Sugano, N.; Kyono, A.
There are a large number of natural and synthetic zeolites having a microporous structure, which is generally composed of Si/AlO4 three-dimensional framework. Analcime, NaAlSi2O6·H2O, is one of the most common naturally occurring zeolites. It forms a variety of solid solutions with wairakite, (Ca,Na2)Al2Si4O12·2H2O, pollucite (CsAlSi2O6·nH2O), and hsianghualite (Ca3Li2Be3Si3O12·F2). This study aimed to clarify structural variations in the solid solution between analcime and wairakite. Single crystals with compositions between analcime and wairakite were synthesized using hydrothermal synthesis method. Aluminium sulfate and sodium metasilicate nonahydrate gelled with distilled water were heated for 24 hours under 200 °C. The hydrothermally synthesized crystalline materials were analyzed by scanning electron microscope (SEM). SEM images showed that the grown single crystals exhibited euhedral trapezohedron shape up to 400μm in size. The effect of the cations substitution on the structural variation was examined by single-crystal X-ray diffraction analysis and electron probe micro-analyser (EPMA). Structure refinements based on the single-crystal X-ray diffraction data exhibited that crystal structures between analcime and wairakite belong to the cubic Ia-3d and kept approximately unchanged. Lattice parameter was monotonously reduced from 13.713 (1) Å to 13.650 (1) Å as a function of Ca concentration. In addition, the lattice parameter was also varied with Si/Al framework cation ratio. The contraction of the 6-membered oxygen rings was closely associated with exchanged cations and substituted framework cations. This study indicates that a geometry of micro-porous zeolite structure is significantly influenced by substitution of not only extra-framework cations but framework cations.
Espejel-Ayala, F; Corella, R Chora; Pérez, A Morales; Pérez-Hernández, R; Ramírez-Zamora, R M
The present work introduces the study of the CO2 capture process by zeolites synthesized from paper sludge and scrap glass. Zeolites ZSM-5, analcime and wairakite were produced by means of two types of Structure Directing Agents (SDA): tetrapropilamonium (TPA) and ethanol. On the one hand, zeolite ZSM-5 was synthesized using TPA; on the other hand, analcime and wairakite were produced with ethanol. The temperature programmed desorption (TPD) technique was performed for determining the CO2 sorption capacity of these zeolites at two sorption temperatures: 50 and 100 °C. CO2 sorption capacity of zeolite ZSM-5 synthesized at 50 °C was 0.683 mmol/g representing 38.2% of the value measured for a zeolite ZSM-5 commercial. Zeolite analcime showed a higher CO2 sorption capacity (1.698 mmol/g) at 50 °C and its regeneration temperature was relatively low. Zeolites synthesized in this study can be used in the purification of biogas and this will produce energy without increasing the atmospheric CO2 concentrations.
Offler, R.; Aguirre, L.; Levi, B.; Child, S.
An unconformity bound, episodic pattern of burial metamorphism is preserved in marine and terrestrial volcanic and sedimentary rocks which were deposited in the West Peruvian Trough during the Mesozoic and Cenozoic Eras. A particular metamorphic facies series is developed in each of the stratigraphic-structural units bounded by unconformities. In each unit, grade increases with stratigraphic depth and covers part or all of the range from zeolite to greenschist facies. At every unconformity a mineralogic break occurs where higher grade assemblages on top of the unconformity plane overlie lower grade assemblages. The presence of wairakite and the development of a wide range of metamorphic facies in thin sequences suggest high geothermal gradients, possibly related to generation of magma at depth.
Schiffman, P.; Elders, W.A.; Williams, A.E.; McDowell, S.D.; Bird, D.K.
