The use of geochemical indicator elements in the exploration for hot water sources within geothermal fields

Soils, rocks, altered rocks, hot and cold waters, and hot spring precipitates were sampled within and on the outskirts of geothermal fields in China. The contents of thirty trace elements in soils and rocks show that Hg, As, Sb, Bi, Li, Rb, Cs, Au, Ag, B, W, Sn, Pb, Zn, Mn, Ni and Co can serve as direct and indirect indicators for geothermal field exploration. Large amounts of data indicate that Hg, As and Sb are the best indicators of hot water sources. Altered rocks contain higher Hg, As, Sb, Bi and Be than unaltered rocks. Based on their abundances in hot waters, it is suggested that the following elements may be used as hydrochemical indicators of high-temperature hot-water geothermal systems: K⁺, Na⁺, Ca²⁺, Mg²⁺, SO²⁻₄, HCO⁻₃, F⁻, Cl⁻, SiO₂, HBO₂, CO₂, pH, total dissolved solids and hydrochemical types, as well as Hg, As, Sb, Be, Li, Rb and Cs. Modern precipitates associated with hot springs have high contents of Ba, Be, Fe, Ti, Hg, As, Sb and Bi. Using these geochemical data, the authors have had much success in locating hot water drill sites within geothermal fields. Case histories are described for five geothermal areas.     

Soil CO2 flux measurements in volcanic and geothermal areas

The accumulation chamber methodology allows one to obtain reliable values of the soil CO₂ flux, ϕ_{soil CO2}, in the range 0.2 to over 10 000 g m⁻² d⁻¹, as proven by both laboratory tests and field surveys in geothermal and volcanic areas. A strong negative correlation is observed between Δϕ_{soil CO2}/Δt and ΔP_atm/Δt. Maps of classes of log ϕ_{soil CO2} for the northern sector of Vulcano Island, Solfatara of Pozzuoli, Nea Kameni Islet and Yanbajain geothermal field evidence that active faults and fractures act as uprising channels of deep, CO₂-rich geothermal or magmatic gases. The total diffuse CO₂ output was evaluated for each surveyed area.     

Geological and geochemical characteristics of the Baogudi Carlin-type gold district (Southwest Guizhou,China) and their geological implications

The newly discovered Baogudi gold district is located in the southwestern Guizhou Province, China, where there are numerous Carlin-type gold deposits. To better understand the geological and geochemical characteristics of the Baogudi gold district, we carried out petrographic observations, elemental analyses, and fluid inclusion and isotopic composition studies. We also compared the results with those of typical Carlin-type gold deposits in southwestern Guizhou. Three mineralization stages, namely, the sedimentation diagenesis, hydrothermal (main-ore and late-ore substages), and supergene stages, were identified based on field and petrographic observations. The main-ore and late-ore stages correspond to Au and Sb mineralization, respectively, which are similar to typical Carlin-type mineralization. The mass transfer associated with alteration and mineralization shows that a significant amount of Au, As, Sb, Hg, Tl, Mo, and S were added to mineralized rocks during the main-ore stage. Remarkably, arsenic, Sb, and S were added to the mineralized rocks during the late-ore stage. Element migration indicates that the sulfidation process was responsible for ore formation. Four types of fluid inclusions were identified in ore-related quartz and fluorite. The main-ore stage fluids are characterized by an H₂O–NaCl–CO₂–CH₄ ± N₂ system, with medium to low temperatures (180–260 °C) and low salinity (0–9.08% NaCl equivalent). The late-ore stage fluids featured H₂O–NaCl ± CO₂ ± CH₄, with low temperature (120–200 °C) and low salinity (0–7.48% NaCl equivalent). The temperature, salinity, and CO₂ and CH₄ concentrations of ore-forming fluids decreased from the main-ore stage to the late-ore stage. The calculated δ¹³C, δD, and δ¹⁸O values of the ore-forming fluids range from − 14.3 to − 7.0‰, −76 to −55.7‰, and 4.5–15.0‰, respectively. Late-ore-stage stibnite had δ³⁴S values ranging from − 0.6 to 1.9‰. These stable isotopic compositions indicate that the ore-forming fluids originated mainly from deep magmatic hydrothermal fluids, with minor contributions from strata. Collectively, the Baogudi metallogenic district has geological and geochemical characteristics that are typical of Carlin-type gold deposits in southwest Guizhou. It is likely that the Baogudi gold district, together with other Carlin-type gold deposits in southwestern Guizhou, was formed in response to a single widespread metallogenic event.

