Nitrogen isotope, total organic carbon and element concentration data for piston core M77/2-024-5 from the Peruvian continental margin

Piston core M77/2-024-5 was retrieved during the M77/2 cruise of Research Vessel Meteor in December 2008. Total organic carbon concentrations were determined using a Carlo Erba Element Analyzer (NA1500). Prior to analysis carbon bound to carbonate minerals was removed by leaching the sediment with 1 M HCl. Bulk nitrogen isotope ratios were determined using a Carlo Erba Element Analyzer (NA1500) coupled to a DeltaPlusXL isotope ratio mass spectrometer. Major and trace metals were analyzed after microwave-assisted (CEM MARS-5) acid digestion (HCl, HNO3 and HF) by inductively coupled plasma optical emission spectrometry (aluminum, titanium and iron) (Teledyne Leeman Prodigy) and inductively coupled plasma mass spectrometry (molybdenum and uranium) (THERMO X-Series 2).

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Petrography, minerals and isotopic composition at DSDP Leg 66 Holes

We collected 20 carbonate nodules from the inner trench slope deposits of the Middle America Trench area off Mexico. Carbonate nodules are found only within the methane-rich layer beneath the mixed layer of methane and hydrogen sulfide. They have been investigated by microscopic, scanning electron microscopic (SEM), X-ray diffraction, and stable isotopic analytical methods. Calcite, magnesian calcite, dolomite, and rhodochrosite were recognized as carbonate minerals. Each carbonate nodule is usually represented by single species of carbonate minerals. Carbonate nodules are subdivided into micrite nodules and recrystallized nodules according to textural features. The carbonate crystallites in each micrite nodule are equidimensional. Their sizes range from several to 30 µm, as revealed by SEM micrographs. The chemical composition of calcite is changed from pure calcite to high magnesian calcite, as shown by the shift of the (104) reflection in X-ray diffraction patterns. Fe substitution for Ca in dolomite was also observed. Carbon isotopic composition shows an unusually wide range - from -42.9 to +13.5 per mil - in PDB scale, whereas oxygen isotopic compositions of almost all the carbonate nodules are constantly enriched in 18O from +3.4 to +7.60 per mil in PDB scale. These wide variations in carbon isotopic composition indicate several sources for the carbon in carbonate nodules. Carbon with a negative d13C value was derived from biochemical oxidation of methane with a negative d13C value. On the other hand, carbon with positive d13C value was probably formed during methane production in an anoxic condition.

Organic compounds at DSDP Hole 90-593

Corg and Norg contents in the acid insoluble mineral fraction were studied in sediments of Site 593. Both decrease systematically from Recent to early Miocene over 425 m of carbonate facies. C/N ratios (7-11) are typically marine and indicate that residual organic matter, bound to clay minerals, was originally scavenged from the marine habitat rather than being of terrigenous origin. Variations of Corg and Norg are almost entirely controlled by rates of sedimentation, which gradually increase from Recent to early Miocene. Preliminary results of carbohydrate distribution indicate that epigenetic and diagenetic processes alter both the concentrations and the ratios of individual monomers with depth. Total carbohydrate concentrations in the samples diminish from 91 µg/g sediment at 18 m sub-bottom depth to 49 µg/g at 335 m. In contrast, sugars in the acid insoluble residue increase with depth, suggesting release of structural polysaccharides and their subsequent association with clay minerals. Ratios of arabinose to fucose, which are about 6:1 in Recent carbonaceous sediments intercepted by sediment traps, vary from 1:1 in the youngest sample to 1:2.5 in the oldest.

Composition of rocks, minerals, water, and gases from uplift areas of the Central Atlantic

Original geological, geophysical, lithological, mineralogical data on uplifts of the Central Atlantic are given in the book based on materials of Cruise 1 of the R/V Akademik Nikolaj Strakhov. Geological and geophysical studies include description of the obtained material and analysis of structural and morphological elements of the ocean floor. Results of lithological, petrochemical and geochemical studies were extremely innovative and develop a conceptual model. The latter include studies of petrochemical evolution of tholeiitic alkaline plate volcanism, large-scale hydrothermal transformation of basement rocks - palygorskitization, phosphatization and ferromanganese mineralization. Showing imposition Superposition of hydrogenic alteration on hydrothermally altered rocks and its role in Cenozoic history of sedimentation is shown.

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.

Chemical and isotopic compositions of sediments and some minerals from the Derugin Basin, Sea of Okhotsk

The paper reports specific mineralogical and geochemical characteristics of deposits from local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for presence of hydrogen sulfide in bottom waters. Deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U), but have higher Mn contents.

Descriptions, isotopes and minerals of sediments at DSDP Leg 64 Holes

Mineralogical and oxygen isotopic analyses of samples from Deep Sea Drilling Project Sites 477, 481, and 477 in the Guaymas Basin indicate the existence of two distinct hydrothermal systems. In the first, at Sites 481 and 478, hot dolerite sills intruded into highly porous hemipelagic siliceous mudstones that were moderately rich in organic matter, thermally altered the adjacent sediments, and expelled hydrothermal pore fluids. The second, at Site 477 and active at present, is most probably caused by a recent igneous intrusion forming a magma chamber at shallow depth. In the first hydrothermal system, the main thermal reactions above and below the sills are dissolution of opal-A and formation of quartz, either directly or through opal-CT; formation of smectite; formation of analcime only above the sills; dissolution and recrystallization of calcite and occasional formation of dolomite or protodolomite. The d18O values of the hydrothermally altered sediments range from 9.9 to 12.2 per mil (SMOW). The d18O values of recrystallized calcites above the first sill complex, Site 481, indicate temperatures of 140° to 170°C. No fluid recharge is required in this system. The thickness of the sill complexes and the sequence and depth of intrusion into the sediment column determine the thickness of the alteration zones, which ranges from 2 or 3 to approximately 50 meters. Generally, the hydrothermally altered zone is thicker above than below the sill. In the second type, the sediments are extensively recrystallized. The characteristic greenschist-facies mineral assemblage of quartz-albite-chlorite-epidote predominates. Considerable amounts of pyrite, pyrrhotite, and sphene are also present. The lowest d18O value of the greenschist facies rocks is 6.6 per mil, and the highest d18O value of the associated pore fluids is +1.38 per mil (SMOW). The paragenesis and the oxygen isotopes of individual phases indicate alteration temperatures of 300 ± 50°C. On the basis of the oxygen isotopes of the solids and associated fluids, it is concluded that recharge of fluids is required. The water/rock ratio in wt.% is moderate, approximately 2/1 to 3/1 - higher than the calculated water/rock ratio of the hydrothermal system at the East Pacific Rise, 21 °N.

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.

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.