A hydrochemical study of the Hammam Righa geothermal waters in north-central Algeria

This study focuses on the hydrochemical characteristics of 47 water samples collected from thermal and cold springs that emerge from the Hammam Righa geothermal field, located in north-central Algeria. The aquifer that feeds these springs is mainly situated in the deeply fractured Jurassic limestone and dolomite of the Zaccar Mount. Measured discharge temperatures of the cold waters range from 16.0 to 26.5 °C and the hot waters from 32.1 to 68.2 °C. All waters exhibited a near-neutral pH of 6.0–7.6. The thermal waters had a high total dissolved solids (TDS) content of up to 2527 mg/l, while the TDS for cold waters was 659.0–852.0 mg/l. Chemical analyses suggest that two main types of water exist: hot waters in the upflow area of the Ca–Na–SO₄ type (Hammam Righa) and cold waters in the recharge zone of the Ca–Na–HCO₃ type (Zaccar Mount). Reservoir temperatures were estimated using silica geothermometers and fluid/mineral equilibria at 78, 92, and 95 °C for HR4, HR2, and HR1, respectively. Stable isotopic analyses of the δ¹⁸O and δD composition of the waters suggest that the thermal waters of Hammam Righa are of meteoric origin. We conclude that meteoric recharge infiltrates through the fractured dolomitic limestones of the Zaccar Mount and is conductively heated at a depth of 2.1–2.2 km. The hot waters then interact at depth with Triassic evaporites located in the hydrothermal conduit (fault), giving rise to the Ca–Na–SO₄ water type. As they ascend to the surface, the thermal waters mix with shallower Mg-rich groundwater, resulting in waters that plot in the immature water field in the Na–K–Mg diagram. The mixing trend between cold groundwaters from the recharge zone area (Zaccar Mount) and hot waters in the upflow area (Hammam Righa) is apparent via a chloride-enthalpy diagram that shows a mixing ratio of 22.6 < R < 29.2 %. We summarize these results with a geothermal conceptual model of the Hammam Righa geothermal field.     

Stable isotopes (2H, 18O and 13C) in groundwaters from the northwestern portion of the Guarani Aquifer System (Brazil)

The groundwater flow pattern of the western part of the Guarani Aquifer System (GAS), Brazil, is characterized by three regional recharge areas in the north, and a potentiometric divide in the south, which trends north–south approximately. Groundwater flow is radial from these regional recharge areas toward the center of Paraná Sedimentary Basin and toward the western outcrop areas at the border of the Pantanal Matogrossense, because of the potentiometric divide. The isotopic composition of GAS groundwater leads to understanding the paleoclimatic conditions in the regional recharge areas. The δ¹⁸O and δ²H isotopic ratios of GAS groundwaters vary, respectively, from –9.1 to –4.8‰ V-SMOW and –58.4 to –21.7‰ V-SMOW. In the recharge zones, enriched δ¹⁸O values are observed, while in the confined zone lighter δ¹⁸O values are observed. These suggest that climatic conditions were 10°C cooler than the present during the recharge of these waters. The δ¹³C ratios in groundwater of GAS, in the study area, vary from –19.5 to –6.5‰ VPDB, increasing along the regional flow lines toward the confined zone. This variation is related to dissolution of carbonate cement in the sandstones.     

The origin of thermal waters in the northeastern part of the Eger Rift,Czech Republic

