Geochemistry of ODP Leg 135 igneous rock samples

Ocean Drilling Program Leg 135 provided igneous rock cores from six sites drilled on a transect across the Lau Basin between the Lau Ridge remnant arc and the modem spreading ridges of the Central and Eastern Lau Spreading Centers. The drill cores sampled crust from the earliest stage of backarc extension (latest Miocene time, about 6 Ma), and younger crust (late Pliocene, about 3.8-2 Ma, and middle Pleistocene, about 0.64-0.8 Ma). Nearly all of the igneous samples are from tholeiitic basalt flows; many of them are interbedded with arc-composition volcaniclastic sediments. Rock compositions range from olivine-plagioclase-clinopyroxene basalt, with up to 8% MgO, to oceanic andesites with less than 3.2% MgO and silica contents as high as 56%. The oldest rocks recovered are close in composition to rocks formed at the modern Central and Eastern Lau Spreading Centers and have MORB-like characteristics. Generation of the oldest units was coeval with arc-tholeiitic volcanism on the Lau Ridge less than 100 km to the west. The arc and backarc melts came from different mantle sources. At three sites near the center of the basin, the crust is arc-tholeiitic basalt, two-pyroxene basaltic-andesite, and two-pyroxene andesite. These rocks have many similarities to modem Tofua Arc lavas yet they were drilled within 70 km of the MORB-like Eastern Lau Spreading Center. Estimates of the minimum age for these arc-like rocks indicate that they are late Pliocene (about 2 Ma). These ages overlap the age of the nearby Eastern Lau Spreading Center. The heterogeneous crust of the Lau Basin carries many of the signatures of supra-subduction zone (SSZ) melts but also has a distinct MORB-like component. Mixing between SSZ and MORB mantle sources may explain the variations and the spatial distribution of magma types.

Geochemistry of ODP Hole 176-735B igneous and hydrothermal veins

During Legs 118 and 176, Ocean Drilling Program Hole 735B, located on Atlantis Bank on the Southwest Indian Ridge, was drilled to a total depth of 1508 meters below seafloor (mbsf) with nearly 87% recovery. The recovered core provides a unique section of oceanic Layer 3 produced at an ultraslow spreading ridge. Metamorphism and alteration are extensive in the section but decrease markedly downward. Both magmatic and hydrothermal veins are present in the core, and these were active conduits for melt and fluid in the crust. We have identified seven major types of veins in the core: felsic and plagioclase rich, plagioclase + amphibole, amphibole, diopside and diopside + plagioclase, smectite ± prehnite ± carbonate, zeolite ± prehnite ± carbonate, and carbonate. A few epidote and chlorite veins are also present but are volumetrically insignificant. Amphibole veins are most abundant in the upper 50 m of the core and disappear entirely below 520 mbsf. Felsic and plagioclase ± amphibole ± diopside veins dominate between ~50 and 800 mbsf, and low-temperature smectite, zeolite, and prehnite veins are present in the lower 500 m of the core. Carbonate veinlets are randomly present throughout the core but are most abundant in the lower portions. The amphibole veins are closely associated with zones of intense crystal plastic deformation formed at the brittle/ductile boundary at temperatures above 700°C. The felsic and plagioclase-rich veins were formed originally by late magmatic fluids at temperatures above 800°C, but nearly all of these have been overprinted by intense hydrothermal alteration at temperatures between 300° and 600°C. The zeolite, prehnite, and smectite veins formed at temperatures <100°C. The chemistry of the felsic veins closely reflects their dominant minerals, chiefly plagioclase and amphibole. The plagioclase is highly zoned with cores of calcic andesine and rims of sodic oligoclase or albite. In the felsic veins the amphibole ranges from magnesio-hornblende to actinolite or ferro-actinolite, whereas in the monomineralic amphibole veins it is largely edenite and magnesio-hornblende. Diopside has a very narrow range of composition but does exhibit some zoning in Fe and Mg. The felsic and plagioclase-rich veins were originally intruded during brittle fracture at the ridge crest. The monomineralic amphibole veins also formed near the ridge axis during detachment faulting at a time of low magmatic activity. The overprinting of the igneous veins and the formation of the hydrothermal veins occurred as the crustal section migrated across the floor of the rift valley over a period of ~500,000 yr. The late-stage, low-temperature veins were deposited as the section migrated out of the rift valley and into the transverse ridge along the margin of the fracture zone.

