Mineralogy and distribution of hydrothermal mineral zones in Los Azufres (Mexico) geothermal field

The general features of the geometry of Los Azufres reservoir have been defined through the mapping of hydrothermal mineral alteration zones. Hydrothermal alteration has been studied in cuttings and drill cores from most of the active wells. X-ray diffraction microprobe analysis and classical optical methods have been employed for the identification of primary and authigenic minerals in fresh and altered samples. Observed patterns of alteration have been correlated with temperature and patterns of fluid circulation. The resulting model depicts a body of geothermal fluid at depth, which ascends and discharges through two main fracture systems. These two circulation zones are characterized by concentric aureoles of increasing hydrothermal alteration towards quasivertical axes. The overall pattern could be described as a dome structure produced by the abnormal thermal gradient, distorted by the effects of active upward circulation of the fluids.     

Major and trace-element enrichments in the Karapınar coals (Konya,Turkey)

Ten major oxides and 27 trace elements were determined in 21 samples collected from four holes that were drilled into the fault-controlled coals of the Karap?nar (Turkey) basin. On the basis of X-ray diffraction analyses, the coals contain, in order of abundance, calcite, quartz, dolomite, feldspar, mica, clay minerals, and gypsum. In samples from the study area, a high level of correlation was determined between Mo, Sb, As, U, and V, and S and TOC (Mo, r = 0.697; Sb, r = 0.902; As, r = 0.927; U, r = 0.653; V, r = 0.721). Relative to coals of the world, USA, Turkey, and China, coals of the study area are seen to be enriched up to 1,000 times with respect to Mg, Ca, Na, and K. The Karap?nar coals were determined to be enriched in Pb, U, Ba, Cs, Nb, Y, Sr, Rb, Ni, Co, V, and Sc relative to average Turkish coals; in Mn, Na, Ca, Mg, Cs, Sr, Ni, and Cr relative to average Chinese coals; in Ti, K, Na, Ca, Mg, U, Ta, Ba, Cs, Sr, Rb, As, Ni, Co, V, and Cr relative to average worldwide coals; in Mn, P, Ti, K, Na, Ca, Mg, Si, U, Ta, Ba, Cs, Nb, Zr, Sr, Ni, Co, V, and Cr relative to average USA coals; and in Mn, P, Ti, K, Ca, Mg, Fe, Sb, Nb, Zr, Sr, Rb, Zn, Cu, Ni, Co, and Sc relative to crustal averages (Clarke values). The aim of the present study was to determine the enrichment factors of the major- and trace-element contents of the Karap?nar coals relative to coals of the world, USA, China, and Turkey, and to crustal averages.     

Main aspects of geothermal energy in Mexico

With an installed geothermal electric capacity of 853 MW_e, Mexico is currently the third largest producer of geothermal power worldwide, after the USA and the Philippines. There are four geothermal fields now under exploitation: Cerro Prieto, Los Azufres, Los Humeros and Las Tres Vírgenes. Cerro Prieto is the second largest field in the world, with 720 MW_e and 138 production wells in operation; sedimentary (sandstone) rocks host its geothermal fluids. Los Azufres (88 MW_e), Los Humeros (35 MW_e) and Las Tres Vírgenes (10 MW_e) are volcanic fields, with fluids hosted by volcanic (andesites) and intrusive (granodiorite) rocks. Four additional units, 25 MW_e each, are under construction in Los Azufres and due to go into operation in April 2003. One small (300 kW) binary-cycle unit is operating in Maguarichi, a small village in an isolated area with no link to the national grid. The geothermal power installed in Mexico represents 2% of the total installed electric capacity, but the electricity generated from geothermal accounts for almost 3% of the national total.     

