layers, and swelling chlorites were presumably formed from detrital chlorite and/or serpentine. (3) The occurrence of tremolite, chlorite, analcime, and talc can be attributed to reworking of gabbroic ophiolite rocks. (4) Dolomite, aragonite, and Mg-calcite, all authigenic, occur in the serpentinitic mud.

Sedimentary facies, clay mineralogy and geochemistry of the Paleogene sediments of ODP Site 105-647

Claystones immediately overlying the early Eocene age ocean-floor basalt, cored at Ocean Drilling Program (ODP) Site 647, underwent hydrothermal and thermal alterations originating from the basalt, which resulted in changes in both the mineralogical and chemical composition of the sediments. Chlorites and higher magnesium and iron concentrations were found in the lowermost sediment sequence. Upcore, changes in the bulk chemical composition of the sediments become smaller, when compensated for variations in the carbonate content originating from biogenic and authigenic components. Chlorite disappears upcore, but still only part of the swelling clay minerals have survived the thermal influence. Thirty meters above the basalt, the clay mineralogy and chemical composition become uniform throughout the Paleogene section. Iron-rich smectites (i.e., nontronitic types), totally dominate the clay mineral assemblage. Biogenic components, responsible for the dominant part of the calcite and cristobalite contents, vary in amount in the upper part, and so do the authigenic carbonate and sulfide contents. Detrital components, such as kaolinite, illite, quartz, and feldspars, make up a very small proportion of the sediment record. The nontronitic smectites are believed to be authigenic, formed by a supply of iron from the continuous formation of ocean-floor basalt in the ridge area that reacted with the detrital and biogenic silicates and alumina silicates.

Chemical and mineral compositions of basalts from the Pacific Ocean, DSDP data

Mineral and chemical alterations of basalts were studied in the upper part of the ocean crust using data of deep-sea drilling from D/S Glomar Challenger in the main structures of the Pacific floor. Extraction of majority of chemical elements (including heavy metals) from basalts results mainly from their interaction with heated sea water. As a result mineralized hydrothermal solutions are formed. On entering the ocean they influence greatly on ocean sedimentation and ore formation.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Seawater carbonate chemistry, the abiotic conditions in the fluid surrounding the embryo, growth, calcification of the cuttlefish Sepia officinalis in a laboratory experiment

This study investigated the effects of seawater pH (i.e., 8.10, 7.85 and 7.60) and temperature (16 and 19 °C) on (a) the abiotic conditions in the fluid surrounding the embryo (viz. the perivitelline fluid), (b) growth, development and (c) cuttlebone calcification of embryonic and juvenile stages of the cephalopod Sepia officinalis. Egg swelling increased in response to acidification or warming, leading to an increase in egg surface while the interactive effects suggested a limited plasticity of the swelling modulation. Embryos experienced elevated pCO2 conditions in the perivitelline fluid (>3-fold higher pCO2 than that of ambient seawater), rendering the medium under-saturated even under ambient conditions. The growth of both embryos and juveniles was unaffected by pH, whereas 45Ca incorporation in cuttlebone increased significantly with decreasing pH at both temperatures. This phenomenon of hypercalcification is limited to only a number of animals but does not guarantee functional performance and calls for better mechanistic understanding of calcification processes.

Chemical composition of soils and rocks from King George Island

Both the olivine-hearing tholeiite basalts of the island and the brown soils which have developed on the basalts contain 2-20% of a swelling clay mineral. It emerges from chemical, optical, X-ray diffraction and differential thermal analytical studies that this clay mineral is a Mg-rich, Fe2+ and AI-bearing tri-octahedral smectite, e. g. Mg-saponite. Due to petrographic and crystal chemical properties the saponite should have been formed by hydrothermal alteration of the primary Mg-Fe-minerals olivine and clinopyroxene. The soils consist of plagioclase, saponite and goethite which has been formed by chemical weathering within the soils. In the uppermost layer some of the soils contain humic substances and phosphatic material, the latter may be related to the recent production of guano.