     

Changes in fluid geochemistry and physico-chemical conditions of geothermal systems caused by magmatic input: The recent abrupt outgassing off the island of Panarea (Aeolian Islands, Italy)

Hydrothermal systems and related vents can exhibit dramatic changes in their physico-chemical conditions over time as a response to varying activity in the feeding magmatic systems. Massive steam condensation and gas scrubbing processes of thermal fluids during their ascent and cooling cause further compositional changes that mask information regarding the conditions evolving at depth in the hydrothermal system. Here we propose a new stability diagram based on the CO₂-CH₄-CO-H₂ concentrations in vapor, which aims at calculating the temperatures and pressures in hydrothermal reservoirs. To filter gas scrubbing effects, we have also developed a model for selective dissolution of CO₂-H₂S-N₂-CH₄-He-Ne mixtures in fresh and/or air-saturated seawater.This methodology has been applied to the recent (November 2002) crisis that affected the geothermal field off the island of Panarea (Italy), where the fluid composition and fluxes have been monitored for the past two decades. The chemical and isotopic compositions of the gases suggest that the volatile elements originate from an active magma, which feeds a boiling saline solution having temperatures of up to 350°C and containing ≈12 mol% CO₂ in vapor. The thermal fluids undergo cooling and re-equilibration processes on account of gas-water-rock interactions during their ascent along fracture networks. Furthermore, steam condensation and removal of acidic species, partial dissolution in cold air-saturated seawater and stripping of atmospheric components, affect the composition of the geothermal gases at shallow levels. The observed geochemical variations are consistent with a new input of magmatic fluids that perturbed the geothermal system and caused the unrest event. The present-state evolution shows that this dramatic input of fluids is probably over, and that the system is now tending towards steady-state conditions on a time scale of months.     

Chemical and isotopic (B, Sr) composition of alluvial sediments as archive of a past hydrothermal outflow

The geochemical and isotopic signature of Quaternary alluvial sediments filling a post-orogenic basin along the Tyrrhenian coasts of Italy (Cornia Plain, Tuscany) was investigated to unravel possible interactions with geothermal fluids from the Larderello geothermal field. Two cores located in the upper (UCP) and lower (LCP) sector of the plain were sampled to depths of up to 80 m. A third core in a neighbouring area not affected by geothermal activity was also sampled (Arno plain at Pisa), and its sediment composition was used as reference. The Cornia sediments (fraction < 65 μm) show high B, Cs and Sb concentrations related to a peculiar chemical enrichment of the clay fraction. They also show remarkable enrichments in As (up to 1000 μg g^− 1) reflecting a contribution from local ore deposits.⁸⁷Sr/⁸⁶Sr ratios, ranging from 0.71022 to 0.71698, reveal the nature of the weathered mother rocks of the alluvial sediments, whereas the boron isotopic composition, varying from − 20‰ to − 10‰, suggests an interaction between the clay fraction and boron-rich fluids at temperatures greater than 50 °C. This implies that hydrothermal fluids widely circulated within the Cornia basin in the past, ultimately leading to the geochemical anomalies currently recorded in local sediments.Although natural (geogenic) in origin, these anomalies cause severe problems to the regional water management (groundwater exploitation) through leaching of trace elements into circulating groundwater, a phenomenon which has to be carefully studied and monitored.     

Carbon dioxide degassing and thermal energy release in the Monte Amiata volcanic-geothermal area (Italy)

The quaternary volcanic complex of Mount Amiata is located in southern Tuscany (Italy) and represents the most recent manifestation of the Tuscan Magmatic Province. The region is characterised by a large thermal anomaly and by the presence of numerous CO₂-rich gas emissions and geothermal features, mainly located at the periphery of the volcanic complex. Two geothermal systems are located, at increasing depths, in the carbonate and metamorphic formations beneath the volcanic complex. The shallow volcanic aquifer is separated from the deep geothermal systems by a low permeability unit (Ligurian Unit). A measured CO₂ discharge through soils of 1.8 × 10⁹ mol a⁻¹ shows that large amounts of CO₂ move from the deep reservoir to the surface. A large range in δ¹³C_TDIC (−21.07 to +3.65) characterises the waters circulating in the aquifers of the region and the mass and isotopic balance of TDIC allows distinguishing a discharge of 0.3 × 10⁹ mol a⁻¹ of deeply sourced CO₂ in spring waters. The total natural CO₂ discharge (2.1 × 10⁹ mol a⁻¹) is slightly less than minimum CO₂ output estimated by an indirect method (2.8 × 10⁹ mol a⁻¹), but present-day release of 5.8 × 10⁹ mol a⁻¹ CO₂ from deep geothermal wells may have reduced natural CO₂ discharge. The heat transported by groundwater, computed considering the increase in temperature from the infiltration area to the discharge from springs, is of the same order of magnitude, or higher, than the regional conductive heat flow (>200 mW m⁻²) and reaches extremely high values (up to 2700 mW m⁻²) in the north-eastern part of the study area. Heat transfer occurs mainly by conductive heating in the volcanic aquifer and by uprising gas and vapor along fault zones and in those areas where low permeability cover is lacking. The comparison of CO₂ flux, heat flow and geological setting shows that near surface geology and hydrogeological setting play a central role in determining CO₂ degassing and heat transfer patterns.     