Hydrothermal alteration of Hercynian granites,its significance to the evolution of geothermal systems in granitic rocks

We discuss geochemical and isotopic (¹⁸O/¹⁶O, ²H/¹H and ⁸⁷Sr/⁸⁶Sr) data recording the hydrothermal alteration of northern Portuguese Hercynian granites by Na–HCO₃–CO₂-rich mineral waters. Whole-rock samples from drill cores of Vilarelho da Raia granite have δ¹⁸O values in the +11.47 to +10.10‰ range. The lower values correspond to highly fractured granite samples displaying vein and pervasive alteration. In the pervasive alteration stage, which probably results from a convective hydrothermal system set up by the intrusion of the granites, the metamorphic waters are in equilibrium with hydrous minerals. In contrast, the vein alteration of these granitic rocks was caused by water of meteoric origin. The oxygen ratios between water (W) and rock (R), the so-called W/R ratios, obtained for the open system (where the heated water is lost from the system by escape to the surface) range between 0.05 and 0.11, suggesting that the recrystallization of the veins was influenced by a small flux of meteoric water. Stable isotope analyses performed on the cores show that the vein alteration stage relates to post-emplacement tectonic stresses acting on the granite, probably of late Hercynian age. Our results are consistent with the existence of two separate alteration events (pervasive and vein) caused by hydrothermal waters of different isotopic characteristics. The studies presented in this paper should be viewed as a natural analogue that uses the alteration features observed in a “fossil” geothermal system at Vilarelho da Raia to assess possible water–rock reactions presently occurring at depth in granitic rocks of the nearby Chaves area.     

Hydrothermal alteration and fluid inclusion geothermometry of los humeros geothermal field, Mexico

The Los Humeros geothermal field, located in Puebla State, Mexico, occurs in a caldera; drillholes to 3000 m depth encountered a sequence of Quaternary lavas and pyroclastic rocks that range in composition from rhyolite to basalt but are dominantly andesitic. These rest upon the local basement comprising limestone and siltstone of Cretaceous age, which was encountered below 2500 m in the northern part of the field and 1000 m in its southern part.Examination of 29 cores, mostly from below 900 m depth, from 14 wells show that the hydrothermal minerals that occur in the volcanic host rocks include quartz, calcite, epidote, amphibole, sericite, smectite, illite, chlorite, biotite, pyrite and hematite. Their distribution mainly reflects the prevailing hydrological and thermal regime where temperatures locally exceed 300°C. The limestone basement rocks, however, have altered to an assemblage that includes calcite, quartz, wairakite, garnet, wollastonite, parawollastonite, sericite and fluorite.The homogenization temperatures of 356 fluid inclusions were measured and the freezing temperatures of 200 determined. All except two sets of inclusions homogenized into the liquid phase and neither daughter minerals nor a clathrate phase were seen. The homogenization temperatures mostly match measured bore temperatures that range from 250 to 360°C and the apparent salinities are from 0.2 to 2.7 weight per cent NaCl equivalent, but some contribution to freezing point depression by CO₂ is likely.A preliminary model for the hydrology of the field based upon the hydrothermal alteration mineralogy and fluid inclusion data suggests that dilute hot water ascends via faults in the Central Caldera collapse area of the field and moves laterally outward to elsewhere within the caldera.     

Theoretical study of ZrCoH3 and the anti-disproportionation ability of alloying elements

First-principles calculations were performed to investigate the bonding characteristics of the undoped and doped ZrCoH₃ and predict the anti-disproportionation abilities of alloying elements (i.e. Y, V, Nb, Ta, Zr, Cr, Mn, Ru, Rh, Pd and Zn). The binding between H and Zr (or its substitute elements) shows strong ionic and weak covalent feature, and that between H and Co (or its substitute elements) displays the opposite characteristic. The H diffusion process, the size of the 8e site and the corresponding ZrH distance were calculated, and the substitute elements of Zr (i.e. Nb, Ta and especially V) are predicted to be helpful to improve the ZrCo alloy against the hydrogen-induced disproportionation, and the substitute elements of Co may be not suitable.     