In the Cerro Prieto geothermal field, carbonate-cemented, quartzofeldspathic sediments of the Colorado River delta are being actively metasomatized into calc-silicate metamorphic rocks by reaction with alkali chloride brines between 200/sup 0/ and 370/sup 0/C, low fluid and lithostatic pressures, and low oxygen fugacities. Petrologic investigations of drill cores and cutting from over 50 wells in this field identified a prograde series of calc-silicate mineral zones which include as index minerals: wairakite, epidote, prehnite, and clinopyroxene. Associated divariant mineral assemblages are indicative of a very low pressure/temperature metamorphic facies series which encompasses the clay-carbonate, zeolite, greenschist, and amphibolite facies. This hydrothermal metamorphic facies series, which is becoming increasingly recognized in other active geothermal systems, is characterized by temperature-telescoped dehydration and decarbonation mineral equilibria. Its equivalent should now be sought in fossil hydrothermal systems.
Schiffman, P.; Elders, W.A.; Williams, A.E.; McDowell, S.D.; Bird, D.K.
In the Cerro Prieto geothermal field, carbonate-cemented, quartzofeldspathic sediments of the Colorado River delta are being actively metasomatized into calc-silicate metamorphic rocks by reaction with alkali chloride brines between 200 and 370 C, at low fluid and lithostatic pressures and low oxygen fugacities. Their petrologic investigations of drill cores and cuttings from more than 50 wells in this field identified a prograde series of zones that include as index minerals wairakite, epidote, prehnite, and clinopyroxene. Associated divariant mineral assemblages are indicate of a very low pressure, low-temperature metamorphic facies series spanning the clay-carbonate, zeolite, greenschist, and amphibolite facies. This hydrothermal facies series, which is now recognized in other active geothermal systems, is characterized by temperature-telescoped dehydration and decarbonation. Its equivalent can now be sought in fossil hydrothermal systems.
Schiffman, P.; Elders, W. A.; Williams, A. E.; McDowell, S. D.; Bird, D. K.
In the Cerro Prieto geothermal field, carbonate-cemented, quartzofeldspathic sediments of the Colorado River delta are being actively metasomatized into calc-silicate metamorphic rocks by reaction with alkali chloride brines between 200 and 370 °C, at low fluid and lithostatic pressures and low oxygen fugacities. Our petrologic investigations of drill cores and cuttings from more than 50 wells in this field identified a prograde series of zones that include as index minerals wairakite, epidote, prehnite, and clinopyroxene. Associated divariant mineral assemblages are indicative of a very low pressure, low-temperature metamorphic facies series spanning the clay-carbonate, zeolite, greenschist, and amphibolite facies. This hydro-thermal facies series, which is now recognized in other active geothermal systems, is characterized by temperature-telescoped dehydration and decarbonation. Its equivalent can now be sought in fossil hydrothermal systems.
Mehegan, James M.; Robinson, Paul T.; Delaney, John R.
Deep crustal drilling in eastern Iceland has allowed study of a fossil hydrothermal system at a constructive plate margin. The drilled sequence consists of partly to completely altered subaerial lava flows, basaltic dikes, and minor clastic material. Alteration and secondary mineralization are most intense in the flow top breccias where water/rock ratios are presumed to have been the highest. In the upper portion of the cored sequence (to a depth of about 1200 m) alteration is characterized by the deposition of clay minerals ± calcite ± quartz ± laumontite into open spaces such as vugs and vesicles. Low-temperature zeolites, such as stilbite, epistilbite, mordenite, and heulandite, are also present but are restricted to the upper 500 m of the drill core. Below 1200 m, alteration is characterized by the dissolution and replacement of both primary minerals and earlier authigenic minerals, followed by partial filling of dissolution cavities. Early mineral assemblages consist of epidote ± quartz ± prehnite ± chlorite ± albite, and a later superimposed assemblage consists of calcite + laumontite ± anhydrite. Authigenic sphene, pyrite, chalcopyrite, pumpellyite, actinolite, and wairakite also occur sporadically in the cored sequence. Secondary mineral assemblages and temperature measurements of fluid inclusions suggest a maximum temperature of alteration of about 300°C. Fluid inclusion compositions indicate that the geothermal fluid was meteoric water with very low salinities and high calcium activities. Iron activities and oxygen fugacities were highest in the deeper portions of the systems. The mineral paragenesis suggests that the fluid composition, temperature, and PCO2 varied significantly with time. The thermal energy for the geothermal system was probably derived from a high-level magma chamber associated with nearby Thingmuli volcano. Local contact metamorphism, indicated by the formation of garnet, occurred during late stage emplacement of dikes into
