Petrology and diagenesis of sandstones at DSDP Hole 58-445

The sandstone succession in the lower 240 meters of DSDP Site 445, on the Daito Ridge, provided an opportunity to evaluate the effect of burial diagenesis of sandstones in a deep hole in a tectonic environment (remnant arc) characterized by a history of high heat flow. This report provides preliminary data concerning the petrology and diagenesis of these sandstones and records diagenetic changes which have occurred with increasing depth of burial. Methods used for this study included grain-size analysis (measured from thin sections using the method of Friedman, 1958), polarizing microscopy, X-ray diffraction, and scanning electron microscopy. A JEOL scanning electron microscope fitted with an energydispersive- X-ray detector was used for obtaining qualitative chemical data on certain minerals to aid in identification.

Thermal diagenesis of clay minerals within volcanogenic material from ODP Site 135-841

Clay minerals are examined in detail in the sediment from the Tonga Trench margin at Site 841 (Leg 135 ODP). The changes in amount and nature of secondary clays with depth provide an alternative explanation for the intensive alteration of volcanogenic material at convergent margins. A characteristic distribution of clay minerals with depth shows four distinct zones unexplainable by simple burial diagenesis processes. These are named the upper, reactive, lower and rhyolitic zones. The reactive zone is intercalated with numerous sills and is characterized by the dominant iron-rich clays such as saponite, corrensite and chlorite associated with analcime. The occurrence of such iron-rich clays, mostly associated with a large amount of analcime, yields chemical and mineralogical evidence for thermal diagenesis. The required heat for the diagenetic process was transferred from recently intruded basaltic andesite sills. In the vicinity of these intrusions, the iron-rich clay minerals may have formed at temperatures up to 200°C. A zoning with respect to clay and zeolite minerals indicates that the influence of the palaeoheat flow decreased with the distance from the intrusion. The formation of interlayered I/S, illite, kaolinite and aluminous chlorite, which are recognized as major secondary minerals within the rhyolitic complex, was mainly controlled by both early diagenesis at moderately elevated temperatures, and since the Eocene by burial diagenesis at low temperatures. The occurrence of a steam zone in an early stage of the intrusion is restricted to Miocene tuffs and has overprinted the early alteration of the volcanogenic material within the tuffs and has changed the originally pristine composition of the pore fluids.

Zeolite and silica diagenesis and sandstone petrography at DSDP Sites 57-438 and 57-439

