Late Cretaceous volcaniclastic rocks at DSDP Holes 74-525A and 74-528

Volcaniclastic rocks of Late Cretaceous age occur in four out of five sites (525, 527, 528, 529) drilled on the crest and the northwest flank of the Walvis Ridge during Leg 74. They are mostly interlayered with and overlie basement in the lowermost 10-100 m of the sedimentary section. Rocks from Holes 525A and 528 were studied megascopically and microscopically, by XRD, and XRF chemical analyses of whole-rock major and trace elements were undertaken. The dominant rock of Hole 528 volcaniclastics is a fine-grained (silt to fine sand), mostly matrix-bearing (partly matrix-rich) vitric "tuff," occurring as 5-110 cm thick, partly graded layers, some of which are distinctly bedded. Volcaniclastics of Hole 525A are generally richer in sanidine crystals. Most rocks contain some nonvolcanic clasts, chiefly foraminifers and lesser amounts of shallow-water fossil debris. Scoria shards, clasts of tachylite, and fine-grained basalts as well as chemical analyses suggest a basaltic to intermediate composition for most rocks of Hole 528, whereas volcaniclastics of Hole 525A are more silicic. The occurrence of tachylite and epiclastic, coarse-grained, basaltic clasts throughout the volcaniclastic sequence at Site 528 indicates shallow-water eruptions and perhaps even ocean island volcanism. The minor occurrence in Hole 528 of trachytic? pumice shards with phenocrysts of K-feldspar and the abundance of such shards in rocks from Hole 525A indicate Plinian eruptions characteristic of more mature stages of ocean island evolution. The sedimentary structures of volcaniclastic layers and their occurrence within deep sea calcareous oozes indicate a mass flow origin. Diagenetic alteration of the volcaniclastic rocks is pronounced, and four major stages of glass shard alteration are distinguished. Despite the effects of alteration and small-scale redistribution of elements and the admixture of nonvolcanic components, there were no drastic changes in the chemical composition of the rocks, except for pronounced increases in K and Rb and decreases in Ca and Fe. The basaltic volcaniclastic rocks very much resemble basement basalts in that they are moderately evolved tholeiites derived from an LIL-enriched mantle source with Zr/Nb ratios (Hole 528) of 5 to 6. This, in conjunction with the interbedding of volcaniclastic rocks and basement lavas, indicates contemporaneous seamount or island and basement volcanic activity involving magmas derived from similar sources.

Mineral composition and geochemistry of sediments from ODP Leg 127 sites

The lithostratigraphy of Neogene hemipelagic sediments recovered from the Japan Sea during Leg 127 was revised to improve intersite consistency and to remove confusion stemming from diagenetic modification of the lithology through the opal-A to opal-CT transformation. Special emphasis was put on the presence and nature of dark-light cycles in revising the lithostratigraphy. Mineral composition analysis was conducted for samples from Sites 794, 795, and 797. In addition, major element chemical composition analysis was conducted for these same sample sets from Site 794. The result of mineral composition analysis suggests that the detrital component, which consists of such minerals as quartz, plagioclase, illite, and kaolinite plus chlorite, is diluted to various degrees by biogenic silica (opal-A) and its diagenetic equivalents (opal-CT and quartz). Smectite, on the other hand, may be a diagenetic or hydrothermal alteration product of volcanic material, although more study is necessary to confirm its origin. As a whole, vertical variation in the sediment composition is consistent with the revised lithostratigraphy and helps to characterize the redefined lithologic units quantitatively.

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.

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.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

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.

Mineralogy of Hawaiian Arch sediments

The mineralogy of both bulk- and clay-sized (<2 µm) fractions of sediments from Holes 842A and 842B of Ocean Drilling Program Leg 136 was determined by X-ray diffraction. The sediments consist of a combination of terrigenous (quartz, plagioclase, smectite, illite, kaolinite, and chlorite), volcaniclastic (augite, plagioclase, and volcanic glass), and diagenetic minerals (smectite, phillipsite, clinoptilolite, and opal-CT). Although biogenic silica (radiolarians and diatoms) is common in near-seafloor (<10 mbsf) sediments, biogenic calcite is rare. Variations with depth in abundances of the terrigenous minerals reflect temporal changes in the flux of eolian material to the site. Volcanogenic material derived from the Hawaiian Islands is present in lithologic Unit 1 (0-19.9 meters below seafloor) both as discrete layers and as finely disseminated silt- and clay-sized material. Volcanic glass is present only in the upper 10 m of the sediment column. In Unit 2 (19.9-35.7 mbsf), increased smectite and zeolite abundances with depth as well as indurated, zeolite-rich layers are thought to be the alteration products of volcanogenic material. The source of this older (late Oligocene to middle Miocene) volcanogenic detritus may be continental volcanism. Microfabrics imaged using back-scattered electron imaging reflect the effects of compaction and diagenesis on sediment porosity and matrix structure. As porosity decreases during burial, the matrix changes from an open, floc-like fabric, to an interlocking network of clay mineral domains, and finally to a dense intergrowth of clay minerals and zeolites. Despite the substantial changes in sediment microfabric and mineralogy, correlations between physical and acoustic properties and mineralogy are weak or absent. The sediment has maintained high porosity (>70%), and water content appears to dominate the sediment's physical character and acoustic response.

