Chemistry of primary and secondary phases in intraplate basalts and volcaniclastic sediments at DSDP Leg 89 Holes

Electron microprobe data are presented for clinopyroxenes, plagioclases, palagonites, smectites, celadonites, and zeolites in Hole 462A sheet-flow basalts and Site 585 volcaniclastic sediments. Glomerocrystic clinopyroxenes in Hole 462A are predominantly Ti-poor augites with minor fractionation to ferroaugites in rim portions. Quenched plumose clinopyroxenes show considerable variation from Ca-rich to Ca-poor augites, although all are characterized by being Tirich and Cr-poor relative to the glomerocrysts. Two differentiated series of Site 585 pyroxene compositions, calcic augite and diopside-salite, demonstrate the coexistence, in the vitric and lithic clasts, of tholeiitic and alkali basalt types, respectively. Plagioclase compositions in all samples are mainly labradorites, although some zoned Hole 462A glomerocrysts range from An73 to An20 and are characterized by high Mg and Fe contents in the more calcic varieties. The K content of the plagioclases is highest in the more sodic crystals, although the overall higher orthoclase component of Site 585 plagioclases reflects the generally higher bulk-rock K content. The compositions of both secondary smectites and celadonites are similar irrespective of the alteration location (glass, matrix, vesicles, etc.), although brown smectites replacing interstitial glass have marginally higher total Fe contents than pale green and yellow smectites. Analyzed zeolites are mainly phillipsites with variable alkali content, and, together with associated celadonite, represent late-stage alteration repositories for K under mildly oxidizing conditions. The compositions of both early and late secondary minerals are typical of those formed by the submarine alteration of basaltic rocks at low temperatures.

Chemical and mineral compositions of Northwest Pacific bottom sediments and their grain size fractions

A detailed study of chemical composition of bottom sediments along a profile through the Northwest Pacific Basin has allowed to identify and describe four lithofacies types of bottom sediments. Distinguished types of sediments form a genetic series reflecting changing conditions of sedimentation from near-shore to central regions of the ocean. Along the strike of pelagic clays a gradual transition from ash containing clays to zeolite containing clays is established. Ash particles and zeolites have similar forms of occurrence. Together with other data it suggests that zeolites have been formed by diagenetic transformation of rhyolitic glass. Regular changes of CaCO3, amorphous SiO2, Fe and Mn contents in bottom sediments from the coast to the pelagic zone are shown.

Chemical composition of Fe-Mn ores from the North Pacific seamounts

Ore crusts from the Mid-Pacific Seamounts were studied by scanning electron microscopy and by atomic-absorption and chemical analysis. Characteristic ultramicroscopic structures of ore material of these crusts are globular, fibrous, conchoidal and cellular. Non-ore components are represented by fragments of bedrocks, zeolites, biogenic carbonates, and apatite. Contents of ore elements are: Fe 5.53-15.82%; Mn 14.92-23.45%; Co 0.32-0.82%; Ni 0.22-0.70%; Cu 0.02-0.12%, Mn/Fe ratio varies from 1.02 to 3.39. In general elevated contents of Co (>0.55%) in Fe-Mn crusts correspond to elevated (>1) Mn/Fe ratios.

Ash layers, hyaloclastite, and alteration of basaltic glass at DSDP Leg 65 Holes

Three types of tephra deposits were recovered on Leg 65 of the Deep Sea Drilling Project (DSDP) from three drill sites at the mouth of the Gulf of California: (1) a series of white ash layers at Sites 483, 484, and 485; (2) a layer of plagioclase- phyric sideromelane shards at Site 483; and (3) an indurated, cross-bedded hyaloclastite in Hole 483B. The ash layers in (1) are composed of colorless, fresh rhyolitic glass shards with minor dacitic and rare basaltic shards. These are thought to be derived from explosive volcanoes on the Mexican mainland. Most of the shards in (2) are fresh, but some show marginal to complete alteration to palagonite. The composition of the glass is that of a MORB-type tholeiite, low in Fe and moderately high in Ti, and possibly erupted from off-axis seamounts. Basaltic glass shards occurring in silt about 45 meters above the basement at Site 484 A in the Tamayo Fracture Zone show a distinctly alkalic composition similar to that of the single basement basalt specimen drilled at this site. The hyaloclastite in (3) is made up chiefly of angular sideromelane shards altered to smectite and zeolites (mainly phillipsite) and minor admixtures of terrigenous silt. A very high K and Ba content indicates significant uptake of at least these elements from seawater. Nevertheless, the unusual chemical composition of the underlying massive basalt flow is believed to be reflected in that of the hyaloclastite. This is a powerful argument for interpreting the massive basalt as a surface flow rather than an intrusion. Glass alteration is different in the glassy margins of flows than in thicker glassy pillow rinds. Also, it appears to proceed faster in coarse- than fine-grained sediments.

Semiquantitative occurence of various minerals in sediment core CRP-2A

The mineralogy of the lower Oligocene to Quaternary sediments of core CRP-2/2A drilled on the continental shelf of McMurdo Sound in Ross Sea, Antarctica, was examined by the X-ray diffraction method. Quartz, plagioclase feldspar and K-feldspar are the most important non-clay minerals. Pyroxene and amphibole occur in minor amounts throughout the core. The composition of the sediments points to an origin in the Transantarctic Mountains for the majority of the detrital components. There, the plutonic and metamorphic rocks of the basement, the sediments of the Beacon Supergroup and the volcanic rocks of the Ferrar Group could serve as possible source lithologies. The distribution of the detrital minerals reflects a long-term history of successive erosion and valley incision. During the deposition of the lower part of the core, the detrital minerals were probably mainly derived from the sediments of the Beacon Supergroup, as indicated by the high quartz but relatively low feldspar abundances. In the upper c. 350 m of the core, the influence of a source in the basement became stronger and results in lower quartz contents but increasing abundance of feldspar. Some diagenetic alteration of the sediments is indicated by the occurrence of zeolites below c. 320 mbsf and of opal-CT above c. 320 mbsf.