Chemical variations in hydrothermal minerals of the Los Humeros geothermal system, Mexico

The Los Humeros geothermal system is composed of more than 2200 m of Quaternary altered volcanic rocks and an underlying Cretaceous sedimentary sequence. The low salinity of the fluids discharged at present (Na⁺ and Cl⁻ concentrations <500 ppm), and the excess steam, indicate that the reservoir contains a mixture of steam and dilute groundwater. Water-rock equilibrium is not attained. Hydrothermal minerals are present in veinlets, vugs, and replacing primary minerals. Three mineral zones are recognized: 1) a shallow argillic zone (<400 m depth), 2) a propylitic zone (ranging between 500 and 1800 m) and 3) a skarn zone (>1800 m). Petrographic examination of cuttings from five wells and temperature data indicate at least two stages of hydrothermal activity. Temperature is the main factor that affects the chemical composition of chlorite, epidote and biotite. Fe²⁺ and Al^IV increase in chlorite with temperature [from 1.4 formula position unit (fpu) to 2.8, and from 0.7 to 2.4 fpu, respectively]. The pistacite content of epidote varies from 18 to 33 mol% in high-temperature regions (>270 °C) and from 13 to 26 mol% in low-temperature regions (<250 °C). Biotite displays a slight increase in Al^IV contents (1.55–2.8) and octahedral occupancy (5.93–6.0 fpu) with temperature. Whole rock composition and variations in oxygen fugacity conditions are factors that also affect the concentrations of Fe, Al and Mg in the octahedral sites of chlorite, epidote, biotite and amphiboles. Chemical variations observed in alteration minerals at different depths in the Colapso Central-Xalapazco region could be used as indicators of relict physico-chemical conditions in the reservoir, before the present economic exploitation.     

Geochemical characteristics of major and trace elements in Sahinali Coals,Aydin, Turkey

In this study, geochemical behavior of elements is investigated in 25 coal samples collected at 10 locations of ?ahinli coaliferous units at southeast of Ayd?n, Turkey. In all the samples, X-ray powder diffraction and inductively coupled plasma mass spectrometry analyses were performed and element and mineral compositions were determined. Total organic carbon (TOC) values of coals are between 14.6 and 37.7 wt% with average of 28.5 wt%. Samples are composed of quartz, calcite, feldspar, dolomite, mica, gypsum, and salt minerals which are accompanied by illite-, kaolinite-, and smectite-type clay minerals. Comparison of average element contents of world coals and studied samples yields that K > Fe > As > U > Cs > Y > Er > Al > Th > Rb > Yb > W > Tb > Dy > Lu > Ce > Sm > La > Ho > Si > Nd > Gd > Tm > Eu > Nb > Pr > Pb > Sn > Ni > Cu > Ga > Ta > Sb > Zr > Cd > V > Zn > Co > Mo > P > Hf > Ba are found to be enriched, while Mn > Be > Ca > Sr > Bi > Mg are found to be depleted. Statistically elements are correlated with TOC.     

Simulation of water–rock interaction in the Yellowstone geothermal system using TOUGHREACT

The Yellowstone geothermal system provides an ideal opportunity to test the ability of reactive transport models to simulate the chemical and hydrological effects of water–rock interaction. Previous studies of the Yellowstone geothermal system have characterized water–rock interaction through analysis of rocks and fluids obtained from both surface and downhole samples. Fluid chemistry, rock mineralogy, permeability, porosity, and thermal data obtained from the Y-8 borehole in Upper Geyser Basin were used to constrain a series of reactive transport simulations of the Yellowstone geothermal system using TOUGHREACT. Three distinct stratigraphic units were encountered in the 153.4 m deep Y-8 drill core: volcaniclastic sandstone, perlitic rhyolitic lava, and nonwelded pumiceous tuff. The main alteration phases identified in the Y-8 core samples include clay minerals, zeolites, silica polymorphs, adularia, and calcite. Temperatures observed in the Y-8 borehole increase with depth from sub-boiling conditions at the surface to a maximum of 169.8 °C at a depth of 104.1 m, with near-isothermal conditions persisting down to the well bottom. 1-D models of the Y-8 core hole were constructed to simulate the observed alteration mineral assemblage given the initial rock mineralogy and observed fluid chemistry and temperatures. Preliminary simulations involving the perlitic rhyolitic lava unit are consistent with the observed alteration of rhyolitic glass to form celadonite.     