An investigation of the thermal waters in the Ústí nad Labem area in the northeastern part of the Eger Rift has been carried out, with the principal objective of determining their origin. Waters from geothermal reservoirs in the aquifers of the Bohemian Cretaceous Basin (BCB) from depths of 240 to 616 m are exploited here. For comparison, thermal waters of the adjacent Teplice Spa area were also incorporated into the study. Results based on water chemistry and isotopes indicate mixing of groundwater from aquifers of the BCB with groundwater derived from underlying crystalline rocks of the Erzgebirge Mts. Unlike thermal waters in Dě?ín, which are of Ca–HCO₃ type, there are two types of thermal waters in Ústí nad Labem, Na–HCO₃–Cl–SO₄ type with high TDS values and Na–Ca–HCO₃–SO₄ type with low TDS values. Carbon isotope data, speciation calculations, and inverse geochemical modeling suggest a significant input of endogenous CO₂ at Ústí nad Labem in the case of high TDS groundwaters. Besides CO₂ input, both silicate dissolution and cation exchange coupled with dissolution of carbonates may explain the origin of high TDS thermal waters equally well. This is a consequence of similar δ¹³C and ¹⁴C values in endogenous CO₂ and carbonates (both sources have ¹⁴C of 0 pmc, endogenous CO₂ δ¹³C around −3‰, carbonates in the range from −5‰ to +3‰ V-PDB). The source of Cl⁻ seems to be relict brine formed in Tertiary lakes, which infiltrated into the deep rift zone and is being flushed out. The difference between high and low TDS groundwaters in Ústí nad Labem is caused by location of the high mineralization groundwater wells in CO₂ emanation centers linked to channel-like conduits. This results in high dissolution rates of minerals and in different δ¹³C(DIC) and ¹⁴C(DIC) fingerprints. A combined δ³⁴S and δ¹⁸O study of dissolved SO₄ indicates multiple SO₄ sources, involving SO₄ from relict brines and oxidation of H₂S. The study clearly demonstrates potential problems encountered at sites with multiple sources of C, where several evolutionary groundwater scenarios are possible.     

Hydrogeochemistry and possible sulfate sources in karst groundwater in Chongqing, China

Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are affected by both natural environment and people. Therefore, the study of karst groundwater hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. This paper focused on the major ion chemistry and sulfate isotope of karst groundwater in Chongqing for tracing the sulfate sources and related hydrochemical processes. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO₃ type or Ca(Mg)-HCO₃ type. However, some hydrochemical types were the K + Na + Ca-SO₄ type (G25 site) or Ca-HCO₃ + SO₄ type (G26 and G14 sites), indicating that the hydrochemistry of these sites may be strongly influenced by anthropogenic activities or unique geological characteristics. The δ³⁴S-SO₄ ^2? of collected karst groundwater sample fell into a range of ?6.8 to 21.5 ‰, with a mean value of 5.6 ‰. In dolomite aquifer, the δ³⁴S-SO₄ ^2? value ranges from ?4.3 to 11.0 ‰, and in limestone aquifer, it ranged from ?6.8 to 21.5 ‰. The groundwater samples from different land use types showed distinctive δ³⁴S-SO₄ ^2? value. The δ³⁴S-SO₄ ^2? value of groundwater samples had range of ?6.8 to 16.7 ‰ (mean 4.0 ‰, n = 11) in cultivated land areas, 1.5–21.5 ‰ (mean 7.2 ‰, n = 20) in forested land areas, and ?4.3 to 0.8 ‰ (mean ?1.7 ‰, n = 2) in coalmine areas. The δ³⁴S-SO₄ ^2? values of groundwater samples collected from factory area and town area were 2.2 and 9.9 ‰, respectively. According to the δ³⁴S information of potential sulfate sources, this paper discussed the possible sulfate sources of collected karst groundwater samples in Chongqing. The variations of both δ³⁴S and 1/SO₄ ^2? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sulfide mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) contributed to sulfate in karst groundwater. The influence of oxidation of sulfide mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread. For protecting, sustaining, and utilizing the groundwater resources, the sewage possibly originating from urban, mine or industrial area must be controlled and treated, and the use of fertilizer should be limited.     

The Use of Stable Sulfur, Oxygen and Hydrogen Isotope Ratios as Geochemical Tracers of Sulfates in the Podwiśniówka Acid Drainage Area (South-Central Poland)