(Table 1) Clay and non-clay mineral composition of dirty ice samples from across the Arctic

Extensive dirty ice patches with up to 7 kg/m**2 sediment concentrations in layers of up to 10 cm thickness were encountered in 2005 and 2007 in numerous areas across the central Arctic. The Fe grain fingerprint determination of sources for these sampled dirty ice floes indicated both Russian and Canadian sources, with the latter dominating. The presence of benthic shells and sea weeds along with thick layers (2-10 cm) of sediment covering 5-10 m2 indicates an anchor ice entrainment origin as opposed to suspension freezing for some of these floes. The anchor ice origin might explain the dominance of Canadian sources where only narrow flaw leads occur that would not favor suspension freezing as an entrainment process. Expandable clays, commonly used as an indicator of a Kara Sea origin for dirty sea ice, are present in moderately high percentages (>20%) in many circum-Arctic source areas, including the Arctic coasts of North America. Some differences between the Russian and the North American coastal areas are found in clay mineral abundance, primarily the much higher abundance of chlorite in North America and the northern Barents Sea as opposed to the rest of the Russian Arctic. However, sea ice clay mineralogy matched many source areas, making it difficult to use as a provenance tool by itself. The bulk mineralogy (clay and non-clay) does not match specific sources possibly due to reworking of the sediment in dirty floes through summer melting or the failure to characterize all possible source areas.

Chemical composition of igneous rocks and origin of the sill and pillow-basalt complex at DSDP Site 61-462

The sill and pillow complex cored on Deep Sea Drilling Project Leg 61 (Site 462) is divided into two groups, A and B types, on the basis of chemical composition and volcanostratigraphy. The A-type basalt is characterized by a higher FeO*/MgO ratio and abundant TiO2, whereas the B-type basalt is characterized by a lower FeO*/MgO ratio and scarcity of TiO2. The A type is composed of sills interbedded with hyaloclastic sediments, and the B type consists of basalt sills and pillow basalt with minor amounts of sediment. However, the structure of pillow basalts in the B type is atypical; they might be eruptive. From paleontological study of the interbedded sediments and radiometric age determination of the basalt, the volcanic event of A type is assumed to be Cenomanian to Aptian, and that of B type somewhat older. The oceanic crust in the Nauru Basin was assumed to be Oxfordian, based on the Mesozoic magnetic anomaly. Consequently, two events of intraplate volcanism are recognized. It is thus assumed that the sill-pillow complex did not come from a normal oceanic ridge, and that normal oceanic basement could therefore underlie the complex. The Site 462 basalts are quartz-normative, and strongly hypersthene-normative, and have a higher FeO*/MgO ratio and lower TiO2 content. Olivine from the Nauru Basin basalts has a lower Mg/(Mg + Fe**2+) ratio (0.83-0.84) and coexists with spinel of lower Mg/(Mg + Fe**2+) ratio when compared to olivine-spinel pairs from mid-ocean ridge (MAR) basalt. The glass of spinel-bearing basalts has a higher FeO*/(FeO* + MgO) ratio (0.58-0.60) than that of MAR (<0.575). Therefore, the Nauru Basin basalts are chemically and mineralogically distinct from ocean-ridge tholeiite. That the Nauru Basin basalts are quartz-normative and strongly hypersthene-normative and have a lower TiO2 content suggests that the basaltic liquids of Site 462 were generated at shallower depths (<5 kbar) than ocean-ridge tholeiite: Site 462 basalts are similar to basalts from the Manihiki Plateau and the Ontong-Java Plateau, but different from Hawaiian tholeiite of hot-spot type, with lower K2O and TiO2 content. We propose a new type of basalt, ocean-plateau tholeiite, a product of intraplate volcanism.

