Fluid-inclusion evidence for previous higher temperatures in the miravalles geothermal field, Costa Rica

Heating and freezing data were obtained for liquid-rich secondary fluid inclusions in magmatic quartz, hydrothermal calcite and hydrothermal quartz crystals from 19 sampled depths in eight production drill holes (PGM-1, 2, 3, 5, 10, 11, 12 and 15) of the Miravalles geothermal field in northwestern Costa Rica. Homogenization temperatures for 386 fluid inclusions range from near the present measured temperatures to as much as 70°C higher than the maximum measured well temperature of about 240°C. Melting-point temperature measurements for 76 fluid inclusions suggest a calculated salinity range of about 0.2–1.9 wt% NaCl equivalent. Calculated salinities as high as 3.1–4.0 wt% NaCl equivalent for 20 fluid inclusions from the lower part of drill hole PGM-15 (the deepest drill hole) indicate that higher salinity water probably was present in the deeper part of the Miravalles geothermal field at the time these fluid inclusions were formed.     

Thermal and petrologic study of the CH-A well from the Chipilapa-Ahuachapán geothermal area, el salvador

Systematic petrological studies were performed at 10-m intervals along the 2700-m-deep Ch-A well. Results show mineralogical variations that define four zones which, in turn, represent different thermal zones. The shallowest zone (Zone l) is characterized by the presence of chalcedony + zeolites + amorphous silica + saponite + montmorillonite + minor amounts of pyrite and calcite; Zone 2 by chlorite + quartz + smectite + zeolites; Zone 3by chlorite + quartz + calcite + epidote + abundant pyrite and hematite + mixed-layeredillite-smectite + chalcopyrite; andZone4 byepidote + clinozoisite + gypsum + sericite + mixed-layered chlorite-illitesmectite + anyhdrite. Fluid inclusion analyses performed at 100-m intervals indicate that a low-to-moderate salinity fluid with ice-melting temperatures of -0.7 to -2.2°C was involved in the hydrothermal alteration of the rocks. At shallow depths, positive values of + 1.6°C were found, which probably indicate an increase in volatile components. Minimum homogenization temperatures gradually increased with depth. They range from 110°C at very shallow depths (153 m) to 244°C at total depth (2700 m); however, peak or maximum temperatures of 265–286°C are found at various depths between 1400 and 2500 m. Bottom-hole fluid inclusion temperatures agree well with static temperatures derived from the Homer (1951) and the Ascencio et al. (1994) methods. Comparisons at other depths show that, in general, Homer temperatures are the lowest and that fluid inclusion temperatures are the highest, except at about 1200 m depth where the Ascencio et al. (1994) method gives the largest values. It is believed that well Ch-A encountered a mineral paragenesis that does not correspond with present thermodynamic conditions of the reservoir and that the geothermal system has undergone natural cooling.     

Fluid-inclusion evidence for past temperature fluctuations in the Kilauea East Rift Zone geothermal area, Hawaii

Heating and freezing data were obtained for fluid inclusions in hydrothermal quartz, calcite, and anhydrite from several depths in three scientific observation holes drilled along the lower East Rift Zone of Kilauea volcano, Hawaii. Compositions of the inclusion fluids range from dilute meteoric water to highly modified sea water concentrated by boiling. Comparison of measured drill-hole temperatures with fluid-inclusion homogenization-temperature (T_h) data indicates that only about 15% of the fluid inclusions could have formed under the present thermal conditions. The majority of fluid inclusions studied must have formed during one or more times in the past when temperatures fluctuated in response to the emplacement of nearby dikes and their subsequent cooling. The fluid-inclusion data indicate that past temperatures in SOH-4 well were as much as 64°C hotter than present temperatures between 1000 and 1500 m depth and they were a maximum of 68°C cooler than present temperatures below 1500 m depth. Similarly, the data show that past temperatures near the bottoms of SOH-1 and SOH-2 wells were up to 45 and 59°C, respectively, cooler than the present thermal conditions; however, the remainder of fluid-inclusion T_h values for these two drill holes suggest that the temperatures of the trapped waters were nearly the same as the present temperatures at these slightly shallower depths. Several hydrothermal minerals (erionite, mordenite, truscottite, smectite, chlorite-smectite, chalcedony, anhydrite, and hematite), occurring in the drill holes at higher temperatures than they are found in geothermal drill holes of Iceland or other geothermal areas, provide additional evidence for a recent heating trend.     