Geochemical study of fluids on Lesbos island, Greece

Sixty-five water samples and seven associated gas samples have been collected on Lesbos island. The lithology and structural setting have resulted in two main types of hydrological circulation: a shallow circulation hosting low-salinity cold waters and a deeper one, hosting high-salinity hot waters that often emerge in thermal springs near the coast. The cold waters are characterized by Ca(Mg)-HCO₃(SO₄) composition, while the thermal waters generally have an Na-Cl composition. The chemical features of the former can be explained by their circulation in the ophiolite-bearing phyllitic basement and volcanic rocks. Waters circulating in the ultramafic layers of the basement are richer in Mg than the waters whose circulation is mainly within marble levels or volcanic rocks. The Na-Cl thermal waters are characterized by salinities ranging from 1910 to 35,700 mg/kg. As indicated by previous hydrogeochemical and isotopic studies, the Na-Cl composition of the thermal waters on Lesbos is the result of mixing between shallow meteoric waters and marine waters. While interacting with the minerals of the geothermal reservoir, the saline waters retain the Na/Cl sea water ratio but become enriched in Ca²⁺ and depleted in Mg²⁺ with respect to sea water.Processes of hydrothermal alteration at depth are activated by a gas phase enriched in CO₂, which reaches the geothermal reservoir by rising along the deep fractures of the basement. Thermodynamic calculations based on hydrothermal alteration processes occurring at the estimated temperatures of the geothermal reservoir (about 120 °C) indicate that the thermal waters of Lesbos are in equilibrium with talc and dolomite.     

Evaluation of the reconnaissance results in geothermal exploration using GIS

Geographical Information System (GIS) is used to determine the spatial association between geophysical and geological evidence and production zones in a well-known geothermal field (Los Azufres, Mexico). Surface observations in Los Azufres were used to delineate areas characterized by high permeability and hot fluid transport from the reservoir: main faults, superficial fracture density, surface manifestations, contacts with the most recent rhyolite domes, and low values in the apparent resistivity surveys. Three knowledge-driven models were constructed based on a conceptual model of the field: a hydrothermal system in rough terrain with secondary permeability. Boolean, Index Overlay and Fuzzy scheme models were proposed and the results obtained show a good correlation with the location of the producing and non-producing wells that have been drilled in the field. The results obtained are useful for well siting (Boolean and Low-Risk Fuzzy models) or for planning further detailed exploration (Index Overlay and High-Risk Fuzzy models).     

Development of a numerical hydraulic model of the Los Azufres steam pipeline network

The development and documentation of a hydraulic model of the steam pipeline network at the Los Azufres geothermal field is presented, as well as the results obtained using one- and two-phase numerical simulators. Flow simulations were performed to determine pressure and heat losses, flow directions and velocities in that network. Computed well pressures agree within ±10% with measured values, except in three of the 41 wells in the system where the differences are between 10% and 13%. Computed and measured steam flow rates entering the Los Azufres geothermal power plants agree within 10%, with the exception of one that showed a 26.7% difference. This is most likely due to a mismatch between the reported and actual flow rates delivered by the pipeline network. The computed results are considered highly satisfactory given the complexity of the Los Azufres network.     