Geochemical composition of minerals obtained from ODP Sites 180-1109, 180-1117 and 180-1118

During the last 8 m.y. the Papuan Peninsula region of Papua New Guinea has been affected by extension which opened the Woodlark Basin. The present-day spreading tip is located at the foot of the Moresby Seamount, a crustal block whose northern flank is an active low-angle normal fault related to this extension. During Ocean Drilling Program Leg 180 (7 June-11 August 1998), 11 sites (1108-1118) were drilled along a north-south-trending transect across the Woodlark Basin just ahead of the spreading tip. Four of these sites (1118, 1109, 1114, and 1117) reached the crystalline basement, which is composed of diabase and gabbro. Sites 1118 and 1109, located on the Woodlark Rise, belong to the hanging wall block, and Sites 1114 and 1117, located on the crest of the Moresby Seamount, belong to the footwall block and the fault zone itself. Most of the basalt, diabase, and gabbro that were recovered show a well-preserved magmatic texture. The diabase, which is the most abundant rock type, has a coarse-grained ophitic texture composed of poikilitic clinopyroxene including radiating, locally skeletal plagioclase laths with interstitial iron oxide grains. Secondary mineralogy consists of chlorite, zeolite, calcite, albite, and quartz. The gabbro shows a medium-grained granular texture. The magmatic mineralogy consists of euhedral laths of plagioclase and anhedral interstitial clinopyroxene. Secondary mineralogy consists of a magnesio to actinolitic hornblende, chlorite, clinozoisite, zeolite, quartz, and calcite. The retrograde metamorphic evolution of both gabbro and diabase occurred under low amphibolite to subgreenschist facies conditions associated mainly with brittle deformation and the development of a local low-temperature shear zone. This shows no evidence for high thermal gradient in the crust during the continental rifting.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

Major element compositions, minerals and trace elements at DSDP Leg 67 Holes

Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 18 samples of volcanic rocks from the Guatemala Trench area (Deep Sea Drilling Project Leg 67). Typical fresh oceanic tholeiites occur in the trench itself (Hole 500) and in its immediate vicinity on the Cocos Plate (Site 495). Several samples (often reworked) of "spilitic" oceanic tholeiites are also described from the Trench: their mineralogy (greenschist facies association - actinolite + plagioclase + chlorite) and geochemistry (alteration, sometimes linked to manganese and zinc mineralization) are shown to result from high-temperature (300°-475°C) hydrothermal sea water-basalt interactions. The samples studied are depleted in light rare-earth elements (LREE), with the exception of the slightly LREE-enriched basalts from Hole 500. The occurrence of such different oceanic tholeiites in the same area is problematic. Volcanic rocks from the Guatemala continental slope (Hole 494A) are described as greenschist facies metabasites (actinolite + epidote + chlorite + plagioclase + calcite + quartz), mineralogically different from the spilites exposed on the Costa Rica coastal range (Nicoya Peninsula). Their primary magmatic affinity is uncertain: clinopyroxene and plagioclase compositions, together with titanium and other hygromagmaphile element contents, support an "active margin" affinity. The LREE-depleted patterns encountered in the present case, however, are not frequently found in orogenic samples but are typical of many oceanic tholeiites.