We detected authigenic clinoptilolites in two core samples of tuffaceous, siliceous mudstone in the lower Miocene section of Hole 439. They occur as prismatic and tabular crystals as long as 0.03 mm in various voids of dissolved glass shards, radiolarian shells, calcareous foraminifers, and calcareous algae. They are high in alkalies, especially Na, and in silica varieties. There is a slight difference in composition among them. The Si : (Al+ Fe3+) ratio is highest (4.65) in radiolarian voids, intermediate (4.34) in dissolved glass voids, and lowest (4.26) in voids of calcareous organisms. This difference corresponds to the association of authigenic silica minerals revealed by the scanning electron microscope: There are abundant opal-CT lepispheres in radiolarian voids, low cristobalite and some lepispheres in dissolved glass voids, and a lack of silica minerals in the voids of calcareous organisms. Although it contains some silica from biogenic opal and alkalies from trapped sea water, clinoptilolite derives principally from dissolved glass. Although they are scattered in core samples of Quaternary through lower Miocene diatomaceous and siliceous deposits, acidic glass fragments react with interstitial water to form clinoptilolite only at a sub-bottom depth of 935 meters at approximately 25°C. Analcimes occur in sand-sized clasts of altered acidic vitric tuff in the uppermost Oligocene sandstones. The analcimic tuff clasts were probably reworked from the Upper Cretaceous terrain adjacent to Site 439. Low cristobalite and opal-CT are found in tuffaceous, siliceous mudstone of the middle and lower Miocene sections at Sites 438 and 439. Low cristobalite derives from acidic volcanic glass and opal-CT from biogenic silica. Both siliceous organic remains and acidic glass fragments occur in sediments from the Quaternary through lower Miocene sections. However, the shallowest occurrence is at 700 meters subbottom in Hole 438A, where temperature is estimated to be 21°C. The d(101) spacing of opal-CT varies from 4.09 to 4.11 Å and that of low cristobalite from 4.04 to 4.06 Å. Some opal-CT lepispheres are precipitated onto clinoptilolites in the voids of radiolarian shells at a sub-bottom depth of 950 meters in Hole 439. Sandstone interlaminated with Upper Cretaceous shale is chlorite- calcite cemented and feldspathic. Sandstones in the uppermost Oligocene section are lithic graywacke and consist of large amounts of lithic clasts grouped into older sedimentary and weakly metamorphosed rocks, younger sedimentary rocks, and acidic volcanic rocks. The acidic volcanic clasts probably originated from the volcanic high, which supplied the basal conglomerate with dacite gravels. The older sedimentary and weakly metamorphosed rocks and green rock correspond to the lithologies of the lower Mesozoic to upper Paleozoic Sorachi Group, including the chert, limestone, and slate in south-central Hokkaido. However, the angular shape and coarseness of the clasts and the abundance of carbonate rock fragments indicate a nearby provenance, which is probably the southern offshore extension of the Sorachi Group. The younger sedimentary rocks, including mudstone, carbonaceous shale, and analcime-bearing tuff, correspond to the lithologies of the Upper Cretaceous strata in south-central Hokkaido. Their clasts were reworked from the southern offshore extension of the strata. Because of the discontinuity of the zeolite zoning due to burial diagenesis, an overburden several kilometers thick must have been denuded before the deposition of sediments in the early Oligocene.

Diagenesis and aquifer characteristics of the Sherwood Sandstone Group in North Nottinghamshire

The Sherwood Sandstone Group forms an important aquifer in Eastern England, which in North Nottinghamshire comprises the Nottingham Castle and Lenton Sandstone Formations. The aquifer is formed by an alluvial red-bed sequence dominated by medium-coarse grained sandstones which are texturally immature to submature and have only been subjected to shallow burial diagenesis. These sandstones reached the mature stage of the meso diagenetic regime, and four stages are recognized in their diagenetic history depending upon the physical/chemical processes prevailing and the subsequent effect on porosity and permeability. Stage "One" represents changes including dissolution of unstable silicates, clay replacement, red colouration and precipitation of authigenic minerals (quartz, feldspar, illite, l/S, kaolinite, dolomite, ferroan calcite, calcite). The net result of these changes was porosity reduction. Stage "Two" included changes due to mechanical compaction which resulted in minor porosity reduction. Stage "Three" was the main phase of secondary porosity enhancement. Stage "Four" represents changes taking place in the present groundwater where porosity and permeability may have been increased by dissolution and partly reduced by kaolinite precipitation. Porosity measured by water-resaturation and Hg-injection gave average values of 25.63% and 24.85% respectively. The results are comparable and showed marked correlation especially in highly porous/permeable rocks. Porosity measurements from photomicrographs were markedly offset from laboratory results. Horizontal Kw ranged between 1.43 x 10-5 and 1.13 x 10-1 mm/sec, with an average of  1.68 x 10-2 mm/sec. The estimated KHg ranged between 7.29 x 10-6 and 6.99 x 10-2 mm/sec with an average of 1.47 x 10-2 mm/sec. Both results are significantly correlated for highly porous/permeable rocks. The hydraulic properties are highly dependent upon the diagenetic properties (as most of the pores present are of secondary origin) as well as the pore size distribution. The chemistry of these groundwaters indicates that they are under-saturated with respect to dolomite, calcite, K-feldspar, l/S clay, and montmorillonite. The precipitation of kaolinite,and to a lesser extent illite, is favoured in the present groundwater regime.