Petrographic study and preliminary conceptual model of the Ixtlan de los Hervores geothermal zone, Michoacan, Mexico; Estudio petrografico y modelo conceptual preliminar de la zona geotermica de Ixtlan de los Hervores, Michoacan, Mexico
Viggiano-Guerra, Julio C; Gutierrez-Negrin, Luis C.A [Comision Federal de Electricidad (Mexico)
Petrographic studies of cuttings from the shallow well Ixtlan 2, drilled in the Ixtlan de los Hervores geothermal zone, State of Michoacan, Mexico, at a maximum depth of 159 meters, together with results of previous exploration studies, allow to delineate a preliminary conceptual model of the probable geothermal system. It is formed by a wide-fracture zone system, with low topographic relief and shallow water level. Its hydrothermal fluids are of sodium-chloride type, neutral pH, silica oversaturated in the discharge and with temperatures between 125 and 225 degrees Celsius, based on the geothermometry and the hydrothermal mineral assemblage encountered in the well. The assemblage of laumontite + quartz + calcite + chlorite/smectite + pyrite is typical for the zeolitic facies, beneath of which it is possible to encounter the epidote-wairakite facies, with higher temperatures. The favorable conditions of the zone allow to recommend continuation of exploration in the same. [Spanish] El estudio petrografico de muestras de canal de la perforacion del pozo somero Ixtlan 2, con una profundidad maxima de 159 metros y ubicado en la zona geotermica de Ixtlan de Los Hervores, Michoacan, Mexico, aunado a los resultados de estudios previos de exploracion superficial, han permitido la configuracion de un modelo conceptual preliminar del probable yacimiento geotermico. Se trata de un sistema zona de fractura ancha, bajo relieve y nivel freatico somero, con fluidos hidrotermales de tipo clorurado-sodico, pH neutro, sobresaturados de silice en la descarga, y con temperatura entre 125 y 225 grados Celsius, de acuerdo con la geotermometria + cuarzo + calcita + clorita/esmectita + pirita es tipica de la facies zeolitica, debajo de la cual podria hallarse la facies de epidota-wairakita, con temperaturas mas altas. Las condiciones favorables de la zona permiten recomendar la continuacion de la exploracion en la misma.
Fuentes, Francisco; Aguirre, Luis; Vergara, Mario; Valdebenito, Leticia; Fonseca, Eugenia
Cenozoic deposits in the Andes of central Chile have been affected by very low-grade burial metamorphism. At about 33°S in the Cuesta de Chacabuco area, approximately 53 km north of Santiago, two Oligocene and Miocene volcanic units form a ca. 1300-m-thick rock pile. The Miocene unit corresponds to a volcanic complex composed of two eroded stratovolcanoes. Secondary mineral assemblages in both units were studied petrographically and using X-ray diffraction and electron microprobe analyses. Most of the igneous minerals are wholly or partially preserved, and the ubiquitous secondary minerals are zeolites and mafic phyllosilicates. The alteration pattern observed is characterized by a lateral zonation in secondary mineralogy related to a lateral increase in temperature but not to stratigraphic depth. The following three zones were established, mainly based on the distribution of zeolites: zone I comprises heulandite, thomsonite, mesolite, stilbite and tri-smectite; zone II contains laumontite, yugawaralite, prehnite, epidote and chlorite; and zone III comprises wairakite, epidote, chlorite, diopside, biotite and titanite. For each zone, the following temperature ranges were estimated: zone I, 100-180 °C; zone II, 180-270 °C; and zone III, 245-310 °C. The alteration episode was characterized by a high Pfluid/ Ptotal ratio (ca. 1.0), although slightly variable, a high geothermal gradient of ca. 160 °C km -1 and fluid pressures below 500 bars. Although temperature was the main control on the mineral zonation, several interrelated parameters, mainly fluid composition, porosity and permeability, were also important. Hot, near neutral to slightly alkaline pH, alkali chloride hydrothermal fluids with very low dissolved CO 2 contents deposited the secondary minerals. The alteration pattern is the result of depositing fluids in outflow regions from a hydrothermal system developed inside a volcanic complex during the Miocene. The hydrothermal system has been eroded to a
Schiffman, P. (Univ. of California, Riverside); Elders, W.A.; Williams, A.E.; McDowell, S.D.; Bird, D.K.