The origin of the fumaroles of La Solfatara (Campi Flegrei, South Italy)

The analysis of gaseous compositions from Solfatara (Campi Flegrei, South Italy) fumaroles since the early 1980s, clearly reveals a double thermobarometric signature. A first signature at temperatures of about 360 °C was inferred by methane-based chemical-isotopic geoindicators and by the H₂/Ar geothermometer. These high temperatures, close to the critical point of water, are representative of a deep zone where magmatic gases flash the hydrothermal liquid, forming a gas plume. A second signature was found to be at around 200-240 °C. At these temperatures, the kinetically fast reactive species (H₂ and CO) re-equilibrate in a pure vapor phase during the rise of the plume. A combination of these observations with an original interpretation of the oxygen isotopic composition of the two dominant species, i.e. H₂O and CO₂, shed light on the origin of fumarolic fluids by showing that effluents are mixture between fluids degassed from a magma body and the vapor generated at about 360 °C by the vaporization of hydrothermal liquids. A typical ‘andesitic’ water type (δD ∼ −20‰, δ¹⁸O ∼10‰) and a CO₂-rich composition (X_CO2∼0.4) has been inferred for the magmatic fluids, while for the hydrothermal component a meteoric origin and a CO₂ fugacity fixed by fluid-rock reaction at high temperatures have been estimated. In the time the fraction of magmatic fluids in the fumaroles increased (up to ∼0.5) at each seismic and ground uplift crisis (bradyseism) which occurred at Campi Flegrei, suggesting that bradyseismic crises are triggered by periodic injections of CO₂-rich magmatic fluids at the bottom of the hydrothermal system.     

Fluid Geochemistry as Indicator of Tectonically-Related,Deep Water Circulations in the Sardinian Rift-Campidano Graben (Italy): New Insights from Environmental Isotopes

The EC funded Geochemical Seismic Zonation program (EEC GSZ Project 1996–1998) chose Sardinia as a low-seismicity site, in which the relationships between fluid geochemistry and seismo-tectonics had to be investigated and results compared with outcomes from other selected high-seismicity sites. A first article, examining the role of fault segmentation and seismic quiescence on the geochemical composition of groundwaters and gases, has already been presented (Angelone et al. 2005). This article deals with environmental isotopes which, together with selected hydrochemical data, give hints on tectonically-related fluid circulations. Four water-dominated hydrothermal systems were considered, all located along regional fault systems and discharging groundwaters belonging to the Na–HCO₃ and Na–Cl facies. In the considered systems, groundwater circulation takes place, principally, in the Palaeozoic Crystalline Basement (PCB), with the exception of the Logudoro system, where hydrological circuits develop in the Mesozoic Carbonate Platform (MCP). The high CO₂ contents, the non-attainment of fluid-rock equilibrium and the large lithological variability prevent the construction of a unique hydrogeological–geochemical conceptual model. In this case, stable isotopes provide a useful tool to describe the origin of fluids and their subterranean movements. Stable isotopes of water, integrated with hydrochemical data, indicate that fluids are derived from three main end members. The dominant component is a relatively recent local meteoric water; the second one is marine water; and the third one is a fossil freshwater, depleted in heavy isotopes with respect to modern rains. The latter end member entered the aquifer system in the past, when climatic conditions were greatly different from today. At least two circulation systems can be recognised, namely a shallow cold system and a deep hydrothermal system, as well as two distinct hydrological processes: (1) gravity-controlled descent of cold water towards greater depths and (2) convection linked to a thermal gradient, causing deep fluids to rise up from the hydrothermal reservoir towards the surface. The highly variable δ¹³C_TDIC values suggest the presence of two distinct CO₂ sources, namely, a biogenic one and a thermogenic one. The relation between the isotopic compositions of CO₂ and He indicates an increased mantle signature in uprising CO₂-rich fluids.     