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 geochemistry at DSDP Leg 64 Holes

At DSDP Site 477, late Quaternary diatomaceous muds and delta-derived silty-sand turbidites at 2000 meters water depth have been extensively and progressively altered by a deep-seated heat source beneath a sill. Bulk petrologic and microprobe analyses have identified a crudely zoned paragenesis within 260 meters sub-bottom which ranges from unaltered to slightly altered oozes (0-50 m), anhydrite-dolomite claystones (105-125 m), illite-chlorite-pyrite claystones (125-140 m), chlorite-pyrite-calcite-carbonaceous claystones with traces of K-feldspar, albite, epidote (140-190 m), and chlorite-epidote-quartz-albite-pyrrhotite-sphene sandstone (190-260 m). Several petrologic features suggest rapid processes of ocean floor metamorphism: (1) friable and porous textures, (2) abundant relict grains with overgrowths, (3) idiomorphic habits on epidotes, feldspars, and quartz, and (4) a steep gradient in levels of alteration. Many aspects of this hydrothermal assemblage are similar to hydrothermally metamorphosed sandstones of the Cerro Prieto, Mexico, geothermal area.

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).

(Supplement) Groundwater quality in Lahore Pakistan: emphasis on Arsenic and Fluoride levels

The dataset provides detailed information on the study that was conducted in Lahore's 7 major towns. The sample was taken from 472 tubewells and analyzed for major cations and anions using APHA 2012 techniques as explained herein. Besides, E.coli determination was done to check for microbial contamination. The data includes results from PHREEQC modeling of As(III)/ As(V) species and saturation indices as well as Aquachem's computed hydrochemical water facies. The WHO (2011) and EPA standards included in Aquachem identified the parameters that where in violation. Bicarbonates dominated the groundwater types with 50.21% of the samples exceeding the EPA maximum permissible limit of 250 mg/L in drinking water. Similarly, 30.51% of the samples had TDS values greater than 500 mg/L while 85.38 % of the samples exceed 10 µg/L threshold limit value of arsenic. Also, instances of high magnesium hazard values were observed which requires constant assessment if the groundwater is used for irrigation. Higher than 50% MH values are detrimental to crops which may reduce the expected yields. The membrane filtration technique using m-Endo Agar indicated that 3.59% samples had TNC (too numerous to count) values for E.coli while 5.06% showed values higher than 0 cfu/ 100 ml acceptable value in drinking water. Any traces of E-coli in a groundwater sample indicate recent fecal contamination. Such outcomes signify presence of enteric pathogens. If the groundwater is not properly dosed with disinfectants it may cause harm to human health. It is concluded that more studies are needed and proper groundwater management implement to safeguard the lives of communities that depend solely on groundwater in the city.

Minerals of bulk samples and clay fraction at DSDP Leg 80 Holes

At the request of the Leg 80 scientific party, selected samples of Cretaceous age were processed by X-ray diffraction at the mineralogy laboratories at the Ecole des Mines (Albian to Late Cretaceous samples) and at the Institut de Géologie at Dijon (Barremian samples). The results were used in developing the lithostratigraphy and sedimentology discussed in this volume by Rat et al. 1985 (doi:10.2973/dsdp.proc.80.140.1985) in their study of Barremian-Albian paleoenvironment, by Graciansky and Gillot in their study of Albian and Cenomanian limestones, and by Graciansky and Bourbon in their paleoenvironmental reconstructions for the Late Cretaceous chalks.

Mineral and chemical compositions of clay sediments from the Pacific Ocean, DSDP data

Mineral and chemical compositions, as well as conditions of formation of clay sediments in major structural elements of the Pacific Ocean floor with different ages are under consideration in the monograph. Depending on evolution of the region two ways of clay sediment formation are identified: terrigenous and authigenic. It is shown that terrigenous clay sediments predominate in marginal parts of the Pacific Ocean. Authigenic mineral formation occurring in the basal part of the sedimentary cover primarily results from removal of material from underlying basalts. This material is released during secondary alteration of the basalts due to their interaction with sea water, as well as with deep solutions.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.