The paper presents the results of determinations of stable S and O isotopes of dissolved sulfates and O and H stable isotopes of waters from three ponds, that is, Marczakowe Do?y acid pond, Marczakowe Do?y fish pond and Podwi?niówka acid pit pond, located in the Holy Cross Mountains (south-central Poland). The δ³⁴S_V-CDT and δ¹⁸O_V-SMOW of SO₄ ^2? in waters of three ponds (n = 14) varied from ?16.2 to ?9.5 ‰ (mean of ?13.6 ‰) and from ?8.1 to ?3.2 ‰ (mean of ?4.8 ‰), respectively. The mean δ³⁴S–SO₄ ^2? values were closer to those of pyrite (mean of ?25.4 ‰) and efflorescent sulfate salts (mean of ?25.6 ‰), recorded previously in the Podwi?niówka quarry, than to sulfates derived from other anthropogenic or soil and bedrock sources. The SO₄ ^2? ions formed by bacterially induced pyrite oxidation combined with bacterial (dissimilatory) dissolved sulfate reduction, and presumably with subordinate mineralization of carbon-bonded sulfur compounds, especially in both Marczakowe Do?y ponds. In addition, the comparison of δ¹⁸O–SO₄ ^2? and δ¹⁸O–H₂O values indicated that 75–100 % of sulfate oxygen was derived from water. Due to the largest size, the Podwi?niówka acid pit pond revealed distinct seasonal variations in both δ¹⁸O–H₂O (?9.2 to ?1.6) and δD–H₂O (?29.7 to ?71.3) values. The strong correlation coefficient (r ² = 0.99) was noted between δ¹⁸O–H₂O and δD–H₂O values, which points to atmospheric precipitation as the only source of water. The sediments of both acid ponds display different mineral inventory: the Marczakowe Do?y acid pond sediment consists of schwertmannite and goethite, whereas Podwi?niówka acid pit pond sediment is composed of quartz, illite, chlorite and kaolinite with some admixture of jarosite reflecting a more acidic environment. Geochemical modeling of two acid ponds indicated that the saturation indices of schwertmannite and nanosized ε-Fe₂O₃ (Fe³⁺ oxide polymorph) were closest to thermodynamic equilibrium state with water, varying from ?1.44 to 3.05 and from ?3.42 to 6.04, respectively. This evidence matches well with the obtained mineralogical results.     

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (～50–140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0–25 wt.% NaCl eq.), low fluid δ¹⁸O values (?10 to +2 ‰ V-SMOW), low fluid δ¹³C values (?9 to ?15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO₄/Cl, NO₃/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na–Ca–Cl basinal brines or shield brines, (3) SO₄–NO₃–Cl–(H)CO₃ playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.     

Conditions of the formation of thermomineral waters in the Talysh fold zone of the Lesser Caucasus (Azerbaijan) based on isotope-geochemical data (3Не/4Не, $${\delta ^{13}}{C_{c{o_2}}},{\delta ^{13}}{C_{c{h_4}}},{\delta ^{15}}{N_{{N_2}}}{,^{87}}Sr{/^{86}}Sr,\delta {D_{{H_2}O}},and{\delta ^{18}}{O_{{H_2}O}}$$)

It is shown that the gas and water phases of the thermal nitrogen–methane waters in the Talysh fold zone of the Lesser Caucasus mountain system contain helium and strontium with mantle isotope signatures (³Не/⁴Не from 200 × 10^–8 to 401 × 10^–8 and ⁸⁷Sr/⁸⁶Sr from 0.70490 to 0.70562). At the same time, clear signs of the mantle component in other gases (nitrogen, methane, and carbon dioxide) are absent. The δ¹⁵N value in nitrogen varies from +0.3 to +1.7‰, methane is mainly characterized by δ¹³C from–57.4 to–38.0‰, while δ¹³C(CО₂) varies from–24.4 to–11.3‰. An increase of the CО₂ content is accompanied by the decrease of δ¹³C in CО₂, against the background of increasing SO₄ content in the salt composition of waters. This indicates a microbial nature of CO₂ in the studied gases. Thus, the presence of mantle helium and strontium in the thermal waters is likely related to their leaching from the Pleogene–Neogene host volcanic rocks. The studies of the oxygen and hydrogen isotope composition in water revealed quite different mechanisms for the formation of cold and thermal waters of the region. The cold waters are mainly fed by local infiltration, whereas the feeding of thermal nitrogen–methane waters is strongly provided by transit atmogenic waters (>50%), which are formed in the mountain ranges at altitudes no less than 1600 m and spaced at 20–40 km or more from the thermal discharge sites.     

Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill,Staten Island,New York,USA

A study was conducted at the Fresh Kills landfill, Staten Island, New York to investigate the use of B and Li isotopes as tracers of mixing and flow in the groundwater environment. Four end-member waters are present at the Fresh Kills: freshwater, seawater, a geochemically distinct transitional groundwater (that occurs in the zone of mixing between seawater and freshwater) and landfill leachate. The δ¹¹B and δ⁶Li values of end-member waters are distinct and have isotopic compositions that reflect the solute sources: freshwater δ¹¹B∼+30‰, δ⁶Li∼−22‰; transition zone groundwaters δ¹¹B∼+20‰, δ⁶Li∼−27‰; seawater δ¹¹B+40 to +75‰, δ⁶Li−37 to−44‰; leachate δ¹¹B∼+10‰ (δ⁶Li not determined). Those wells influenced by seawater exhibited a clear chemical mixing trend, with seawater contributions ranging from 3 to 85%. Well waters with a high percentage of seawater (>30%) had δ¹¹B values that were within 1‰ of the seawater value (+40‰), whereas a trend of increasing δ¹¹B values (+55 to +75‰) was observed for wells with a lower percentage of seawater (<30%). δ⁶Li values for well waters impacted by mixing with seawater ranged from−37 to−44‰, significantly more negative than pure seawater (−31‰). This deviation from the isotopic composition of seawater, for both δ¹¹B and δ⁶Li values, represents non-conservative behavior and is likely the result of isotopic fractionation during ion exchange reactions. The wide range of δ¹¹B and δ⁶Li values and the distinct isotopic compositions of end-member waters makes B and Li isotopes useful for recognizing solute sources, however isotopic fractionation may limit their use as simple tracers of groundwater flow and mixing.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

Controls on δ34S and δ18O of dissolved sulfate in aquifers of the Murray Basin,Australia and their use as indicators of flow processes

The usefulness of stable isotopes of dissolved SO₄ (δ³⁴S and δ¹⁸O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ³⁴S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO₄/Cl ratios, as well as relatively low δ¹⁸O_SO4 values, suggest that vertical input of biogenically derived SO₄ via diffuse recharge is the predominant source of dissolved SO₄ to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ³⁴S values in the unconfined Murray Group Aquifer increase, and SO₄/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO₄/Cl and high δ³⁴S (14.9–56.4‰). Relatively positive δ³⁴S and δ¹⁸O_SO4 values, and low SO₄/Cl in the Renmark Group Aquifer is typical of SO₄ removal by bacterial reduction. The S isotope fractionation between SO₄ and HS⁻ of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ³⁴S and SO₄/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.     

An “On-Line” Method for Oxygen Isotope Exchange Between Gas-Phase CO<Subscript>2</Subscript> and Water

An “on-line” mixing system has been developed and evaluated for continuous oxygen isotope exchange between gas-phase CO₂ and liquid water. The system is composed of three basic parts: equipment and materials used to introduce water and gas into a mixing reservoir, the mixing and exchange reservoir, and a vessel used to separate gas and water phases exiting the system. A series of experiments were performed to monitor the isotope exchange process over a range of temperatures (5–40 °C) and CO₂ partial pressures (202–15,200 Pa). Isotopic exchange was evaluated using CO₂ having δ¹⁸O values of 30.4 and 37.8 ‰ and waters of two distinct oxygen isotope compositions (?6.5 to ?5 and 6 to 7.5 ‰). Isotope ratios were determined by isotope ratio mass spectrometry and cavity ring-down spectroscopy. CO₂ did not reach oxygen isotope equilibrium under the conditions described here. However, oxygen isotope exchange rate constants were determined at different temperatures and regressed to yield the expression k (h^?1) = 0.020 × T (°C) + 0.28. Using this expression, the residence time required to reach oxygen isotope equilibrium may be estimated for a given set of environmental conditions (e.g., δ¹⁸O value of water, temperature). System parameters can be modified to achieve a specific δ¹⁸O value for CO₂. Consequently, the exchange system described here has the ability to deliver a constant flow of CO₂ at a desired oxygen isotope composition. This ability is attractive for a variety of applications such as experiments that utilize flow-through reactors and environmental chambers or require static chemical conditions.     