Geology,fluid inclusions,and geochemistry of the Zhazixi Sb–W deposit,Hunan, South China

The Zhazixi Sb–W deposit in the Xuefeng uplift, South China, exhibits a unique metal association of W and Sb, where the W orebodies are hosted by interlayer fractures and the Sb orebodies are contained within NW-trending faults. This study proposes that the W and Sb mineralization took place in two separate periods. The mineral paragenesis of the W mineralization reveals a mass of quartz, scheelite and minor calcite. The mineral assemblage of the Sb mineralization developed after W mineralization and consists of predominantly quartz and stibnite, and small amounts of native Sb, berthierite, chalcostibnite, pyrite, and chalcopyrite. Fluid inclusions in quartz and coexisting scheelite are dominated by two-phase, liquid-rich, aqueous inclusions at room temperature. Microthermometric studies suggest that ore-forming fluids for W mineralization are characterized by moderate temperatures (170–270 °C), low salinity (3–7 wt% NaCl equiv.), low density (0.75–0.95 g/cm³), and moderate to high pressure (57.2–99.7 MPa) and these fluids experienced a cooling and dilution evolution during W mineralization. Ore-forming fluids for Sb mineralization are epithermal types with low temperatures (150–230 °C), low salinity (4–6 wt% NaCl equiv.), moderate density (0.82–0.94 g/cm³), and high pressure (42.2–122.5 MPa) and these fluids display an evident decline in homogenization temperature during Sb mineralization. Laser Raman analyses of the vapor phase indicate that the ore-forming fluids for both W and Sb mineralization contain a small amount of CO₂.The ore-forming fluids for Sb mineralization are identified as predominantly originating from the continental crust, as suggested by the low ³He values (0.009 × 10⁻¹² cc.STP/g) and ³He/⁴He ratios (0.002–0.056 Ra) as well as high ³⁶Ar values (1.93 × 10⁻⁹ cc.STP/g) and ⁴⁰Ar/³⁶Ar ratios (909.5–2279.7). The source of S is identified to be the Neoproterozoic Wuqiangxi Formation, as traced by the δ³⁴S_V-CDT values of stibnite (3.1–9.4‰). The ²⁰⁸Pb/²⁰⁴Pb (37.643–40.222), ²⁰⁷Pb/²⁰⁴Pb (15.456–15.681), and ²⁰⁶Pb/²⁰⁴Pb (17.093–20.042) ratios suggest a mixture of lower crustal and supracrustal Pb sources.It is thus concluded that the ore genesis of the Zhazixi Sb–W deposit is related to the intracontinental orogeny during the early Mesozoic. Fluid mixing is considered to be the critical mechanism involved in W mineralization, whereas a fluid cooling process is responsible for Sb mineralization. Furthermore, the absence of Au is attributed to the low Σa_s content in Sb-mineralizing fluids.     

Mercury, arsenic, antimony, bismuth and boron as geochemical indicators for geothermal areas

From 1982 to 1983, 131 soil samples were collected within an area of 60 km² in known geothermal field and their vicinities in Tengchong, Yunnan Province. Distinct anomalies of Hg, As, Sb and Bi were found on the known geothermal fields. The contour of the multiplicative anomaly of Hg × As × Sb encircled the two known geothermal fields, Reshuitang and Rehai, within its extent, disclosing the interrelation between these two fields, and enlarging their future prospects. The B anomaly is related to structural features. Significant correlations among Hg, As and Sb are shown by correlation analysis. It was concluded that a geochemical survey with a density of two samples per km² could be carried out effectively to delineate promising targets of geothermal resources.     