Geochemistry and stable isotope record of the hydtrothermally altered lower sheeted dike complex in ODP Hole 140-504B

Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18O depletions of the lower dikes (d18O = 3.6-5.0 per mil) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated d34S values of sulfide in the rocks (up to 2.5 per mil). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (d18O = 1 per mil). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18O enrichments, but these were insufficient to offset the 18O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in d34S values of total S in the rocks (up to 12 per mil). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.

Clay mineral distribution in sediment core AND-2A

Clay mineral assemblages in sediments from ANDRILL drill core AND-2A were used to reconstruct the Neogene palaeoenvironment. For the first time a clay mineral data set can be presented for southern McMurdo Sound, Ross Sea, Antarctica, that covers an expanded and fairly continuous Lower and Middle Miocene section. Although the occurrence of some authigenic smectites, zeolites and opal-CT documents diagenetic processes, the clay mineral assemblages allow a subdivision of the core into three intervals that reflect changes in provenance and volcanic activity. Interval I (1000-440 mbsf, 20.0-16.5 Ma) is characterised by a dominant sediment source in the Transantarctic Mountains. Frequent and short-term changes in the illite and smectite concentrations were caused by the influx of volcanic sediment components from southern McMurdo Sound and by diagenesis. Interval II (440-225 mbsf, 16.5-15.0 Ma) has much more uniform illite and smectite contents. The assemblage is derived from the Transantarctic Mountains. Interval III (225-0 mbsf, 15.0-0 Ma, containing major hiatuses) shows a distinctly enhanced volcanic influence and sediment components that come from the south of McMurdo Sound. The AND-2A clay mineral assemblages indicate persistent physical weathering conditions and do not mirror the Mid-Miocene Climatic Optimum. They indicate that the climatic changes were probably not strong enough to cause a modification in the weathering regime on the Antarctic continent.

(Table 1) Chemical composition of phillipsites from pelagic bottom sediments of the Transpacific profile

Results of petrographic, chemical and X-ray studies of zeolites in sediments in the Transpacific lithological profile from the coast of Japan to the coast of Mexico are reported. For ocean phillipsites constancy of Si/Al ratio (2.44-2.87) and unstable cation composition in quantitative predominance of potassium over sodium are characteristic. Two groups of ocean phillipsites are distinguished: of deep-water basins and of submarine rises. The first spread over broad areas of the pelagic zone, and are formed by diagenetic transformation of fine dispersed pyroclastic material in minimum sedimentation rates, the latter occur locally - in areas of basaltic volcanism manifestations.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

(Table 1) Pore-water composition of ODP Leg 126 sites

The Ocean Drilling Program Leg 126 sites may be classified into two categories depending on the presence (Group I: Sites 787, 792, and 793) or absence (Group II: Sites 788, 790, and 791) of steep concentration gradients. Shipboard X-ray diffraction analyses of bulk sediments from Group I sites revealed the presence of a number of diagenetic minerals (some of which are incompatible), but no systematic diagenetic zonation. The results of the chemical analyses of the pore waters from Group I have been used to estimate the activities of dissolved species. Thermodynamic analyses of the composition of the pore waters and the stability of authigenic minerals (gypsum, zeolites, feldspars, smectites, chlorites, and micas) show that the pore waters are close to equilibrium with most of the observed phases. Thus, only a small perturbation of the system (substitution in minerals and fluctuations in pore-water composition, in particular, in pH and SiO2 activity) will cause any of these phases to precipitate. Therefore, one would not expect mineralogical observations to show systematic vertical zonations at these sites. It is suggested that chlorites and high-temperature zeolites are not diagenetic sensu stricto, but were eroded from volcaniclastic highs. The absence of concentration gradients at the Group II sites has been analyzed in terms of reaction kinetics, hydrothermal advection, and temperature distribution. The absence of diagenetic imprints on the pore-water concentration profiles at these sites is probably caused by the slow nucleation of silica phases.

(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.

Geochemistry of sheeted dike complex minerals of ODP Hole 140-504B

Diabases were recovered during Legs 137 and 140 at Hole 504B from depths between 1621.5 and 2000.4 meters below seafloor in the lower sheeted dike complex. The samples contain multiple generations of millimetric to centimetric veins. The orientation of the measured veins suggests that two main vein sets exist: one characterized by shallow dipping and the other by random trend. Thermal contraction during rock cooling is considered the main mechanism responsible for fracture formation. Vein infill is related to the circulation of hydrothermal fluids near the spreading axis. Some veins are surrounded by millimeter-sized alteration halos due to fluid percolation from the fractures through the host rock. Vein-filling minerals are essentially amphibole, chlorite, and zeolites. Amphibole composition is controlled by the microstructural site of the rock. Actinolite is the main amphibole occurring in the veins and also in the groundmass away from the halos. In the alteration halos, amphibole shows composition of actinolitic hornblende and Mg-hornblende. Late-stage tension gashes and interstitial spaces in some amphibole-bearing veins are filled with zeolites, suggesting that the veins likely suffered multiple opening stages that record the cooling history of the circulating fluids. Evidence of deformation recorded by the recovered samples seems to be restricted to veins that clearly represent elements of weakness of the rock. On the basis of vein geometry and microstructure we infer structural interpretations for the formation mechanism and for deformation of veins.