In the Cerro Prieto geothermal system, carbonate-cemented, quartzo-feldspathic sediments of the Colorado River delta are being actively recrystallized into calc-silicate metamorphic rocks through intense fluid/rock interaction with alkali chloride brine (1.5 x 10/sup 4/ ppM TDS) at temperatures between 200/sup 0/ and 370/sup 0/C, fluid pressures <0.25 Kb, lithostatic pressures <1.0 Kb, and oxygen fugacities close to the QFM buffer. Petrologic investigations of cuttings and core from more than 50 wells in this field reveal a prograde series of calc-silicate mineral zones with index metamorphic minerals: wairakite (wr), epidote (ep), prehnite (pr), and calcic clinopyrosene (cpx). The compositions of these and other key phases: wr (Ca/Ca + Na + K + 0.97), ep (Fe/Fe + Al/sup vi/ = 0.11 to 0.31), pr (Fe/Fe + Al/sup vi/ = 0.01 to 0.28), cps (close to Wo/sub 50/ and Mg/Mg + Fe + Mn = 0.23 to 0.90), actinolite (0.20 Al/sup iv//15 cations and Mg/Mg + Fe + Mn = 0.67 to 0.82), biotite (Mg/Mg + Fe + Mn = 0.58 to 0.87) and microcline (Or/sub 96 to 100/) reflect recrystallization under low fluid pressures, relatively low f/sub O/sub 2//, and varying brine compositions. Divariant mineral assemblages in this system comprise a very low P/T facies series encompassing the clay-carbonate, zeolite, greenschist, and amphibolite facies and reflect equilibrium occurring in response to both increasing temperature and decreasing CO/sub 2/ pressure. Similar facies series, characterized by telescoped devolatization mineral reactions, are becoming increasingly recognized in other active geothermal systems above 300/sup 0/C. However, close analogues in the fossil geologic record are as yet unidentified.
Stelling, P. L.; Tobin, B.; Knapp, P.
Exploration for geothermal energy in Hot Springs Bay Valley (HSBV) on Akutan Island, Alaska, has revealed a rich hydrothermal history, including what appears to be a stage of peak activity during a significant glacial period. Alteration mineralogy observed in 754 m of drill core recovered from the outflow zone is dominated by chlorite and includes minor smectite clays, a suite of zeolite species and several moderately high-temperature hydrothermal minerals (epidote/clinozoisite, prehnite, adularia and wairakite). The latter minerals each have minimum formation temperatures exceeding 200 oC, and fluid inclusion results in related calcite crystals indicate temperatures of formation to be as high as 275 oC, some 100 oC hotter than the modern boiling point with depth (BPD) curve at that depth (>62 m). In order to maintain liquid temperatures this high, the pressure during mineralization must have been substantially greater (~680 bar), a pressure change equivalent to erosion of ~280 m of rock (ρ=2.5 g/cm3). Although glacial erosion rates are too low (0.034 mm/yr; Bekele et al., 2003) for this amount of erosion to occur in a single glaciation, glacial melting and ablation are substantially more rapid (~100 mm/yr; Bekele et al., 2003; Person et al., 2012). Thus, a more probable scenario than pure erosion is that peak hydrothermal conditions occurred during a large glacial event, with the added pressure from the overlying ice allowing the high temperature minerals to form closer to the ground surface. Subsequent melting of the ice eroded upper tributary valleys and upper levels of the originally smectite-rich alteration assemblage, explaining the paucity of swelling clays in the region. We present mineralogical, fluid inclusion and geochronologic evidence to support these conclusions, and discuss the general implications of sub-glacial hydrothermal system formation and geothermal resource potential. References: Bekele, E., Rostron, B. and Person, M. (2003) Fluid pressure
Triana J M