Application of fluid inclusions to the study of Bagnore geothermal field (Tuscany, Italy)

A fluid inclusion study of the hydrothermal minerals in two breccias from two wells in the Bagnore geothermal field (Italy) has provided information on the evolution of the fluids, and has also demonstrated that fluid inclusions can be utilized as geothermometers in this geothermal field. Both breccias come from reservoir zones: one (Bagnore 3bis (Bg 3bis)) was cored at a depth of 3111 m below ground level (b.g.l.), whereas the other (Bagnore 22 (Bg 22)) was ejected during a blow-out, probably from a fractured zone present between 2200 and 2300 m b.g.l. The hydrothermal cement of the breccias is mostly made up of quartz, K-feldspar, Na-rich plagioclase, calcite, chlorite and illite. Fluid inclusion studies were carried out on quartz (Bg 3bis and Bg 22 breccias) and adularia (Bg 22 breccia). Three types of fluid inclusions were recognized in the Bg 3bis breccia. Type I (liquid-rich) inclusions trapped an aqueous fluid with a CO₂ concentration (1.7–2.7 mol/kg) that is significantly higher than present-day fluids (0.5 mol/kg). Type II (liquid-rich) inclusions formed after type I, and trapped a fluid with less CO₂ (0.6–1.0 mol/kg). Type III (vapor-rich) coexist with type I inclusions, and record an early fluid circulation under boiling conditions. The decrease of the CO₂ (and total gas) concentrations from type I inclusions to type II inclusions, and on to present-day conditions can be related to boiling with gas loss and/or mixing. Only one type of fluid inclusion (type II), with moderate CO₂ concentration (0.7–0.3 mol/kg), was found in the Bg 22 breccia. Boiling and/or mixing explain the variation of the CO₂ content in the Bg 22 reservoir fluid from inclusion formation to modern CO₂ concentration (0.3 mol/kg). The absence of any type I inclusions in Bg 22 breccia may be related to non-uniform CO₂ concentrations in different parts of the field. Present-day temperatures (295±10 °C for Bg 3bis and 320±10 °C for Bg 22) are close or equal to fluid inclusion average total homogenization temperatures (around 290 °C for Bg 3bis and 320 °C for Bg 22), suggesting that fluid inclusions can be useful for estimating local temperatures when direct measurements are not available or dubious.     

Hydrothermal alteration in the Aluto-Langano geothermal field, Ethiopia

The hydrothermal mineral assemblages found in eight wells (with a depth range of 1320–2500 m) of the active geothermal field of Aluto-Langano (Ethiopia) indicate a complex evolution of water-rock interaction processes. The zone of upflow is characterized by high temperatures (up to 335°C) and the presence of a propylitic alteration (epidote, calcite, quartz and chlorite, as major phases) coexisting with calcite and clay minerals. The zone of lateral outflow is characterized by mixing of deep and shallow waters and the occurrence of a calcite-clay alteration that overprints a previous propylitic assemblage. Clay minerals have a mushroom-shaped zonal distribution consistent with the present thermal structure of the field. Microprobe analyses have been carried out on chlorite and illite in order to apply several geothermometers. Most of the chlorite is iron-rich chlorite. It is found that the temperatures calculated from the chlorite geothermometer (159–292°C) after Cathelineau and Nieva [Contrib. Mineral. Petrol. 91, 235–244 (1985)] are in good agreement with in-hole measured temperatures (155–300°C). In the upflow zone, temperatures calculated from this geothermometer (217–292°C), together with fluid inclusion data of Valori et al. [Eur. J. Mineral. 4, 907–919 (1992)], and computed saturation indices of alteration minerals, indicate thermal stability or slight heating. On the other hand, evidence of a significant cooling process (up to 171°C) in the outflow zone is provided by the comparison between fluid inclusion homogenization temperature (240–326°C) and in-hole temperature (155–250°C). The apparent salinities (0.8–2.3 wt% NaCl eq.) of the fluid inclusions are generally higher than the salinity of the present reservoir fluid (0.29–0.36 wt% NaCl eq.). Clay minerals (illite, smectite, Ill/S mixed layers, vermiculite and chloritic intergrades) generally occur at temperatures consistent with their stability fields.     