Evolution of Sb mineralisation in modern fold belts: a comparison of the Sb mineralisation in the Central Andes (Bolivia) and the Western Carpathians (Slovakia)

In the Central Andes (Bolivia) and the Western Carpathians (Slovakia) Sb-(Au) deposits are of wide-spread occurrence. They may be subdivided into two principal types: (I) shear zone-hosted and (II) stockwork-like Sb deposits. Type I Sb deposits are widespread in fine-grained metasedimentary, granitic and gneissic rocks. Type II is only found in volcanic rocks and may be further subdivided into acid sulphate-type (IIa) and low sulphidation-type (IIb). This more subtle classification is based upon the presence or absence of sulphate and K feldspar and applied in the same way as for epithermal Au deposits elsewhere. Type III is a composite vein type transitional between types I and II Sb deposits. Mesothermal deposits (type I) were emplaced syntectonically and synmetamorphically under low grade to very low grade stage metamorphic conditions. The mineralising fluids are likely to have been derived from crustal sources through devolatalisation. Epithermal types (IIa) and (IIb) are related in time and space with the formation of acidic to intermediate (sub)volcanic rocks of Miocene age. To distinguish the various types of Sb mineralisation, Bi, Ag, As and Hg have proven most diagnostic. These elements are anomalously enriched in the volcanic-hosted types IIa and IIb, whereas type I mineralisation are poor in Bi, Ag and As. The element contents of these trace elements in type III deposits vary according to the position of the host mineralisation relative to the Tertiary igneous rocks. Hg tends to be enriched in type II mineralisations. Even so there are also some Sb mineralisations of type I abundant in Hg, possibly due to tetrahedrite intergrown with stibnite. In contrast to porphyry copper deposits, Sb deposits are distal relative to the subduction zone. They are confined to sections of the fold belt where the continental crust is thick and was subject to strong horizontal displacements. The ratio of horizontal to vertical crustal movements during the structural evolution of the fold belt and the resultant skewness of the geothermal gradient played a decisive role for the type of volcanic-hosted Sb deposits (types IIa and IIb) to develop and to what extent composite stibnite deposits (type III) evolved. Received: 14 February 1997 / Accepted: 28 August 1997     

Geochemical constraint on origin and evolution of solutes in geothermal springs in western Yunnan,China

Geothermal resources are very rich in Yunnan, China. However, source of dissolved solutes in geothermal water and chemical evolution processes remain unclear. Geochemical and isotopic studies on geothermal springs and river waters were conducted in different petrological-tectonic units of western Yunnan, China. Geothermal waters contain Ca–HCO₃, Na–HCO₃, and Na (Ca)–SO₄ type, and demonstrate strong rock-related trace elemental distributions. Enhanced water–rock interaction increases the concentration of major and trace elements of geothermal waters. The chemical compositions of geothermal waters in the Rehai geothermal field are very complicated and different because of the magma chamber developed at the shallow depth in this area. In this geothermal field, neutral-alkaline geothermal waters with high Cl, B, Li, Rb Cs, As, Sb, and Tl contents and acid–sulfate waters with high Al, Mn, Fe, and Pb contents are both controlled by magma degassing and water–rock interaction. Geothermal waters from metamorphic, granite, and sedimentary regions (except in the Rehai area) exhibit varying B contents ranging from 3.31 mg/L to 4.49 mg/L, 0.23 mg/L to 1.24 mg/L, and <0.07 mg/L, respectively, and their corresponding δ¹¹B values range from −4.95‰ to −9.45‰, −2.57‰ to −8.85‰, and −4.02‰ to +0.06‰. The B contents of these geothermal waters are mainly controlled by leaching host rocks in the reservoir, and their δ¹¹B values usually decrease and achieve further equilibrium with its surrounding rocks, which can also be proven by the positive δ¹⁸O-shift. In addition to fluid–rock reactions, the geothermal waters from Rehai hot springs exhibit higher δ¹¹B values (−3.43‰ to +1.54‰) than those yielded from other areas because mixing with the magmatic fluids from the shallow magma. The highest δ¹¹B of steam–heated waters (pH 3.25) from the Zhenzhu spring in Rehai is caused by the fractionation induced by pH and the phase separation of coexisting steam and fluids. Given the strong water–rock interaction, some geothermal springs in western Yunnan show reservoir temperatures higher than 180 °C, which demonstrate potential for electricity generation and direct-use applications. The most potential geothermal field in western Yunnan is located in the Rehai area because of the heat transfer from the shallow magma chamber.     

