Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.

Characteristics and distribution of Neogene turbidites at ODP Site 108-657

Numerous and variable silty-sandy siliciclastic turbidites were observed in Neogene pelagic sediments (late Miocene to Holocene) at Site 657: (1) thick-bedded, coarse-grained and thin-bedded, fine-grained turbidites; and (2) turbidites composed of eolian dune sand and shallow-water bioclasts or of fluvial-sand or mixed sandy component assemblages. The stratigraphic distribution of these turbidites indicates five periods during which climatic conditions and material sources change. Turbidite occurrence prior to 6.2 Ma (late Miocene) is sparse; the deposits contain coarse and fine-grained turbidites with quartz grains of eolian or mixed origin suggesting the existence of arid conditions at about 8.5 and 6.5 Ma. A coarse-grained turbidite of fluvial origin, recording a humid climate, occurs at about 6.2 Ma. During the early Pliocene, turbidites are frequent (15/Ma); they contain only fine-grained sequences comprising material of mixed origin, which indicates a more humid climate perhaps. The late Pliocene starts with rare coarse-grained turbidites of wind-transported sand while the uppermost Pliocene deposits show a higher frequency of fine-grained sequences (10/0.7 Ma) composed mainly of fluvial material. During the early Pleistocene, similar high turbidite frequency was observed (20/1.3 Ma) but with a total lack of eolian supply. During the last 0.7 Ma, the frequency decreases and the sequences are characterized by highly variable sediment components that could be related to strong variations of climatic conditions. The sedimentary characteristics of turbidites are mainly controlled by sediment source and climate. The frequency must be influenced by sea-level variations, by cyclic processes of climatic origin, and possibly by variations in the continental slope morphology. Clay mineral assemblages suggest a south Saharan source of terrigenous material during the late Miocene and the Pliocene and a northwest Saharan source during the Pleistocene.

Mineralogy and petrographic summary of ODP Leg 198 sites and DSDP Hole 62-463, Shatsky Rise

This petrological study of the lower Aptian Oceanic Anoxic Event (OAE1a) focused on the nature of the organic-rich interval as well as the tuffaceous units above and below it. The volcaniclastic debris deposited just prior to the OAE1a is consistent with reactivation of volcanic centers across the Shatsky Rise, concurrent with volcanism on the Ontong Java Plateau. This reactivation may have been responsible for the sub-OAE1a unconformity. Soon after this volcanic pulse, anomalous amounts of organic matter accumulated on the rise, forming a black shale horizon. The complex textures in the organic-rich intervals suggest a history of periodic anoxia, overprinted by bioturbation. Components include pellets, radiolarians, and fish debris. The presence of carbonate-cemented radiolarite under the OAE1a intervals suggests that there has been large-scale remobilization of carbonate in the system, which in turn may explain the absence of calcareous microfossils in the section. The volcanic debris in the overlying tuffaceous interval differs in that it is significantly epiclastic and glauconitic. It was likely derived from an emergent volcanic edifice.

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.