Hydrothermal alteration mineralogy as an indicator of hydrology at the Ngawha geothermal field,New Zealand

Interaction between geothermal fluids and the rocks through which they migrate alters many earlier formed minerals and produces others. The minerals thus formed preserved evidence of hydrological conditions prevailing within an active geothermal system; in particular, they can reflect the range of temperatures under which they formed. This feature was tested at the Ngawha geothermal system, which is different from others in New Zealand in that its reservoir comprises fractured basement rocks covered by a 500–600m thick sequence of sedimentary rocks. Petrographic examination of cores and cuttings recovered from drillholes at Ngawha shows that the secondary minerals present within the rock matrices and veins are of different ages. The thermally sensitive minerals include epidote, titanite, biotite and clays, including some that are interlayered. Comparison of the measured downwell temperatures with those deduced from the secondary mineralogy and by homogenizing fluid inclusions, shows that the central part of the field has remained thermally stable since the youngest secondary minerals deposited there but its southern margin has cooled by 20–40°C or perhaps more. A likely cause of this is an inflow of cooler water from the east, which also causes the temperature inversion clearly evident in hole Ng8. By contrast, some fluid inclusion geothermometry results suggest that the northern part of the drilled field has heated since their host hydrothermal quartz crystals formed.     

Hydrothermal alteration minerals in Aluto Langano geothermal wells, Ethiopia

Aluto Langano geothermal field is characterized by alteration mineral assemblages of calcite, quartz, chlorite, undifferentiated clays, hematite, biotite and epidote. The presence of garnet and sphene is also reported for one of the wells. Measured temperature for the reservoir is above 300°C. Permeability of the reservoir is highly influenced by the deposition of hydrothermal minerals.     

Element mobility during the hydrothermal alteration of rhyolitic rocks of the Los Azufres geothermal field, Mexico

The effects of hydrothermal alteration on major, rare-earth, and other trace-element concentrations in rhyolitic rocks of the Los Azufres geothermal field, Mexico, were investigated by statistically comparing the chemical compositions of altered drill cuttings (taken above 450 m depth) with those of fresh rock outcrop samples. Altered rhyolitic rocks show predominantly vitreous and fluidal textures, with alteration products (mainly clay minerals, chlorites and, less commonly, sericite) comprising up to 40% of the rock mass; cryptocrystalline quartz, chlorite, and zeolites fill fractures and vesicles. In altered rocks the greater statistical variances of several elements (Y, Ce, Pr, Nd, Sm, Lu, and Pb) are probably due to alteration effects, whereas smaller variances for CaO, Sr, Rb/Sr, and Rb/Ba suggest that alteration processes have resulted in more uniform chemical compositions. Only MnO, P₂O₅, Ta, Zr, and Nb have significantly different concentrations in hydrothermal altered rocks as compared to fresh rocks. MnO, P₂O₅, Ta, Rb/Zr, and Rb/Nb decrease, whereas Zr, Nb, and Nb/Y increase in the altered rocks. The present study stresses that caution should be taken when using these chemical parameters for petrogenetic studies of old hydrothermally altered areas, particularly with rhyolitic rocks. Rare-earth element (REE) concentrations were not significantly different between fresh and altered rhyolitic rocks. This may indicate that these elements were relatively immobile during the hydrothermal alteration processes affecting the rhyolites at Los Azufres, or more likely that they were reincorporated into hydrothermal minerals after being mobilized from the primary phases.     