Migration paths and precipitation mechanisms of ore-forming fluids at the Shuiyindong Carlin-type gold deposit,Guizhou, China

Shuiyindong is one of the largest and highest grade stratabound Carlin-type gold deposits in China. This paper reports on the results of petrographic studies, electron microprobe analyses (EMPA) of arsenian pyrite, and the mass transfer during mineralization and alteration, and it presents the deposit-scale distributions of Au, As, Sb, Hg, Tl, and trace elements in a representative cross section across the Shuiyindong Carlin-type gold deposit, Guizhou Province. The main objectives were to identify the precipitation mechanisms of minerals, or elements from fluids, and the migration paths of ore-forming fluids.Petrographic and EMPA studies indicate that gold in the primary ores is mainly hosted by arsenian pyrite. Mass transfer associated with alteration and mineralization shows that Au, As, Sb, Hg, Tl, and S were significantly added to all mineralized rocks, Fe₂O₃ and SiO₂ were immobile in the main orebodies that are hosted in bioclastic limestone, and CaO, Na₂O, Sr, and Li were removed from country rocks. The relations between Fe and S indicate that the sedimentary rocks at the Shuiyindong deposit contain more iron than is needed to combine with all of their contained sulfur to form pyrite. This suggests that sulfidation and decarbonation were the principal mechanism of gold precipitation at the Shuiyindong deposit. Hg, Sb, and As commonly formed sulfide minerals, such as stibnite, realgar, and orpiment, in late-stage quartz–calcite veins, or absorbed by organic matter in argillite. Fluid cooling presumably led to depositions of stibnite, realgar, and orpiment in late-stage quartz–calcite veins. Organic matter likely served as a reductant in argillite for the ore fluids, causing the precipitation of As, Sb, Hg, and S, as well as Au.Deposit-scale distributions of gold and other relevant elements reflect the passage of fluids through the rocks. Rock strata and structures allowed the ore-forming fluids to migrate horizontally along the unconformity surface of the Middle–Upper Permian, converge on the high position of an anticline, and then ascend into the overlying strata along the anticlinal axis. The distributions of the major and trace elements show that elements that accompanied the ore-forming fluids include Au, As, Sb, Hg, Tl, and S, and that Na₂O and Li were exhausted in the Longtan Formation at the anticlinal core during gold mineralization. The enrichment of Co, Cr, and Ni in the Longtan Formation at the anticlinal core might be associated with deformation that formed the anticline, or with gold mineralization. Different host rocks were preferentially mineralized by different elements. The bioclastic limestone is commonly enriched in Au, whereas the argillite is preferentially enriched in As, Hg, Sb, and Tl. The zonation of ore-forming elements in the deposit appears to be Sb–Tl–As–Hg–Au–Hg–As (from bottom to top). Enrichment of Au, As, Sb, Hg, and Tl provides useful guidance for the exploration for Carlin-type gold deposits in Guizhou. Anomalies of As and Hg in soil or stream sediment might be an important clue and these elements can be used as indicator elements. Ore-forming fluids migrated along the unconformity surface of the Middle–Upper Permian and the anticlinal axis, so these are favorable sites for exploration for Carlin-type gold deposits in Guizhou.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

Fluid inclusion characteristics of hematite-bearing quartz vein from the Daenam mine, Republic of Korea

The Daenam mine, which produced over 9250 tons of iron oxide ore from 1958 to 1962, is situated in the Early Cretaceous Yeongyang subbasin of the Gyeongsang basin. It consists of two lens-shaped, hematite-bearing quartz veins that occur along faults in Cretaceous leucocratic granite. The hematite-bearing quartz veins are mainly composed of massive and euhedral quartz and hematite with minor amounts of pyrite, pyrrhotite, mica, feldspar and chlorite.Fluid inclusions in quartz can be divided into three main types: CO₂-rich, CO₂–H₂O, and H₂O-rich. Hydrothermal fluids related to the formation of hematite are composed of either H₂O–CO₂–NaCl ± CH₄ (homogenization temperature: 262–455 °C, salinity <7 eq. wt.% NaCl) or H₂O–NaCl (homogenization temperature: 182–266 °C, and salinity <5.1 eq. wt.% NaCl), both of which evolved by mixing with deeply circulating meteoric water. Hematite from the quartz veins in the Daenam mine was mainly deposited by unmixing of H₂O–CO₂–NaCl ± CH₄ fluids with loss of the CO₂ + CH₄ vapor phase and mixing with downward percolating meteoric water providing oxidizing conditions.     