Petrographic and isotope constraints on the origin of authigenic carbonate minerals and the associated fluid evolution in Late Permian coal measures, Bowen Basin (Queensland), Australia

Authigenic carbonate minerals are ubiquitous throughout the Late Permian coal measures of the Bowen Basin, Queensland, Australia. In the northern Bowen Basin, carbonates include the following assemblages: siderite I (delta O-18(SMOW) = +11.4 to + 17%, delta C-13(PDB) = - 5.3 to + 120), Fe-Mg calcite-ankerite-siderite II mineral association (delta O-18(SMOW) = +7.2 to + 10.20, delta C-13(PDB) = 10.9 to - 1.80 for ankerite) and a later calcite (delta O-18(SMOW) = +5.9 to + 14.60, delta C-13(PDB) = -11.4 to + 4.40). In the southern Bowen Basin, the carbonate phase consists only of calcite (delta O-18(SMOW) = +12.5 to + 14.80, delta C-13(PDB) = -19.4 to + 0.80), where it occurs extensively throughout all stratigraphic levels. Siderite I occurs in mudrocks and sandstones and predates all other carbonate minerals. This carbonate phase is interpreted to have formed as an early diagenetic mineral from meteoric waters under cold climate and reducing conditions. Fe-Mg calcite-ankerite-siderite Il occur in sandstones as replacement of volcanic rock fragments. Clay minerals (illite-smectite, chlorite and kaolinite) postdate Ca-Fe-Mg carbonates, and precipitation of the later calcite is associated with clay mineral formation. The Ca-Fe-Mg carbonates and later calcite of the northern Bowen Basin are regarded as having formed as a result of hydrothermal activity during the latest Triassic extensional tectonic event which affected this part of the basin, rather than deep burial diagenesis during the Middle to Late Triassic as previously reported. This hypothesis is based on the timing relationships of the authigenic mineral phases and the low delta O-18 values of ankerite and calcite, together with radiometric dating of illitic clays and recently published regional geological evidence. Following the precipitation of the Ca-Fe-Mg carbonates from strongly O-18-depleted meteoric-hydrothermal fluids, continuing fluid circulation and water-rock interaction resulted in dissolution of these carbonate phases as well as labile fragments of volcaniclastic rocks. Subsequently, the later calcite and day minerals precipitated from relatively evolved (O-18-enriched) fluids. The nearly uniform delta O-18 values of the southern Bowen Basin calcite have been attributed to very low water/rock ratio in the system, where the fluid isotropic composition was buffered by the delta O-18 values of rocks. (C) 2000 Elsevier Science B.V. All rights reserved.

Biostratigraphy, mineralogy and geochemistry of the Trabakua Pass and Ermua sections in Spain: Paleocene-Eocene transition

Isotopic, geochemical and bulk mineralogical analyses in the Trabakua and Ermua sections, Basque Basin, reveal major changes across the Paleocene-Eocene transition. Expanded sedimentary records exhibit a gradual decrease of 1.0 parts per thousand in delta(13)C values in the lower part of Zone P5 followed by a more rapid 3 parts per thousand negative excursion. The 3 parts per thousand delta(13)C excursion is associated with an abrupt decrease in carbonate sedimentation, increased detrital flux and decreased grain size which suggest changes in marine/atmospheric currents and/or size and structure of the ocean carbon reservoir. The clays recognized at Trabakua record a deep burial diagenesis as indicated by two generations of chlorite, the presence of mixed-layers chlorite-smectite and illite-smectite, the absence of smectite and the near absence of kaolinite. The very low delta(18)O values (<-3.5 parts per thousand) throughout the Trabakua and Ermua sections reflect diagenetic alteration rather than paleotemperatures. Because of deep burial diagenesis and very poorly preserved microfossils, the Trabakua Pass and Ermua sections are not optimal potential stratotypes for the Paleocene-Eocene boundary.