Fluid-rock interaction processes in the Te Kopia geothermal field (New Zealand) revealed by SEM-CL imaging

Scanning electron microscopy-cathodoluminescence (SEM-CL) imaging of hydrothermal quartz exposed by weathering in the Te Kopia geothermal field (New Zealand) has revealed a history of crystal growth, dissolution, overprinting and fracturing that cannot be detected using other observational techniques (e.g. transmitted or reflected light microscopy, back-scattered electron imaging or secondary electron imaging). The crystals initially grew as CL-dark quartz, at least 350 m below their present location on the Paeroa Fault scarp, in a neutral pH, 215±10 °C liquid reservoir (inferred from the analysis of primary liquid fluid inclusions: mean T_h of 213 °C; 0.2–0.4 wt.% NaCl_eq.). Relict quartz–adularia–illite alteration occurs at the surface, in the vicinity of the quartz crystals, and in drillcores from the nearby TK-1 exploration well. Repeated movement on the Paeroa Fault uplifted pyroclastic rocks hosting the quartz crystals, but also provided pathways for “pulses” of hot fluids to move through the system. Quartz precipitation occurred at the edge of the crystals as the reservoir fluids cooled, as indicated by micron-scale alternating CL-dark/CL-bright quartz growth bands, which contain fluid inclusions with T_h values of 210±40 °C. Pressure fluctuations were the likely cause of dissolution, marked by corroded crystal edges, with subsequent precipitation of quartz into open space. SEM-CL imaging shows that the quartz crystals contain healed fractures, which trapped low salinity fluids with T_h values of 201±6 °C. Low-pH fluids in the near-surface setting also rounded the quartz crystals, and coated them with kaolinite and CL-grey amorphous “silica residue”.     

Hydrothermal mineral zones in the geothermal reservoir of Cerro Prieto

Detailed petrologic studies completed to date on ditch cuttings and core from 23 wells in the Cerro Prieto field have led to recognition of regularly distributed prograde metamorphic mineral zones. The progressive changes in mineralogy exhibit a systematic relationship with reservoir temperature.The Cerro Prieto reservoir consists of a series of sandstones, siltstones, and shales composing part of the Colorado River delta. The western part of the field contains relatively coarser sediments apparently also derived from the delta and not from the basin margins as formerly thought. The most abundant detrital minerals in the sediments include quartz, feldspar, kaolinite, montmorillonite, illite, chlorite, mixed-layer clays, calcite, dolomite and iron hydroxides. Some of these minerals were also formed diagenetically.The following progressive stages of post-depositional alteration in response to increasing temperature have been observed: (1) diagenetic zone (low temperature), (2) illite-chlorite zone (above ~ 150°C), (3) calc-aluminum silicate zone (above ~ 230°C) and the biotite zone (above ~ 325°C). These zones are transitional to some degree and can be further subdivided based on the appearance or disappearance of various minerals.One immediate application of these studies is the ability, from a study of cuttings obtained during drilling of a well, to predict the temperatures which will be observed when the well is completed.     

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.     

The shallow structure of Los Humeros and Las Derrumbadas geothermal fields, Mexico

Los Humeros caldera and Las Derrumbadas rhyolitic domes located in the State of Puebla (Mexico) are being extensively studied by Comisión Federal de Electricidad (CFE) to assess the geothermal potential of that area. Both geothermal sites have been locally studied with geological, geochemical and geophysical methods. In order to get a geological picture of the sub-surface of the area comprising both sites, a regional structural survey was conducted together with gravity and magnetics studies. These studies showed a regional weakness zone (the Libres-Oriental depression), where the volcanic activity related to the geothermal manifestations took place.The tectonic events in the area are represented by two systems of structures. The first one (N140°–N170°) gave rise to the folds and overthrusts affecting the sequence of calcareous rocks resting upon the basement. This system is affected by a second system (N40°–70°E). Regionally these tectonic events remodelled the sedimentary sequence giving rise to a series of topographic highs that constitute the core of several ranges, and to depressions that were filled with volcano-sediments during the ensuing volcanic activity.The rhyolitic domes of Las Derrumbadas are emplaced in a regional NW-SE lineament, which reflects clearly on the Bouguer anomaly, and is interpreted as a front of overthrust affecting the marine sedimentary sequence. Estimations of depths to the basement, based on magnetic data, showed that the basement under Los Humeros caldera is shallower than in Las Derrumbadas. The gravity data were interpreted in terms of tabular bodies associated to calcareous rocks, of igneous intrusions, and of depressions filled with volcano-sediments. A joint interpretation of the geological and geophysical data led to a model of the structure of the shallow crust in the area.     