Geochemistry of shallow aquifers and soil gas surveys in a feasibility study at the Rivara natural gas storage site (Po Plain,Northern Italy)

A geochemical survey, in shallow aquifers and soils, has been carried out to evaluate the feasibility of natural gas (CH₄) storage in a deep saline aquifer at Rivara (MO), Northern Italy. This paper discusses the areal distribution of CO₂ and CH₄ fluxes and CO₂, CH₄, Rn, He, H₂ concentrations both in soils and shallow aquifers above the proposed storage reservoir. The distribution of pathfinder elements such as ²²²Rn, He and H₂ has been studied in order to identify potential faults and/or fractures related to preferential migration pathways and the possible interactions between the reservoir and surface. A geochemical and isotopic characterization of the ground waters circulating in the first 200 m has allowed to investigation of (i) the origin of the circulating fluids, (ii) the gas–water–rock interaction processes, (iii) the amount of dissolved gases and/or their saturation status. In the first 200 m, the presence of CH₄-rich reducing waters are probably related to organic matter (peat) bearing strata which generate shallow-derived CH₄, as elsewhere in the Po Plain. On the basis of isotopic analysis, no hints of thermogenic CH₄ gas leakage from a deeper reservoir have been shown. The δ¹³C(CO₂) both in ground waters and free gases suggests a prevalent shallow origin of CO₂ (i.e. organic and/or soil-derived). The acquisition of pre-injection data is strategic for the natural gas storage development project and as a baseline for future monitoring during the gas injection/withdrawing period. Such a geochemical approach is considered as a methodological reference model for future CO₂/CH₄ storage projects.     

Sb–Hg ore deposit distribution controlled by brittle structures: The case of the Selvena mining district (Monte Amiata, Tuscany, Italy)

This paper deals with the tectonic control on the hydrothermal system that gave rise to Sb–Hg ore deposits in the Monte Amiata area that was one of the most relevant mining district for the exploitation of mercury in Italy. The study area (Selvena mining district) is located in southern Tuscany (inner Northern Apennines) one of the most important mineralized area in the western Mediterranean region. Southern Tuscany was severely affected by Middle–Late Miocene low-angle normal faults, later dissected by Pliocene–Pleistocene faults, coeval magmatism (Late Miocene–Pleistocene) and hydrothermal activity (Pliocene–Present). The Selvena mining district is located south of Middle Pleistocene Monte Amiata volcanic complex. Our structural and kinematic study is based on the integration among fieldwork, borehole and mine data. The results highlight two Pleistocene–Holocene left-lateral transtensional shear zones linked by normal faults, defining a coeval pull-apart structure. Here, the Sb–Hg mineralization, transported by meteoric hydrothermal fluids mainly, is particularly diffuse and concentrated in the cataclasites and in damage zones of the normal faults. Furthermore, a widespread mineralization also occurs in the cataclasites of Miocene low-angle normal faults. Mine evidence suggests that ore-bearing fluids percolated through structural conduits located along the fault planes and resulting parallel to the intermediate stress axis. Geological structures and ore deposit distribution are related to a single hydrothermal circuit, with meteoric water channelled to depth through conduits parallel to the intermediate stress axis of the transcurrent shear zones; then, hydrothermal fluids mainly ascended through the almost vertical deformation zones located at the intersection between normal and strike-slip faults. Thus, hydrothermal fluids permeated also the Middle–Late Miocene cataclasites. This study shed light on the relationships between geological structures and mineralization in southern Tuscany and underlines the importance to investigate mine areas to understand hydrothermal fluids path.     

Paleogene magmatism and gold metallogeny of the Jinping terrane in the Ailaoshan ore belt,Sanjiang Tethyan Orogen (SW China): Geology,deposit type and tectonic setting

The Jinping terrane is situated in the southern segment of the Ailaoshan ore belt, Sanjiang Tethyan Orogen (SW China). The Paleogene intrusions in Jinping consist of syenite porphyry, fine-grained syenite and biotite granite stocks/dikes, and contain relatively low TiO₂ (0.21–0.38 wt%), P₂O₅ (0.01–0.35 wt%), and high Na₂O (2.00–4.62 wt%) and K₂O (4.48–7.06 wt%), belonging to high-K alkaline series. Paleogene gold mineralization in Jinping comprises four genetic types, i.e., orogenic, alkali-rich intrusion-related, porphyry and supergene laterite. The NW–NNW-trending faults and their subsidiaries are the major ore-controlling structures. The orogenic Au mineralization, dominated by polymetallic sulfide-quartz veins, occurs in the diorite and minor in Silurian-Devonian sedimentary rocks. It contains a CO₂-rich mesothermal fluid system generated from the mixing of mantle-derived fluids with crustal-derived metamorphic fluids, and the ore-forming materials were upper crustal- or orogenic-derived. The alkali-rich intrusion-related Au mineralization is hosted in the Ordovician-Silurian sedimentary rocks and minor in the Paleogene alkaline intrusions, and the Au orebodies occur predominantly in the alteration halos. It contains a CO₂-bearing, largely metamorphic-sourced mesothermal fluid system, and the ore-forming materials were derived from the ore-hosting rocks and minor from the alkali-rich intrusions. The porphyry Cu-Mo-Au mineralization occurs in the granite/syenite porphyries and/or along their contact skarn, with the mineralizing fluids being magmatic-hydrothermal in origin. The former two hypogene Au mineralization types in Jinping were mainly formed in the late Eocene (ca. 34–33 Ma) and slightly after the porphyry Cu-Mo-Au mineralization (ca. 35–34 Ma), which is coeval with the regional Himalayan orogenic event. Subsequent weathering produced the laterite Au mineralization above or near the hypogene Au orebodies.     

