Mineralogy and chemistry of basalts and secondary minerals from DSDP Site 417, Atlantic Ocean

Basalts from DSDP Site 417 (109 Ma) exhibit the effects of several stages of alteration reflecting the evolution of seawater-derived solution compositions and control by the structure and permeability of the crust. Characteristic secondary mineral assemblages occur in often superimposed alteration zones within individual basalt fragments. By combining bulk rock and single phase chemical analyses with detailed mineralogic and petrographic studies, chemical changes have been determined for most of the alteration stages identified in the basalts. 1) Minor amounts of saponite, chlorite, and pyrite formed locally in coarse grained portions of massive units, possibly at high temperatures during initial cooling of the basalts. No chemical changes could be determined for this stage. 2) Possible mixing of cooled hydrothermal fluids with seawater resulted in the formation of celadonite-nontronite and Fe-hydroxide-rich black halos around cracks and pillow rims. Gains of K, Rb, H20, increase of Fe 3 +/FeT and possibly some losses of Ca and Mg occurred during this stage. 3a) Extensive circulation of oxygenated seawater resulted in the formation of various smectites, K-feldspar, and Fe-hydroxides in brown and light grey alteration zones around formerly exposed surfaces. K, Rb, H20, and occasionally P were added to the rocks, Fe3+/FeT increased, and Ca, Mg, Si and occasionally Al and Na were lost. 3 b) Anoxic alteration occurred during reaction of basalt with seawater at low water-rock ratios, or with seawater that had previously reacted with basalt. Saponite-rich dark grey alteration zones formed which exhibit very little chemical change: generally only slight increases in Fe 3 +/FeT and H20 occurred. 4) Zeolites and calcite formed from seawater-derived fluids modified by previous reactions with basalt. Chemical changes involved increases of Ca, Na, H20 , and CO2 in the rocks. 5) A late stage of anoxic conditions resulted in the formation of minor amounts of Mn-calcites and secondary sulfides in previously oxidized rocks. No chemical changes were determined for this stage. Recognition of such alteration sequences is important in understanding the evolution of submarine hydrothermal systems and in interpreting chemical exchange due to seawater-basalt reactions.

Chemical composition of siderites and clay minerals from DSDP Holes 70-506G and 70-507B

As soon as they are emplaced on the sea floor, oceanic basalts go through a low-temperature alteration process which produces black halos concentrical with exposed surfaces and cracks, whereas the grey internal parts of the basaltic pieces apparently remain unaltered. This paper reports for the first time the occurrence of authigenic siderite and ankerite in oceanic basalts and more particularly in the grey internal parts of the latter. Small (8-50 µm) crystals of zoned siderite and ankerite have been observed in ten vesicles of two samples recovered from DSDP Holes 506G and 507B drilled south of the Galápagos Spreading Center (GSC). These Fe-carbonates show a large range of chemical composition (FeCO3 = 47-88%; CaCO3 = 5-40%; MgCO3 = 1-20%; MnCO3 = 0-11%). Most of them are Ca-richer than siderite reported in the literature. The chemical composition of the carbonate clearly reflects the fluctuation of the fluid chemical composition during crystallization. Mn and at least part of the Fe are thought to be hydrothermal in origin, whereas Mg and probably Ca were provided by seawater. It is proposed that siderite and ankerite formed at relatively low temperature (<85°C) and is metastable. The alteration of the GSC basalts seems to have proceeded in two stages: during the first, reducing stage, pyrite precipitated from hydrothermal fluids. A little further in the rock, siderite precipitated from the fluid which had already been modified by the formation of pyrite, and thus in a microenvironment where particular conditions prevailed (high P_CO2, increasing p_S**2- or increasing pH or increasing or decreasing pe). During the second, oxidizing, stage of alteration, a seawater-dominated fluid allowed crystallization of mixtures of Fe-rich smectites and micas, and Fe-hydroxides forming the black halos in the external portion of the basalt pieces and locally oxidizing pyrite and siderite in their innermost part. It is shown in this paper that, even at its earliest stage, and at low temperature, alteration of the upper oceanic crust (lavas) involves fluids enriched in Fe and Mn, interpreted to be of hydrothermal origin.