Genesis of the plutonic-hydrothermal system around quaternary granite in the kakkonda geothermal system, Japan

The Kakkonda plutonic-hydrothermal system has as its heat source the Quaternary Kakkonda granite. The Kakkonda granite has a thick (1.3 km) contact-metamorphic zone, known mainly from the geothermal survey well WD-1a (total depth: 3729 m) drilled by the New Energy and Industrial Technology Development Organization (NEDO). The Kakkonda granite is a stock several tens of square kilometers in area with an upper contact about 1.5–3 km deep. It is a composite pluton varying from tonalite to granite. The early-stage granitic rocks are slightly metamorphosed to biotite grade by late-stage granitic rocks. K-Ar ages of separated minerals from the granitic rocks in both stages show the same cooling ages of 0.24–0.11 Ma for hornblende, 0.21–0.02 Ma for biotite, and 0.14–0.01 Ma for potassium feldspar. These are the youngest ages for granite in the world. The K-Ar ages become almost zero at 580°C for biotite and potassium feldspar, and at 350°C for illite. The Kakkonda granite intruded into a regional stress field in which the minimum principal stress was ENE–WSW and nearly horizontal. The regional stress field coincides with that of a previously recognized F2 fracture system before 0.4–0.3 Ma. Both stages of the Kakkonda granite and the contact aureole are fractured by recent tectonism, resulting in a zone of hydrothermal convection from about 2.5–3.1 km depth up to the surface. The boundary between the zone of hydrothermal convection and the underlying zone of heat conduction occurs 250–550 m below the upper contact of the Kakkonda granite, and has a temperature of 380–400°C.     

Observations on the application of chemical geothermometers to some hydrothermal systems in Sardinia

There are many empirical geothermometers that utilize the composition of the elements dissolved in water, yet it is difficult to judge just how reliable they are when applied to low enthalpy thermal systems.The main objective of this paper is to show how a reasonable estimate of the temperature of some typical thermal systems in Sardinia can be obtained from the calculation of the saturation indices of water with some silicates in the local rock matrix. Despite some uncertainties, mainly regarding possible mixing phenomena, the applied methodology appears to give more reliable reservoir temperature values than those given by the empirical geothermometers.The method has been applied to thermal waters circulating in the crystalline basement rocks (granites) and in the sedimentary cover rocks (mainly volcanic effusive products, andesitic lava, ignimbrites, etc.). The temperatures calculated for the hydrothermal systems range between 50 and 110°C.     

Geochemistry of the thermal waters of Salbardi and Tatapani, India

Geochemical studies have been carried out on water samples collected from Tatapani and Salbardi hot springs. The waters of these hot springs are classified as NaHCO₃ type. Waters in deep aquifers are associated with quartz, shale and clay terrains. Activity studies of the minerals and the waters present in the aquifers suggest that the thermal waters are within equilibrium with montmorillonite, kaolinite and quartz at about 150°C. The geochemical thermometers also estimate 150 ± 10°C as aquifer temperatures for Tatapani and Salbardi.     