Chemical analyses of geothermal waters and strategic petroleum reserve brines for metals of economic importance

Waters from seven hydrothermal-geothermal, one geopressured-geothermal, and six Strategic Petroleum Reserve wells have been surveyed for 12 metals of economic importance using trace chemical analysis techniques. The elements sought were Cr, Co, Mn, Ta, Sn, V, Nb, Li, Sr, Pt, Au and Ag. Platinum was found at a concentration of 50 ppb in a brine from the Salton Sea geothermal area. Brine from this region, as has been known from previous studies, is also rich in Li, Sr and Mn. Higher concentrations (900 ppm) of Sr are found in the high-salinity geopressured brines. None of the fluids contained interesting concentrations of the other metals. Good recovery of precious metals at sub-ppm concentrations from synthetic high salinity brines was achieved using Amborane reductive resin, but similar recovery in the laboratory using real brines could not be demonstrated. Several analytical techniques were compared in sensitivity for the determination of the precious metals; neutron activation analysis with carrier separation is the best for gold and platinum in geothermal brines.     

Temperature–depth relationships based on log data from the Los Azufres geothermal field,Mexico

Equilibrium temperatures based on log data acquired during drilling stops in the Los Azufres geothermal field were used to study the relationship between temperature, depth and conductive heat flow that differentiate production from non-production areas. Temperature and thermal conductivity data from 62 geothermal wells were analyzed, displaying temperature–depth, gradient–depth, and ternary temperature–gradient–depth plots. In the ternary plot, the production wells of Los Azufres are located near the temperature vertex, where normalized temperatures are over 0.50 units, or where the temperature gradient is over 165°C/km. In addition, the temperature data were used to estimate the depth at which 600°C could be reached (5–9 km) and the regional background conductive heat flow (≈ 106 mW/m²). Estimates are also given for the conductive heat flow associated with the conductive cooling of an intrusive body (≈ 295 mW/m²), and the conductive heat flow component in low-permeability blocks inside the reservoir associated with convection in limiting open faults (from 69 to 667 mW/m²). The method applied in this study may be useful to interpret data from new geothermal areas still under exploration by comparing with the results obtained from Los Azufres.     

Ti/Zr ratio as a geochemical tool for the correlation of weathered coals from geological formations in two Latin American sedimentary basins

Major and trace element concentrations in fresh and altered coals in outcrops and coalfields from Táchira and Mérida states (Venezuela), as well as from Napo and Pastaza provinces (Ecuador), have been determined to establish inorganic parameters not dependent of weathering effects. Noteworthy is that the Ti/Zr ratio is approximately constant in each sedimentary basin even for great distances (>100 km). Worldwide data of trace elements analysis in coal samples support the stated Ti/Zr ratio constancy in different basins for fresh and weathered ones. Therefore, Ti/Zr ratio can be considered a rapid tool to easily identify coal seam correlations.     

Intermetallics as cathode materials in the electrolytic hydrogen production

The intermetallics of transition metals have been investigated as cathode materials for the production of hydrogen by electrolysis from water–KOH solutions, in an attempt to increase the electrolytic process efficiency. We found that the best effect among all investigated cathodes (Hf₂Fe, Zr–Pt, Nb–Pd(I), Pd–Ta, Nb–Pd(II), Ti–Pt) exhibits the Hf₂Fe phase. These materials were compared with conventional cathodes (Fe and Ni), often used in the alkaline electrolysis. A significant upgrade of the electrolytic efficiency using intermetallics, either in pure KOH electrolyte or in combination with ionic activators added in situ, was achieved.The effects of these cathode materials on the process efficiency were discussed in the context of transition metal features that issue from their electronic configuration.     