Coastal salina evaporites of the Triassic-Liassic boundary in the Iberian Peninsula: the Alacón borehole

The evaporite unit (the Lécera Formation), which was formed at the Triassic¿Liassic boundary in the Aragonian Branch of the Iberian Chain, was studied at the 01 Alacón borehole (Alacón village, Teruel province), where it is mainly constituted by a thick (>e and reflect deeper water settings, whereas in the upper part they correspond to shallower water settings. The evaporite sedimentation mainly occurred in a subsiding coastal basin of the salina or lagoon type. In this setting, the subaqueous precipitation of the carbonate and gypsum lithofacies was followed, in each cycle, by the interstitial growth of anhydrite in exposed conditions. As a whole, the evaporite succession reflects an infilling process. The conversion into anhydrite of the selenitic gypsum -probably also of the rest of depositional gypsum lithofaciesstarted under synsedimentary conditions and followed during shallow to moderate burial diagenesis.

Sulfur isotope variations from orebody to hand-specimen scale at the Mezica lead-zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb-Zn ore district at Mezica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mezica covers an area of 64 km(2) with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have delta(34)S values in the range of -24.7 to -1.5% VCDT (-13.5 +/- 5.0%) and -24.7 to -1.4% (-10.7 +/- 5.9%), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide delta(34)S values are negative within a broad range, with delta(34)S(pyrite) < delta(34)S(sphalerite) < delta(34)S(galena) for both conformable and discordant orebodies, indicating isotopically heterogeneous H(2)S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of (34)S-enriched H(2)S to the ore fluid. The variations of delta(34)S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative delta(34)S values with time along the different sphalerite generations are consistent with mixing of different H(2)S sources, with a decreasing contribution of H(2)S from regional TSR, and an increase from a local H(2)S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (-11.9 to -1.7%; -7.0 +/- 2.7%, n=12) tends to be depleted in (34)S compared with conformable ore (-24.7 to -2.8%, -11.7 +/- 6.2%, n=39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide delta(34)S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H(2)S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H(2)S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.

Paleomagnetism and rock magnetism of the Neoproterozoic Itajai Basin of the Rio de la Plata craton (Brazil): Cambrian to Cretaceous widespread remagnetizations of South America

A detailed rock magnetic and paleomagnetic study was performed on samples from the Neoproterozoic Itajai Basin in the state of Santa Catarina, Brazil, in order to better constrain the paleogeographic evolution of the Rio de la Plata craton between 600 and 550 Ma. However, rock magnetic properties typical of remagnetized rocks and negative response in the fold test indicated that these rocks carried a secondary chemical remanent magnetization. After detailed AF and thermal cleaning, almost all samples showed a normal polarity characteristic remanent magnetization component close to the present geomagnetic field. The main magnetic carriers are magnetite and hematite, probably of authigenic origin. The mean paleomagnetic pole of the ltajai Basin is located at Plat= -84 degrees, Plong = 97.5 degrees (A95 = 2 degrees) and overlaps the lower Cretaceous segment of the apparent polar wander path of South America, suggesting a cause and effect with the opening of the South Atlantic Ocean. A compilation of remagnetized paleomagnetic poles from South America is presented that highlights the superposition of several large-scale remagnetization events between the Cambrian and the Cretaceous. It is suggested that some paleomagnetic poles used to calibrate the APWP of Gondwana at Precambrian times need to be revised; the indication of remagnetized areas in southern South America may offer some help in the selection of sites for future paleomagnetic investigations in Precambrian rocks. (C) 2011 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.