Hydrothermal activity in the Tulancingo–Acoculco Caldera Complex,central Mexico: Exploratory studies

Mineral alteration and fluid inclusion studies of drill cuttings and core samples indicate that the sedimentary basement rocks and the volcanic rocks associated with Tulancingo–Acoculco Caldera Complex have been the site of two distinct and major hydrothermal events. The complex, located in the eastern portion of the Trans-Mexican Volcanic Belt, is formed by the Pliocene Tulancingo Caldera and the younger (Pleistocene) Acoculco Caldera, which developed within the older depression. The volcanic rocks are underlain by Cretaceous sedimentary rocks of the Sierra Madre Oriental. The earliest important hydrothermal event occurred during the emplacement of Mid-Tertiary granitic intrusions that metamorphosed the sedimentary rocks; these intrusives are not exposed at the surface. However, granitic rocks were encountered at the bottom of exploratory borehole EAC-1, drilled within the Caldera Complex. The second main event occurred during the formation of the Tulancingo and Acoculco Calderas. Both episodes lead to secondary mineralization that reduced the permeability of the reservoir rocks. A possible third hydrothermal event may be associated with the recent magmatic activity within the Acoculco Caldera.Thermal logs from well EAC-1 display a conductive thermal gradient with maximum temperatures exceeding 300 °C at 2000 m depth. Although there are no active thermal springs in the area, there is extensive fossil surface hydrothermal alteration and cold gas discharges with high He³/He⁴ ratios.     

Contact metasomatic and hydrothermal minerals in the SH2 deep well, Sabatini volcanic district, Latium, Italy

Metasomatic and hydrothermal minerals were logged throughout the SH2 geothermal well, which reached a depth of 2498 m in the Sabatini volcanic district. Below 460 m of volcanics, where the newly formed minerals were mainly chlorite, calcite and zeolites (mostly phillipsite), drilling entered the Allochthonous Flysch Complex. Evidence of the “Cicerchina facies” was found down to 1600 m depth. Starting from 1070 m, down to hole bottom, a contact metasomatic complex was defined by the appearance of garnet. Garnet together with K-feldspar, vesuvianite, wilkeite, cuspidine, harkerite, wollastonite and apatite prevail in the top part of the contact metasomatic complex. Vesuvianite and phlogopite characterize the middle part. Phlogopite, pyroxene, spinel and cancrinite predominate in the bottom part. The 1500 m thick metasomatic complex indicates the presence at depth of the intrusion of a trachytic magma which released hot fluids involved in metasomatic mineral-forming reactions. Minerals such as harkerite, wilkeite, cuspidine, cancrinite, vesuvianite and phlogopite indicate the intrusive melt had a high volatile content which is in agreement with the very high explosivity index of this volcanic district.The system is at present sealed by abundant calcite and anhydrite. It is proposed that most, if not all, of the sulphates formed after reaction of SO₂ with aqueous calcium species rather than from sulphates being remobilized from evaporitic (Triassic) rocks as previously inferred. The hypothesis of a CO₂-rich deep-derived fluid ascending through major fracture systems and contrasting cooling in the hottest areas of Latium is presented.     

Isotopic and fluid inclusion study of hydrothermal and metamorphic carbonates in the Larderello geothermal field and surrounding areas, Italy