Chemistry,isotope values (δD, δ18O, δ34SSO4) and temperatures of the water inflows in two Gotthard tunnels,Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO₃ and Na–Ca–HCO₃ waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO₃ to Na–SO₄ waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO₄ composition. Calcium-Na–SO₄ waters are also present. They can be produced through interaction of either Na–HCO₃ waters with anhydrite or Ca–SO₄ waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO₃ waters are generated through interaction of Ca–HCO₃ waters with a local gneissic rock. The two main SO₄-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ³⁴S_SO4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ³⁴S_SO4 >∼+9‰ are controlled either by bacterial SO₄ reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.     

Geochemistry and14C dating of groundwaters from Jurassic aquifers of North Aquitaine Basin (France)

Twenty-seven samples from a confined Lower-Middle Jurassic aquifer and an unconfined Oxfordian aquifer of the North Aquitaine Basin (France) have been analysed for their major elements, Br⁻,¹⁸O,²H,¹³C and¹⁴C contents. Hydrochemistry indicates (1) a dissolution of carbonate and anhydrite near the recharge zone and (2) a dilution of a saline water derived from a seawater/halite mixing in the deeper part of the aquifer. The mixing is also visible in a δ¹⁸O vs Cl⁻ diagram in which two different groups appear: recent waters and old waters indicating a mixing process between fresh and saline groundwaters. The composition of the saline water is likely to be 34,100±11,200 ppm in Cl, 70±20 ppm in Br and more than −3.5±07‰ vs SMOW in¹⁸O.¹³C contents indicate (1) a C exchange with CaCO₃ matrix for groundwaters near the recharge zone and (2) a participation of organic matter in the deep part of the aquifer.Residence times for waters near the area of the aquifer outcrop correspond to Holocene and Late Pleistocene periods. The depletion in stable isotopes of 10 to 15,000 y B.P. waters show a late glacial period infiltration to the aquifer. After a distance of about 10 km in the aquifer, the¹⁴C activities are 0 pmc showing the presence of ‘old’ groundwaters.     

Hydrogeochemical and isotopic characteristics of the Ilica geothermal system (Erzurum,Turkey)

In this paper, the hydrochemical isotopic characteristics of samples collected from geothermal springs in the Ilica geothermal field, Eastern Anatolia of Turkey, are examined and described. Low-temperature geothermal system of Ilica (Erzurum, Turkey) located along the Eastern Anatolian fault zone was investigated for hydrogeochemical and isotopic characteristics. The study of ionic and isotopic contents shows that the thermal water of Ilica is mainly, locally fed by groundwater, which changes chemically and isotopically during its circulation within the major fault zone reaching depths. The thermal spring has a temperature of 29–39 °C, with electrical conductivity ranging from 4,000 to 7,510 µS/cm and the thermal water is of Na–HCO₃–Cl water type. The chemical geothermometers applied in the Ilica geothermal waters yielded a maximum reservoir temperature of 142 °C according to the silica geothermometers. The thermal waters are undersaturated with respect to gypsum, anhydrite and halite, and oversaturated with respect to dolomite. The dolomite mineral possibly caused scaling when obtaining the thermal waters in the study area. According to the enthalpy chloride-mixing model, cold water to the thermal water-mixing ratio is changing between 69.8 and 75 %. The δ¹⁸O–δ²H compositions obviously indicate meteoric origin of the waters. Thermal water springs derived from continental precipitation falling on to higher elevations in the study area. The δ¹³C ratio for dissolved inorganic carbonate in the waters lies between 4.63 and 6.48 ‰. In low-temperature waters carbon is considered as originating from volcanic (mantle) CO₂.     