辽河坳陷火山岩岩性特征及储层评价

辽河坳陷火山岩主要为玄武岩、粗面岩、响岩、安山岩、流纹岩和凝灰岩,以抗压强度较弱的少含暗色矿物的粗面岩和流纹岩为主.粗面岩主要分布在东部凹陷第三系,流纹岩主要分布在西部凹陷中生界.岩石化学分析表明,以浅色造岩矿物为主的火山岩抗压强度低,在应力作用下容易形成裂缝,而含暗色矿物较多的火山岩,抗压强度高,在相同应力下难以形成裂缝,并且暗色矿物蚀变后形成的绿泥石、方解石等,往往将早期形成的裂缝充填.运用岩石化学分析和测井响应特征,分别建立火山岩岩性和火山岩储层划分标准;同时,根据中子和电阻率测井响应特征,将火山岩划分为轻度蚀变、中度蚀变、重度蚀变和泥化火山岩4类.应用氧化物分析法,可将东部凹陷火山岩区分开;利用能谱测井,可将西部凹陷的火山岩划分出来:采用测井交会图法,可以划分辽河坳陷火山岩储层.     

Geothermal resources of Hachijojima

Hachijojima is a gourd-shaped volcanic island in the Pacific Ocean. Nishiyama and Higashiyama volcanoes consist of basalt lava and associated pyroclastic rocks. A promising geothermal resource was found in south Higashiyama, associated with an uplift of Tertiary rocks consisting of mainly andesite lava and related pyroclastic rocks, overlain by Quaternary volcanic rocks. Steep high-temperature (over 250°C) and high-pressure gradients occur in the deeper portion of the system near the Tertiary–Quaternary contact, indicating the presence of a cap rock. The cap rock formed by deposition of hydrothermal minerals. Geothermal fluid ascends from the deeper portions to shallow depths along vertical fractures through the cap rock. These vertical fractures form the geothermal reservoir in the Tertiary formation. Three wells were drilled into these vertical fractures, and approximately 30 t/h of superheated steam was obtained from each well during flow tests. The geothermal fluid is mainly a mixture of seawater and meteoric water in an approximate ratio of 1 to 2, based on chemical analyses, with a portion of volcanic gas included. At present a 3.3 MW_e, geothermal power plant is being constructed here.     

SolGeo: A new computer program for solute geothermometers and its application to Mexican geothermal fields

The freely available computer program Solute Geothermometers (SolGeo) was written and tested using geochemical data and reported geothermometric temperatures from several geothermal wells from around the world. Subsurface temperatures for the Mexican geothermal fields of Cerro Prieto, Las Tres Vírgenes, Los Azufres, and Los Humeros were estimated based on different solute geothermometers and found to be generally in close agreement with measured well temperatures when considering errors in the calculations and measurements. For Los Humeros wells it was concluded that a better agreement of chemical geothermometric temperatures is observed with static formation than with bottom-hole temperatures (BHTs). It was also found that the widely used Na–K geothermometric equations generally give more consistent and more reliable temperature estimates than the other geothermometers, which should therefore be applied with caution.     

Nano-scale bi-layer Pd/Ta, Pd/Nb, Pd/Ti and Pd/Fe catalysts for hydrogen sorption in magnesium thin films

We analyzed the elevated temperature volumetric hydrogen sorption behavior of magnesium thin films catalyzed by nano-scale bi-layers of Pd/Ta, Pd/Nb, Pd/Ti and Pd/Fe. Sorption of magnesium catalyzed by pure Pd was determined as a baseline. Sorption cycling demonstrated that when utilizing pure Pd and the Pd/Fe bi-layer catalysts the sorption kinetics of the Mg films rapidly degraded. However with the Pd/Nb, Pd/Ti and Pd/Ta bi-layer catalysts the composite remained cycleable. After multiple sorption cycles the Pd/Nb and Pd/Ti catalyst combinations possessed the fastest kinetics. X-ray diffraction analysis showed that NbH_0.5 and TiH₂ are formed during testing. Basic thermodynamic analysis indicates that NbH_0.5 and TiH₂ should be stable both during absorption and during desorption. We believe that this is why Nb and Ti are the most effective intermediate layers: The elements form stable hydrides at the Mg surfaces preventing complete Pd-Mg interdiffusion and/or acting as hydrogen catalysts and pumps.