Fluid inclusions have been studied on six calcite veins from the shallow part (480 to 1515 m below ground level) of the Larderello geothermal field and outcropping in peripheral zones of the geothermal area. Oxygen and carbon isotopic analyses have been carried out on these carbonate veins, as well as on the dolostone layers found inside the Paleozoic metamorphic units of the deep part of the field (from 1939 to 3177 m below ground level). Fluid inclusion observations suggest that boiling processes probably occurred during calcite precipitation in most of the veins. The fluids that formed or interacted with the calcite veins below the uppermost reservoir (made up of Mesozoic marine carbonates), and with the calcite hydrothermal veins of Sassa, were characterised by an apparent salinity from 1.3 to 5.3 wt.% NaCl eq. and a homogenisation temperature from 137 to 245°C. The fluid inclusions related to the calcite veins hosted above the uppermost reservoir show a wide range of apparent salinity (from 1.7 to 22.2 wt.% NaCl eq.) and homogenisation temperatures from 224 to 296°C. Apparent salinity/homogenisation temperature covariations of the latter veins are interpreted as being the result of a mixing process between a low-temperature, high-salinity fluid and a higher-temperature, moderate-salinity fluid. The oxygen isotopic compositions of the calcite veins (δ¹⁸O from 10.34 to 11.45‰) located below the Mesozoic carbonates and in the outcrops (δ¹⁸O from 9.42 to 17.07‰) indicate that the vapour in equilibrium with these veins was isotopically similar to the present-day discharge steam. The aqueous fluids in equilibrium with these veins could be meteoric water that interacted with the Mesozoic carbonates of the upper reservoir. The δ¹³C values of the CO₂ produced at Larderello and the constant concentration of this gas over time are, however, indicative of a deep source inside the reservoir that is probably related to the decarbonation reaction within the metamorphic units that form the present-day deep reservoir. Fluid inclusion salinities (up to 22.2 wt.% NaCl eq.) and isotopic results (δ¹⁸O from 13.43 to 21.99‰, δ¹³C between −1.26 and −0.18‰) on the calcite veins hosted above the uppermost reservoir suggest that the water circulating in these veins has strongly interacted with Mesozoic carbonates or Neogene sediments containing evaporite layers. The isotopic values (δ¹⁸O from 14.09 to 19.91‰, δ¹³C from −4.09 to 1.90‰) of dolomite samples present in the Paleozoic metamorphic rocks indicate a reaction with fluid of variable temperatures under different water/rock ratios. The isotopic composition of one sample reveals equilibrium with present-day discharge fluids. This fact aside, the remaining data indicate that the Paleozoic dolomitic layers do not seem to contribute significantly to the production of CO₂.     

Fluid inclusion study of the Kirishima geothermal system, Japan

Gases from fluid inclusions in quartz and anhydrite were analyzed with a quadrupole mass spectrometer and a capacitance manometer. The quartz and anhydrite occur in hydrothermal veins in volcanic and pelitic rocks collected from geothermal wells in the Kirishima area, southwest Japan. The geothermal wells are located in a graben made up of Quaternary volcanic rocks underlain by sedimentary rocks of the Shimanto Group.Results of individual fluid inclusion analyses show that the fluid inclusions comprise mainly H₂O and a variable but small amount of CO₂. CH₄ and other hydrocarbons are also detected in inclusions in a hydrothermal sample from the pelitic Shimanto Group. Peak ratios of CO₂/H₂0 in individual fluid inclusions are variable in some samples. This indicates that there is a difference in gas compositions of the fluid inclusions, and suggests that the inclusions were formed in multistages or trapped heterogeneous boiling fluids.Results of bulk analyses show that the inclusions are mainly composed of H₂O (98–99 mol%) with small amounts of non-condensable gases, mainly C0₂ and N₂, CH₄ and Ar. The proportion of N₂ is about one order of magnitude lower than C0₂, CH₄ is generally two orders of magnitude lower than C0₂ and Ar is just above the detection limit of the mass spectrometer. The gas concentration in the fluid inclusions is much higher than that in the present-day discharge fluids in this area. CO₂/N₂ and C0₂/CH₄ ratios of the fluid inclusions from the volcanic rocks are lower than those of the present-day discharge fluids. CO₂/N₂ and CO₂/CH₄ ratios in residual fluids increase with progressive degassing, because N₂ and CH₄ are released from the residual fluids more easily than CO₂. Thus, the difference in the CO₂/N₂ and CO₂/CH₄ ratios between the fluid inclusions and the present-day discharge fluids in the Kirishima area may be ascribed to the degree of degassing, and the fluid inclusions in the area were probably formed by trapping fluids that were weakly influenced by degassing. P_co2, values calculated from the gas compositions of the fluid inclusions are higher than that of buffer systems involving alteration minerals in the area. This suggests that the fluid inclusions might be trapped fluids which were not in equilibrium with the alteration mineral assemblages, that is, fluids prior to considerable degassing and alteration.