Physical properties of four profiles from the Triassic in Germany

The Norian Steinmergel-Keuper (SMK) represents a low-latitude cyclically-bedded playa system of the Mid-German Basin. We investigated a drilling site (core Morsleben) and sections from marginal positions. Dolomite/red mudstone beds form rhythmic alternations that were associated with varying monsoon activity. Hence, low K/Al ratios of dolomite beds suggest increased chemical weathering of the crystalline hinterland and therefore increased monsoonal rainfall. High K/Al ratios in red mudstone beds reflect increased physical weathering of the hinterlands during dryer periods. Dolomite layers reflect the lake stage (maximum monsoon) while red mudstones indicate the dry phase (minimum monsoon) of the playa cycle. We distinguished five major types of cyclic facies alternations, representing specific facies zones in the playa system. We have implemented spectrophotometry as a tool for high-resolution cyclostratigraphy. The dense sampling increment (up to 1 cm) allows for the recognition of all orbital frequencies. Sediment colour profiles reveal striking hierarchical cycles from semi-precession (SP, 99 kyr) over precession (P, 19.8 kyr) and obliquity (O, 36 kyr) to eccentricity (E1-2 109 kyr; E3, 413 kyr). A significant about 2 Myr-signal is attributed to the longer-term eccentricity E4. One monsoonal (precession) cycle includes two carbonate precipitation events. We propose that stratified mudstone and red mudstone are associated with maximum and minimum monsoon during the transition of the solstices in perihelion and aphelion, respectively. The two carbonate precipitation events were most likely created when equinoxes were in perihelion and aphelion, respectively. A sedimentary semi-precession response cycle is a novel finding for the Norian strata. The obliquity signal is attributed to incoming atmospheric moisture from the northeast of the SMK basin. The E4 cycle controls lake-level changes over long times. Apparently, E4 is responsible whether or not a threshold value is crossed. Bundles of 109 kyr and 413 kyr in red mudstones suggest a dry system with reduced monsoonal activity. In contrast, humid periods reveal thick layers of dolomite beds, indicating that during those intervals the monsoonal activity was strong enough to prevent the playa system from drying out completely.

Bulk composition and clay mineralogy at DSDP Legs 56 and 57

Altogether 513 samples from sediments of Cretaceous to Pleistocene age from DSDP Legs 56 and 57 were examined by x-ray methods. The main constituents are clay minerals, quartz, feldspar, opaline silica, and volcanic glass. The sediment composition reflects the position of the sites in relation to the main source area, the Japanese Island Arc. For example, relatively coarse-grained material rich in quartz and feldspar was deposited closest to the islands, whereas finer-grained material rich in clay minerals (mainly smectite and illite, with lesser amounts of kaolinite and chlorite) was deposited farther seaward. Vertical fluctuations in the composition of the sediments show the same trend in all sites and are caused mainly by a fluctuating contribution of biogenic silica with time. A trend reversal in the chlorite/kaolinite ratio at Site 438 supports the conclusion that the subsidence of the Oyashio ancient landmass took place during the middle Miocene. That ratio also indicates a northwest drift in the position of Site 436 by sea floor spreading. Oscillations of the illite/smectite ratio during the Pleistocene at Site 436 show the variations of climate during this period. During early diagenesis potassium is fixed in smectite. With increasing depth of burial a smectite-illite mixed layer is formed, with increasing illite layering. At Sites 434, 440, and 441, stepwise changes confirm intensive tectonic process at the midslope terrace and the lower inner slope of the Japan Trench.

Mineralogy and major-element chemistry of volcanic ash of ODP Site 131-808

Mineralogical and major-element compositions of 72 samples of volcanic ash, recovered from Site 808 at Nankai Trough during Leg 131, were analyzed in relation to the early diagenetic alteration. Alteration products are first observed at the following depths: smectite, 200 mbsf; clinoptilolite, 646 mbsf; and analcite, 810 mbsf. Glass decomposition dominates over authigenic mineral formation between 200 and 550 mbsf in the sediment column, whereas mineral formation becomes dominant below 550 mbsf. Based on the X-ray diffraction patterns, a broad and asymmetric peak of 15A suggests a presence of illite/smectite (I/S) mixed-layered minerals in a sample from 646 mbsf. I/S mixed-layered mineral formation, however, rarely occurs even at the bottom of the sediment column (1290 mbsf) at 120° C. This is possibly because zeolite (especially clinoptilolite) formed in the ash interferes with illite formation in the smectite. The formation of alteration minerals affects the major-element chemistry of the ash and the interstitial waters. H4SiO4 concentrations in interstitial waters increase during glass decomposition and decrease with smectite and clinoptilolite formation. K is removed from interstitial water into smectite and/or clinoptilolite. Mg is fixed into smectite (and/or chlorite).