Optimization of wastepaper sludge ash (WSA) in robust cementitious systems

Abstract : Wastepaper sludge ash (WSA) is generated by a cogeneration station by burning wastepaper sludge. It mainly consists of amorphous aluminosilicate phase, anhydrite, gehlenite, calcite, lime, C2S, C3A, quartz, anorthite, traces of mayenite. Because of its free lime content (~10%), WSA suspension has a high pH (13). Previous researchers have found that the WSA composition has poor robustness and the variations lead to some unsoundness for Portland cement (PC) blended WSA concrete. This thesis focused on the use of WSA in different types of concrete mixes to avoid the deleterious effect of the expansion due to the WSA hydration. As a result, WSA were used in making alkali-activated materials (AAMs) as a precursor source and as a potential activator in consideration of its amorphous content and the high alkaline nature. Moreover, the autogenous shrinkage behavior of PC concrete at low w/b ratio was used in order to compensate the expansion effect due to WSA. The concrete properties as well as the volume change were investigated for the modified WSA blended concrete. The reaction mechanism and microstructure of newly formed binder were evaluated by X-ray diffraction (XRD), calorimetry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). When WSA was used as precursor, the results showed incompatible reaction between WSA and alkaline solution. The mixtures were not workable and provided very low compressive strength no matter what kinds of chemical activators were used. This was due to the metallic aluminum in WSA, which releases abundant hydrogen gas when WSA reacts with strong alkaline solution. Besides, the results of this thesis showed that WSA can activate the glassy phase contained in slag, glass powder (GP) and class F fly ash (FFA) with an optimum blended ratio of 50:50. The WSA/slag (mass ratio of 50:50) mortar (w/b of 0.47) attained 46 MPa at 28 days without heat curing assistance. A significant fast setting was noticed for the WSA-activated binder due to the C3A phase, free lime and metallic aluminum contained in the WSA. Adding 5% of gypsum can delay the fast setting, but this greatly increased the potential risk of intern sulfate attack. The XRD, TGA and calorimetry analyses demonstrated the formation of ettringite, C-S-H, portlandite, hydrogarnet and calcium carboaluminate in the hydrated binder. The mechanical performance of different binder was closely related to the microstructure of corresponding binder which was proved by the SEM observation. The hydrated WSA/slag and WSA/FFA binder formed a C-A-S-H type of gel with lower Ca/Si ratio (0.47~1.6). A hybrid gel (i.e. C-N-A-S-H) was observed for the WSA/GP binder with a very low Ca/Si ratio (0.26) and Na/Si ratio (0.03). The SEM/EDX analyses displayed the formation of expansive gel (ettringite and thaumasite) in the gypsum added WSA/slag concrete. The gradual emission of hydrogen gas due to the reaction of WSA with alkaline environment significantly increased the porosity and degraded the microstructure of hydrated matrix after the setting. In the last phase of this research WSA-PC blended binder was tailored to form a high autogenous shrinkage concrete in order to compensate the initial expansion. Different binders were proportioned with PC, WSA, silica fume or slag. The microstructure and mechanical properties of concrete can be improved by decreasing w/b ratios and by incorporating silica fume or slag. The 28-day compressive strength of WSA-blended concrete was above 22 MPa and reached 45 MPa when silica fume was added. The PC concrete incorporating silica fume or slag tended to develop higher autogenous shrinkage at low w/b ratios, and thus the ternary binder with the addition of WSA inhibited the long term shrinkage due to the initial expansion property to WSA. In the restrained shrinkage test, the concrete ring incorporating the ternary binder (PC/WSA/slag) revealed negligible potential to cracking up to 96 days as a result of the offset effect by WSA expansion. The WSA blended regular concrete could be produced for potential applications with reduced expansion, good mechanical property and lower permeability.

Estudo de Matérias-Primas do Rio Grande do Norte para Uso em Revestimento Poroso: Influência do teor de dolomita e temperatura de calcinação nas propriedades físico-mecânicas

The state of Rio Grande do Norte presents a great potentiality for the production of ceramic tiles because of having natural raw material in quantity and quality making its economical exploration possible, beyond the great energetic differential of the state, the natural gás. This works aims to study the influence of the dolomite and granulometry concentration and calcinations temperature in the obtaining of formulations for porous coverings which have to be coherent to the project,s specifications. The experiments have involved the physical-chemical and mineralogical characterizations of raw materials and mechanical tests in the dry and burnt proof bodies preceding a mixture experiment planning with the use of the response surface methodology, in order to get the best raw materials combinations to produce a ceramic mass with specific properties. The twelve ceramic masses studied in this work were prepared by the via dry process, characterized, shaped by uniaxial pressing and sinterized in the temperatures of 940ºC, 1000ºC, 1060ºC, 1120ºC and 1180ºC, using a fast burning cycle. The crystalline phases formed during the sintering in the temperatures in study have revealed the presence of anorthite and diopside beyond quartz with a remaining phase. These phases were the main responsible ones by the physical- mechanical properties of the sinterized proof bodies. The proof bodies after the sintering stage have presented water absorption higher than 10% and a good dimensional stability in all studied temperatures. However, the flexural breaking strength results in the temperatures of 940ºC, 1000ºC and 1060ºC, under the temperature zone of the vitrification of ceramic whiteware do not reach the flexural breaking strength specific for the porous wall tile (15 MPa), but in the temperature of 1120ºC next to the vitrification temperature zone, some whiteware ceramic (formulations) has reached the specified value for the porous wall tile. The results of this work have showed that the studied raw materials have great importance for used in the production of porous wall tiles (BIII)