Foraminiferal assemblages and stable isotopes across the early Paleogene carbonate facies of Perth Abyssal Plain off Western Australia

Bulk carbonate content, planktic and benthic foraminiferal assemblages, stable isotope compositions of bulk carbonate and Nuttallides truempyi (benthic foraminifera), and non-carbonate mineralogy were examined across ~30 m of carbonate-rich Paleogene sediment at Deep Sea Drilling Project (DSDP) Site 259, on Perth Abyssal Plain off Western Australia. Carbonate content, mostly reflecting nannofossil abundance, ranges from 3 to 80% and generally exceeds 50% between 35 and 57 mbsf. A clay-rich horizon with a carbonate content of about 37% occurs between 55.17 and 55.37 mbsf. The carbonate-rich interval spans planktic foraminiferal zones P4c to P6b (~57-52 Ma), with the clay-rich horizon near the base of our Zone P5 (upper)-P6b. Throughout the studied interval, benthic species dominate foraminiferal assemblages, with scarce planktic foraminifera usually of poor preservation and limited species diversity. A prominent Benthic Foraminiferal Extinction Event (BFEE) occurs across the clay-rich horizon, with an influx of large Acarinina immediately above. The delta13C records of bulk carbonate and N. truempyi exhibit trends similar to those observed in upper Paleocene-lower Eocene (~57-52 Ma) sediment from other locations. Two successive decreases in bulk carbonate and N. truempyi delta13C of 0.5 and 1.0? characterize the interval at and immediately above the BFEE. Despite major changes in carbonate content, foraminiferal assemblages and carbon isotopes, the mineralogy of the non-carbonate fraction consistently comprises expanding clay, heulandite (zeolite), quartz, feldspar (sodic or calcic), minor mica, and pyrolusite (MnO2). The uniformity of this mineral assemblage suggests that Site 259 received similar non-carbonate sediment before, during and after pelagic carbonate deposition. The carbonate plug at Site 259 probably represents a drop in the CCD from ~57 to 52-51 Ma, as also recognized at other locations.

Geochemistry and minerals at DSDP Hole 70-504B

In three veins from the lower part of Deep Sea Drilling Project Hole 504B, 298 meters below the top of basement, primary augite is replaced by aegirine-augite. This transformation occurs only in subophitic basalts, at the contact with veins which always include a dark-olive, Mg-rich clay mineral. Talc occurs in one of these veins; it can be regarded either as a vein constituent or as a product of augite alteration. Melanite (Ca,Fe,Ti-rich garnet) appears in only one of these three veins, where a Ca-carbonate is associated with a Mg-rich clay mineral. The occurrence of melanite in Hole 504B could be due to the conjunction of particular conditions: (1) basalt with a subophitic texture, (2) presence of hydrothermal fluids carrying Ca, Fe, Si, Ti, Al, Mg, and Na, (3) rather high temperatures. Possibly the melanite and aegirine-augite formed by deuteric alteration.

Geochemistry and minerals at DSDP Hole 76-534A

Leg 76 sampled 31.5 m of basaltic basement at Deep Sea Drilling Project Hole 534A in the Blake-Bahama Basin. The basalts represent a short section of mineralogically uniform, sparsely plagioclase-phyric pillow flows, composed mainly of plagioclase, augitic clinopyroxene, iron-titanium oxides with variable amounts of alteration products (smectite ± carbonate ± quartz). Their major element chemistry is typical of mid-ocean ridge tholeiites and has normative compositions of olivine tholeiites. Mg/(Mg + Fe**2+) ratios range from 0.58 to 0.60, which suggests that these basalts are evolved compared to primitive mantle melts.