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China: Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of ?7.8‰ and ?53.0‰ for δ18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater (less than a depth of 150 m) in desert plateau range from ?10.6‰ to ?6.0‰ with an average of ?8.4‰ for δ18O and from ?85‰ to ?46‰ with an average of ?63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters (greater than a depth of 275 m) fall in ranges from ?11.6‰ to ?8.8‰ with an average of ?10.2‰ for δ18O and from ?89‰ to ?63‰ with an average of ?76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of 14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.     

Environmental problems at the Nevşehir (Kozakli) geothermal field,central Turkey

The Kozakli–Nev?ehir geothermal field extends a long a NW–SE direction at SE of the Centrum of Kozakli. The area is not rugged and average elevation is 1,000 m. The Kozanözü Creek flows towards north of the area. In the Kozakli thermal Spa area, thermal waters are manifested along a valley with a length of 1.5 km and 200 m width. In this resort some hot waters are discharged with no use. The thermal water used in the area comes from wells drilled by MTA. In addition, these waters from wells are also utilized by hotels, baths and motels belonging to City Private Management, Municipality and private sector. The measured temperature of Kozakli waters ranges from 43–51°C in springs and 80–96°C in wells. Waters are issued in a wide swampy area as a small group of springs through buried faults. Electrical conductivity values of thermal spring and well waters are 1,650–3,595 μS/cm and pH values are 6.72–7.36. Kozakli cold water has an electrical conductivity value of 450 μS/cm and pH of 7.56. All thermal waters are dominated by Na⁺ and Cl–SO₄ while cold waters are dominated by Ca⁺² and HCO₃ ^?. The aim of this study was to investigate the environmental problems around the Kozakli geothermal field and explain the mechanisms of karstic depression which was formed by uncontrolled use of thermal waters in this area and bring up its possible environmental threats. At the Kozakli geothermal field a sinkhole with 30 m diameter and 15 m depth occurred in January, 17th 2007 at the recreation area located 20 m west of the geothermal well which belongs to the government of Nev?ehir province. The management of the geothermal wells should be controlled by a single official institution in order to avoid the creation of such karstic structures affecting the environment at the source area.     

The genesis of sandstone‐type uranium deposits in the Ordos Basin,NW China: constraints provided by fluid inclusions and stable isotopes

Quartz from sandstone‐type uranium deposits in the east part of the Ordos Basin contains abundant secondary fluid inclusions hosted along sealed fractures or in overgrowths. These inclusions consist mainly of water with NaCl, KCl, CO₂ (135–913 ppm) and trace amounts of CO (0.22–16.8 ppm), CH₄ (0.10–1.38 ppm) and [SO₄]^2? (0.35–111 ppm). Homogenization temperatures of the studied fluid inclusions range from 90 to 210°C, with salinities varying from 0.35 to 12.6 wt‐% (converted to NaCl wt%), implying multiple stages of thermal alteration. Although high U is associated with a high homogenization temperature in one case, overall U mineralization is not correlated with homogenization temperature nor with salinity. The H and O isotopic compositions of fluid inclusions show typical characteristics of formation water, with δ¹⁸O ranging from 9.8 to 12.3‰ and δD from 26.9 to ?48.6‰, indicating that these fluid inclusions are mixtures of magmatic and meteoric waters. The oxygen isotope ratios of carbonates in cement are systematically higher than those of the fluid inclusions. Limited fluid inclusion‐cement pairs show that the oxygen closely approaches equilibrium between water and aragonite at 150°C. Highly varied and overall negative δ¹³C in calcite from cement implies different degrees of biogenetic carbon involvement. Correlations between U in bulk rocks and trace components in fluid inclusions are lacking; however, high U contents are typically coupled with high [SO₄]^2?, implying pre‐enrichment of oxidized materials in the U mineralization layer. All these relationships can be plausibly interpreted to indicate that U (IV), [SO₄]^2? as well as Na, K were washed out from the overlying thick sandstone by oxidizing meteoric water, and then were reduced by reducing agents, such as CH₄ and petroleum, likely from underlying coal and petroleum deposits, and possibly also in situ microbes at low temperatures.     