Chemistry of smectite and volcanic glass of ODP Site 159-959

The Ocean Drilling Program (ODP) Site 959 was drilled in the northern border of the Côte d'Ivoire-Ghana Ridge at a water depth of 2100 m. Pleistocene total thickness does not exceed 20 m. Winnowing processes resulted in a low accumulation rate and notable stratigraphic hiatuses. During the Late Pleistocene, bottom circulation was very active and controlled laminae deposition (contourites) which increased the concentration of glauconitic infillings of foraminifera, and of volcanic glass and blue-green grains more rarely, with one or several subordinate ferromagnesian silicates. Volcanic glass generally was X-ray amorphous and schematically classified as basic to intermediate (44-60% SiO2). Opal-A or opal-CT suggested the beginning of the palagonitisation process, and previous smectitic deposits may have been eroded mechanically. The blue-green grains presented two main types of mineralogic composition: (1) neoformed K, Fe-smectite associated with zeolite (like phillipsite) and unequal amounts of quartz and anorthite; (2) feldspathic grains dominated by albite but including quartz, volcanic glass and smectites as accessory components. They were more or less associated with the volcanic glass. On the basis of their chemical composition, the genetic relationship between the blue-green grains and the volcanic glass seemed to be obvious although some heterogeneous grains seemed to be primary ignimbrite and not the result of glass weathering. The most reasonable origin of these pyroclastic ejecta would be explosive events from the Cameroon Volcanic Ridge, especially from the Sao Thome and Principe Islands and Mount Cameroon area. This is supported both by grain geochemistry and the time of volcanic activity, i.e. Pleistocene. After westward wind transport (some 1200 km) and ash fall-out, the subsequent winnowing by bottom currents controlled the concentration of the volcanic grains previously disseminated inside the hemipelagic sediment. Palagonitisation, and especially phillipsite formation, may result from a relatively rapid reaction during burial diagenesis (<1 m.y.), in deep-sea deposits at relatively low sedimentation rate. However, it cannot be excluded that the weathering had begun widely on the Cameroon Ridge before the explosive event.

Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Geochemistry of Neogene volcanic ashs in ODP Leg 124 holes

Mineralogical and geochemical analyses were performed on 40 ash layers of Pleistocene to late Miocene age, recovered during Leg 124 in the Celebes and Sulu Seas (Sites 767, 768, and 769). They provide information on alteration processes related to burial diagenesis. The zonal distribution of secondary volcanic products emphasizes a major diagenetic change, characterized by the complete replacement of volcanic glass by an authigenic smectite-phillipsite assemblage, in tephra layers dated at 3.5-4 Ma. This diagenetic "event" occurs simultaneously in the two basins, and, on the basis of isotopic data, under low-temperature conditions. It is independent of distinct sedimentation rates and related to a relative quiescence of on-land volcanic activity. This period suggests a more uniform paleooceanographic situation having tectonic significance, and probably reflects a kinetic and environmental control of diagenetic reactions.

Diagenetic development of deep-sea carbonate sediments from DSDP Holes 30-228, 30-289 and 33-316

Laboratory measurements of ultrasonic velocity (VP, VS) and attenuation (QP**-1, QS**-1) in deep-sea carbonate sequences at DSDP Sites 288, 289 and 316 in the equatorial Pacific were made in conjunction with studies of sediment density, porosity and pore geometry in order to investigate the role of diagenesis in the development of physical properties. Bulk porosity decrease appears to be related more significantly to depth of burial than to age of strata. Both depth of burial and age, however, are important factors controlling the modal pore diameter. In deep-burial diagenesis the modification of pore geometry is influenced by the presence of silica during diagenesis. In carbonate sequences at the three DSDP sites studied, shear wave attenuation anisotropy (QSHH**-1/QSHV**-1) correlates with the shear wave velocity anisotropy. Pore orientation, resulting from overburden pressure and other deep-burial diagenetic processes, is an important factor controlling the increase of VP anisotropy with age and depth of burial. On the basis of observed minor changes in anisotropy values with increasing pressure for some samples, other contributions to VP anisotropy such as grain orientation and bedding lamination cannot be ruled out.

Mineralogy and geochemistry of latest Miocene deposits in the Tyrrhenian Sea

Late Miocene sediments from ODP Sites 652 and 654, drilled on the Sardinian margin in the Western Tyrrhenian Sea, are investigated through mineralogical, micromorphological, geochemical, and microgeochemical analyses. Clay associations appear to be little controlled by conditions of deposition, and largely depend on pre- and post-depositional conditions. The sedimentary series from Central Mediterranean gives very different geodynamic information, according to the sector considered. While relatively stable conditions, like those encountered in Caltanissetta Basin, Sicily, favor the mineralogical expression of warm-temperate and subarid Messinian climate, the Eastern Sardinia margin (Site 654) clay suites mainly reflect the transition from tectonically active to relaxed conditions. The series deposited at the foot of the same margin above a thinner crust (Site 652) experienced the effects of burial diagenesis, enhanced by strong geothermal gradient.