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.

Physical properties and bulk minerals from IODP Holes 308-U1322B, U1322D and U1324B

How the micro-scale fabric of clay-rich mudstone evolves during consolidation in early burial is critical to how they are interpreted in the deeper portions of sedimentary basins. Core samples from the Integrated Ocean Drilling Program Expedition 308, Ursa Basin, Gulf of Mexico, covering seafloor to 600 meters below sea floor (mbsf) are ideal for studying the micro-scale fabric of mudstones. Mudstones of consistent composition and grain size decrease in porosity from 80% at the seafloor to 37% at 600 mbsf. Argon-ion milling produces flat surfaces to image this pore evolution over a vertical effective stress range of 0.25 (71 mbsf) to 4.05 MPa (597 mbsf). With increasing burial, pores become elongated, mean pore size decreases, and there is preferential loss of the largest pores. There is a small increase in clay mineral preferred orientation as recorded by high resolution X-ray goniometry with burial.

Major elements oxides and mineralogy of primary minerals in ODP Hole 195-1201D basalts

The basement cored at Site 1201 (west Philippine Basin) during Ocean Drilling Program Leg 195 consists of a 91-m-thick sequence of basalts, mostly pillow lavas and perhaps one sheet lava flow, with a few intercalations of hyaloclastite and interpillow sedimentary material. Hydrothermal alteration pervasively affected the basalt sequence, giving rise to a variety of secondary minerals such as K-Fe-Mg-clay minerals, oxyhydroxides and clay minerals mixtures, natrolite group zeolites, analcite, alkali feldspar, and carbonate. The primary minerals of pillow and sheet basalts that survived the intense hydrothermal alteration were investigated by electron microprobe with the aim of characterizing their chemical composition and variability. The primary minerals are mostly plagioclase, ranging in composition from bytownite through labradorite to andesine, chromian-magnesian-diopside, and spinels, both Ti magnetite (partially maghemitized) and chromian spinel. Overall, the chemical features of the primary minerals of Site 1201 basalts correspond to the primitive character of the bulk rocks, suggesting that the parent magma of these basalts was a mafic tholeiitic magma that most likely only suffered limited fractional crystallization and crystallized at high temperatures (slightly below 1200°C) and under increasing fO2 conditions. The major element composition of clinopyroxene suggests a backarc affinity of the mantle source of Site 1201 basement.

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.

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.

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.

Seawater carbonate chemistry and larval growth response of the Portuguese oyster (Crassostrea angulata) in a laboratory experiment

Rising anthropogenic carbon dioxide (CO2) dissolving into coastal waters is decreasing the pH and carbonate ion concentration, thereby lowering the saturation state of calcium carbonate (CaCO3) minerals through a process named ocean acidification (OA). The unprecedented threats posed by such low pH on calcifying larvae of several edible oyster species have not yet been fully explored. Effects of low pH (7.9, 7.6, 7.4) on the early growth phase of Portuguese oyster (Crassostrea angulata) veliger larvae was examined at ambient salinity (34 ppt) and the low-salinity (27 ppt) treatment. Additionally, the combined effect of pH (8.1, 7.6), salinity (24 and 34 ppt) and temperature (24 °C and 30 °C) was examined using factorial experimental design. Surprisingly, the early growth phase from hatching to 5-day-old veliger stage showed high tolerance to pH 7.9 and pH 7.6 at both 34 ppt and 27 ppt. Larval shell area was significantly smaller at pH 7.4 only in low-salinity. In the 3-factor experiment, shell area was affected by salinity and the interaction between salinity and temperature but not by other combinations. Larvae produced the largest shell at the elevated temperature in low-salinity, regardless of pH. Thus the growth of the Portuguese oyster larvae appears to be robust to near-future pH level (> 7.6) when combined with projected elevated temperature and low-salinity in the coastal aquaculture zones of South China Sea.