Calculating groundwater mixing ratios in groundwater-inrushing aquifers based on environmental stable isotopes (D, 18O) and hydrogeochemistry

Conventional hydrogeochemical data and environmental stable isotopes are used to identify the recharge sources and the water–rock interactions in the groundwater-flowing direction within the multilayer groundwater system of the Sulin coal-mining district in the north Anhui province in China. δD and δ ¹⁸O of groundwater in the mining district decrease along the groundwater-flowing direction in the recharge areas, yet in the runoff or discharge areas, they rise and fall along average δ values (δ ¹⁸O = ?8.68 ‰, δD = ?67.4 ‰), which are lower than average δ values of local atmospheric precipitation (δ ¹⁸O = ?7.80 ‰, δD = ?52.4 ‰). Principal component analysis is used to analyze the conventional hydrogeochemical data (K⁺ + Na⁺, Mg²⁺, Ca²⁺, Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?) in the groundwater. The first and second principal components have large variance contributions, and represent “pyrite oxidation or groundwater hardening” and “desulfurization or cation exchange and adsorption,” respectively. From conventional hydrogeochemical data and environmental stable isotopes, it is demonstrated that groundwater of the Sulin coal-mining district is characterized by a mixing type, which is confirmed by three recharge end-members: fresh groundwater, leaching groundwater, and retained groundwater. By means of a sample dot-encompassed triangle in the scatter diagram of load scores for Component 1–Component 2, whose vertexes stand for the three end-members, a model for calculating groundwater mixing ratio is established and applied successfully to the evaluation and management of groundwater hazards in the coal-mining districts.     

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au?±?Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (²⁰⁶Pb/²⁰⁴Pb, 18.669–19.861; ²⁰⁸Pb/²⁰⁴Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ³⁴S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from ?1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ³⁴S values between ?8.1 and ?3.1 ‰. The δ³⁴S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ¹³C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from ?4.9 to 1.1 ‰ and are higher than magmatic values. The δ¹⁸O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively ¹⁸O-depleted (4.2 to 7.9 ‰ and ?6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from ?133 to ?161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7?±?0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25?±?0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9?±?0.3 to 76.2?±?0.3 Ma) and Revenue (77.9?±?0.3 to 78.2?±?0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.     

Fluid inclusion and H–O–C isotope geochemistry of the Yaochong porphyry Mo deposit in Dabie Shan,China: a case study of porphyry systems in continental collision orogens

The Yaochong porphyry Mo deposit in Xinxian County, Henan Province, China, is located in the Hong’an terrane, that is, the western part of the Dabie orogen. The Dabie orogen is part of a >1,500 km long, Triassic continental collision belt between the North China Block and the South China Block. Four types of vein are present. Paragenetically, from early to late, they are as follows: stage 1 quartz + K-feldspar ± pyrite ± magnetite vein; stage 2 quartz + K-feldspar + molybdenite ± pyrite vein; stage 3 quartz + polymetallic sulfides ± K-feldspar vein; and stage 4 quartz ± carbonate ± fluorite vein. Four compositional types of fluid inclusion, pure CO₂, CO₂ bearing, aqueous, and solid bearing, are present in quartz from the first three stages; only low-salinity aqueous fluid inclusions occur in quartz from the last stage. All the estimated salinities are ≤13.1 wt% NaCl eq., and no halite crystals were identified. Homogenization temperatures for the fluid inclusions from stages 1 to 4 are in the ranges of 262–501, 202–380, 168–345, and 128–286 °C, respectively, and estimated depths decrease from 6.9 to 8.9 km, through 6.2–7.2, to ~4.7 km. Quartz separates from the veins yielded a δ¹⁸O value of 7.7–11.2 ‰, corresponding to δ¹⁸O_H2O values of ?1.3 to 6.9 ‰ using temperature estimates from fluid inclusion data; δD_H2O values of fluid inclusion vary from ?80 to ?55 ‰, and δ¹³C_CO2 from ?2.3 to 2.7 ‰, suggesting that the ore-fluids evolved from magmatic to meteoric sources. We conclude that the ore-forming fluid system at Yaochong was initially high temperature, high salinity, and CO₂-rich and then progressively evolved to CO₂-poor, lower salinity, and lower temperature, by mixing with meteoric water, which results in ore precipitation.