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Natural zeolites filling amygdales and veins in tertiary basaltic host rocks on the Isle of Skye (NW Scotland have been studied in some detail by transmitted light microscopy, scanning electron microscopy and X-ray diffraction techniques . The zeolites and associated minerals so identified in order of their relative time of formation from early to late were nontronite, amorphous silica phases, carbonate phases, chabazite, phillipsite, wairakite, thomsonite, analcime, natrolite and stilbite-type minerals . Zeolite formation in the Skye basalts began with low Si/Al ratio Na zeolites and a gradual increase in Ca content and Si/Al ratio, ending up as Ca zeolites . They were probably formed as a consequence of late-stage hydrothermal activity, although, locally, contact metamorphism may control the process of zeolite formation
Las zeolitas naturales como relleno en amígdalas y venas que ocurren en rocas basálticas Terciarias de la Isla de Skye (NW Escocia han sido estudiadas en detalle por técnicas de microscopía de luz transmitida, microscopía electrónica de barrido y difracción de rayos X. Las zeolitas y los minerales asociados identificados, en orden de su tiempo relativo de formación, son nontronita, fases de sílice amorfa, carbonatos, chabazita, filipsita, wairakita, thomsonita, analcima, natrolita y minerales tipo estilbita. La formación de zeolitas en los basaltos de Skye comenzó con una zeolita rica en Na de baja relación Si/Al y con el aumento gradual en el contenido de Ca y Si/Al, terminó con una zeolita rica en Ca Estas probablemente se formaron como consecuencia de una actividad hidrotermal tardía, aunque localmente un metamorfismo de contacto pudo controlar el proceso de formación de las zeolitas
Metamorfismo de muy bajo grado asociado a un sistema geotermal en rocas volcánicas básicas del Jurásico Medio, Formación Lonco Trapial, Paso Berwin, Chubut extra-andino Very low grade metamorphism associated with a geothermal system in basic volcanic rocks of the Middle Jurassic, Lonco Trapial Formation, Paso Berwin, Extra-Andean Chubut
Full Text Available Las rocas volcánicas básicas de la Formación Lonco Trapial, poseen una mineralogía primaria compuesta principalmente por olivino, plagioclasa cálcica y piroxeno, presentando además gran cantidad de amígdalas. La mineralogía metamórfica de muy bajo grado en estas rocas está caracterizada por ceolitas, minerales arcillosos y micáceos. La asociación mineral más característica está compuesta por celadonita, montmorillonita, heulandita, analcima, gonnardita y, además, por levyna y minerales de la serie analcima-wairakita en forma subordinada. Esta asociación pertenece a la facies ceolita y tuvo un origen asociado a un sistema geotermal. La analogía establecida con las zonas de ceolitas conocidas para sistemas geotermales equivalentes y el uso de la grilla petrogénetica para paragénesis ceolíticas, en el sistema An-Ab-SiO2-H2O, permiten establecer un rango de temperatura entre 80°-180°C. En este contexto habría ocurrido un único evento metamórfico hidrotermal en presencia de una fase fluida, muy pobre en CO2, cuya composición química habría cambiado desde un carácter neutro con baja a(SiO2 y a(K2O moderada (permitiendo la precipitación de esmectitas y celadonita a un carácter neutro-alcalino con a(SiO2 que posibilita la estabilidad de la heulandita.The basic volcanic rocks of the Lonco Trapial Formation, have a primary mineralogy mainly composed of olivine, calcic plagioclase and pyroxene, and present a large quantity of amygdales. Their metamorphic mineralogy is characterized by zeolites, clay and micaceous minerals. The main mineral association includes celadonite, montmorillonite, heulandite, analcime, gonnardite and subordinate levyne and minerals of the wairakite-analcime series. This association belongs to the zeolite facies and its origin was associated with a geothermal system. The analogy with known zeolite zones in equivalent geothermal systems and the use of the petrogenetic grid for zeolite parageneses, in