Application of geochemical methods in the search for geothermal fields

From 1983 to 1985, an orientation study was carried out in about 20 geothermal fields in China. Semi-detailed and detailed surveys were conducted in an area of 90 km² in Yangbajing, Tibet. Hg, As, Sb and Bi were used as indicators to extend the promising area of known geothermal fields to 16 km². In the northern part of the extended promising area, three drill holes were sunk and high-temperature thermal water of 160°C was obtained. In the southern part, outside the geochemical anomaly, two holes were drilled but no thermal water was found. The inner zone of the Hg anomaly coincides closely with the distribution of drill holes that met thermal water with temperatures higher than 140°C. The distribution of Bi values may indicate that the thermal water in the southern part is at shallower depth. A semi-regional survey in an area of 200 km² in Tengchong, Yunnan Province delineated several new prospects, which will possibly extend the resources of the Rehai geothermal field. An element zoning pattern similar to that of hydrothermal mineral deposits was discovered in the Rehai geothermal field. A semi-regional survey conducted in Xiaotangshan near Beijing indicated that the possible extent of the Xiaotangshan geothermal field may reach 30 km². Drilling confirmed that the outer zone of the Hg anomaly is in accordance with the distribution of 40°C thermal water, and the intermediate and inner zones of the Hg anomaly are associated with higher temperature thermal water. Research during the three years 1983–1985 demonstrated that exploration geochemistry is an effective tool for finding geothermal fields.     

Fluid-rock interactions in a geothermal Rotliegend/Permo-Carboniferous reservoir (North German Basin)

Comprehensive data on the chemical composition of reservoir rocks and geothermal brines from the geothermal well doublet Groβ Schönebeck (North German Basin) drilled into a Rotliegend sedimentary and Permo-Carboniferous volcanic rock reservoir were sampled over the past years. They were characterized with respect to their major and minor elemental composition including various isotope ratios. The study considered the impact of drilling and reservoir operations on fluid composition and aimed at determining fluid–rock interactions to gain information on fluid origin and hydraulic pathways.The highly saline fluids (up to 265 g/L TDS) show δ ¹⁸O and δD of water (2.7–5.6 and −3.1–15, respectively) as well as δ ³⁴S of sulfate (3.6–5), and ⁸⁷Sr/⁸⁶Sr ratios (0.715–0.716) that resemble Rotliegend brines from an area located around 200 km in the west (the Altmark). Halogen ratios indicated that brines developed predominantly by evaporation of meteoric water (primary brine) together with halite dissolution brine (secondary brine). Indication for mixing with Zechstein brine or with younger meteoric water was not found.No geochemical distinction was possible between fluids deriving from different rock formations (dacites or sedimentary rocks, respectively). This is due to the evolution of the sediments from the effusive rocks resulting in a similar mineralogical and chemical composition and due to a hydraulic connectivity between the two types of rock. This connection existed probably already before reservoir stimulation as indicated by a set of faults identified in the area that could connect the Rotliegend formation with both, the volcanic rocks and the lower units of the Zechstein. Additional geochemical indication for a hydraulic connectivity is given by (1) the very high heavy metal contents (mainly Cu and Pb) in fluids and scaling that derive from the volcanic rocks and were that were also found in increased amounts up at the Zechstein border (Kupferschiefer formation). (2) The ⁸⁷Sr/⁸⁶Sr isotope ratios of fluid samples correspond to the ratios determined for the sedimentary rocks indicating that initially the fluids developed in the sedimentary rocks and circulated later, when faults structures were created by tectonic events into the volcanic rocks.