Clay mineralogy of carbonate-rich sediments of ODP Leg 101 sites

The insoluble residues of samples from ODP Sites 626 and 627 can be subdivided into four groups: (1) illite, 7 A minerals, quartz and feldspar; (2) smectite and zeolite (clinoptilolite); (3) palygorskite and in places sepiolite; and (4) glauconite and pyrite. Whereas group 1 is clearly terrigenous and group 4 authigenic, group 2 is most probably authigenic, as indicated by its abundance in samples with small insoluble residues and its appearance in SEM photographs. Group 3 is authigenic in Albian peritidal dolomite and possibly terrigenous in middle Miocene slumps and debris flows. Smectite crystallinity increases with age. This increase, however, is less pronounced in the Bahamian carbonate-rich samples than in the carbonate-poor silts south of Guatemala (DSDP Leg 84, Sites 569 and 570, the only comparable investigation) as far as can be judged from such a small number of samples.

(Table 2) Petrophysical, petrological, and geochemical characteristics of ODP Hole 163-990A sediments

Ocean Drilling Program Hole 990A penetrated 131 m of subaerially emplaced Paleocene flood basalts on the Southeast Greenland margin with a recovery of 74%. Shipboard P-wave velocity (Vp), density, and magnetic susceptibility were measured with 2- to 15-cm intervals on the core. Individual flow units were divided into four zones based on the observed petrophysical characteristics. From the top, these are Zone I (<7 m thick with a Vp of ~2.5 km/s), Zone II (3-5 m thick with a strongly increasing Vp from 2.5 to 5.5 km/s), Zone III (up to 20 m thick with a Vp of ~5.5-6.0 km/s), and Zone IV (<2 m thick with a strongly decreasing Vp from 6.0 to 2.5 km/s). Eighteen samples were selected from three of the fourteen penetrated basalt units for geochemical, petrological, and petrophysical studies focusing on the altered, low-velocity upper lava Zones I and II. Zone I is strongly altered to >50% clay minerals (smectite) and iron hydroxides, and the petrophysical properties are primarily determined by the clay properties. Zone II is intermediately altered with 5%-20% clay minerals, where the petrophysical properties are a function of both the degree of alteration and porosity variations. Shipboard and shore-based measurements of the same samples show that storage permanently lowers the elastic moduli of basalt from Zones I to III. This is related to the presence of even small quantities of swelling clays. The data show that alteration processes are important in determining the overall seismic properties of flood basalt constructions. The degree and depth of alteration is dependent on the primary lava flow emplacement structures and environment. Thus, the interplay of primary emplacement and secondary alteration structures determine the elastic properties of basalt piles. Rock property theories for sand-clay systems are further used to model the physical property variations in these altered crystalline rocks.

Seawater carbonate chemistry and trace element accumulation during experiments with common cuttlefish, Sepia officinalis, 2009

Cephalopods play a key role in many marine trophic networks and constitute alternative fisheries resources, especially given the ongoing decline in finfish stocks. Along the European coast, the eggs of the cuttlefish Sepia officinalis are characterized by an increasing permeability of the eggshell during development, which leads to selective accumulation of essential and non-essential elements in the embryo. Temperature and pH are two critical factors that affect the metabolism of marine organisms in the coastal shallow waters. In this study, we investigated the effects of pH and temperature through a crossed (3?2; pH 8.1 (pCO2, 400 ppm), 7.85 (900 ppm) and 7.6 (1400 ppm) at 16 and 19°C, respectively) laboratory experiment. Seawater pH showed a strong effect on the egg weight and non-significant impact on the weight of hatchlings at the end of development implying an egg swelling process and embryo growth disturbances. The lower the seawater pH, the more 110 mAg was accumulated in the tissues of hatchlings. The 109Cd concentration factor (CF) decreased with decreasing pH and 65Zn CF reached maximal values pH 7.85, independently of temperature. Our results suggest that pH and temperature affected both the permeability properties of the eggshell and embryonic metabolism. To the best of our knowledge, this is one of the first studies on the consequences of ocean acidification and ocean warming on metal uptake in marine organisms, and our results indicate the need to further evaluate the likely ecotoxicological impact of the global change on the early-life stages of the cuttlefish.