Origin of components in Chilean thermal waters

Thermal waters of northern (18°–27°S) and southern (37°–45°S) Chile occur in two very different climatic, geologic and hydrologic environments: arid closed basins with abundant evaporites in the north; humid climate and well drained valleys in the south. The origin and behavior of the main components of the two groups of waters are examined and compared to each other. The modeling of the alteration of volcanic rocks leads to water compositions very different from those observed both in the north and south. In addition to hydrothermal alteration and deep emanations, the Cl/Br ratio reveals a major contribution of saline waters to the two groups: infiltrating brines from salt lakes in the north; seawater in the south.In the north, concentrations of Cl, Br, Na, K, Ca, SO₄, Li, B, Si result from the mixing of alteration waters with recycled brines. Hydrothermal alteration is obscured by this massive saline input, except for Mg. δ³⁴S values are consistent with an origin of sulfate from salar brines, which are themselves derived from deep Tertiary gypsum. In the south, two processes account for the composition of thermal waters: mixing of alteration waters with seawater and deep magmatic contribution. The mixing process controls the concentration of Cl, Br, Na, Alk, Si, K, Ca, Mg. Magmatic inputs are detectable for SO₄, Li and B. δ³⁴S suggests that sulfate stems from the mixing of alteration waters with either marine SO₄ in coastal waters or with deep SO₂ in inland waters. In both the north and south, the Mg concentration is drastically lowered (<1 μmol/L) by the probable formation of a chlorite-type mineral. In the south, very small amounts of seawater (<1% in volume) are sufficient to imprint a clear signature on thermal waters. Not only coastal springs are affected by seawater mixing, but also remote inland springs, as far as 150 km from the sea. Subduction of marine sediments in the accretive margin could be the source of the marine imprint in thermal waters of southern Chile. Seawater may be expelled from the subducted lithosphere and incorporated into the mantle source.     

Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution

The salt waters from the Emilia-Romagna sector of the Northern Apennine Foredeep have been investigated using major and trace element and stable isotope (δ²H, δ¹⁸O, δ³⁷Cl, δ⁸¹Br and ⁸⁷Sr/⁸⁶Sr ratio). Ca, Mg, Na, K, Sr, Li, B, I, Br and SO₄ vs. Cl diagrams suggest the subaerial evaporation of seawater beyond gypsum and before halite precipitation as primary process to explain the brine’s salinity, whereas saline to brackish waters were formed by mixing of evaporated seawater and water of meteoric origin. A diagenetic end-member may be a third component for mud volcanoes and some brackish waters. Salinization by dissolution of (Triassic) evaporites has been detected only in samples from the Tuscan side of the Apennines and/or interacting with the Tuscan Nappe. In comparison with the seawater evaporation path, Ca–Sr enrichment and Na–K–Mg depletion of the foredeep waters reveal the presence of secondary processes such as dolomitization–chloritization, zeolitization–albitization and illitization. Sulfate concentration, formerly buffered by gypsum-anhydrite deposition, is heavily lowered by bacterial and locally by thermochemical reduction during burial diagenesis. From an isotopic point of view, data of the water molecule confirm mixing between seawater and meteoric end-members. Local ¹⁸O-shift up to +11‰ at Salsomaggiore is related to water–rock interaction at high temperature (≈150°C) as confirmed by chemical (Mg, Li, Ca distribution) and isotopic (SO₄–H₂O) geothermometers. ³⁷Cl/³⁵Cl and ⁸¹Br/⁷⁹Br ratios corroborate the marine origin of the brines and evidence the diffusion of halogens from the deepest and most saline aquifers toward the surface. The ⁸⁷Sr/⁸⁶Sr ratio suggests a Miocene origin of Sr and rule out the hypothesis of a Triassic provenance of the dissolved components for the analyzed waters issuing from the Emilia-Romagna sector of the foredeep. Waters issuing from the Tuscan side of the Apennines and from the Marche sector of the foredeep show higher ⁸⁷Sr/⁸⁶Sr ratios because of the interaction with siliciclastic rocks.     

Origine des eaux des émergences karstiques chlorurées du Languedoc-Roussillon

The origin of chloride-rich karstic spring waters representative of the Languedoc-Roussillon region has been investigated with a hydrochemical approach. To this end, the major and trace elements most often used in the study of saline environments have been considered (Cl, SO₄, Br, B, Li). This study allowed distinguishing the different end-members of the various chloride-rich karstic spring waters (evaporitic, marine, geothermal). Associated with the Cl, Br and B contents, the Li/SO₄ ratio appeared as a relevant tracer for the determination of the origin of lithium and by extension of the considered waters. To cite this article: O. Hébrard et al., C. R. Geoscience 338 (2006).     

Chemical evolution of a gas-capped deep aquifer,southwest of Iran

The Kangan Aquifer (KA) is located below a gas reservoir in the crest of the Kangan Anticline, southwest of Iran. This aquifer is composed of Permo-Triassic limestone, dolomite, sandstone, anhydrite and shale. It is characterized by a total dissolved solid of about 332,000 mg/L and Na–Ca–Cl-type water. A previous study showed that the source of the KA waters is evaporated seawater. Chemical evolution of the KA is the main objective of this study. The major, minor and trace element concentrations of the KA waters were measured. The chemical evolution of KA waters occurred by three different processes: evaporation of seawater, water–rock and water–gas interactions. Due to the seawater evaporation process, the concentration of all ions in the KA waters increased up to saturation levels. In comparison to the evaporated seawater, the higher concentrations of Ca, Li, Sr, I, Mn and B and lower concentrations of Mg, SO₄ and Na and no changes in concentrations of Cl and K ions are observed in the KA waters. Based on the chemical evolution after seawater evaporation, the KA waters are classified into four groups: (1) no evolution (Cl, K ions), (2) water–rock interaction (Na, Ca, Mg, Li and Sr ions), (3) water–gas interaction (SO₄ and I ions) and (4) both water–rock and water–gas interactions (Mn and B ions). The chemical evolution processes of the KA waters include dolomitization, precipitation, ion exchange and recrystallization in water–rock interaction. Bacterial reduction and diagenesis of organic material in water–gas interaction also occur. A new type of chart, Ca_excess versus Mg_deficit, is proposed to evaluate the dolomitization process.     

Geochemistry of deep formation waters in the Canning Basin,Western Australia,and their relationship to Zn‐Pb mineralization

The Canning Basin contains several Mississippi Valley‐type Zn‐Pb sulphide prospects and deposits in Devonian carbonate reef complexes on the northern edge of the Fitzroy Trough, and in Ordovician and Silurian marine sequences on the northern margin of the Willara Sub‐basin. This study uses the ionic composition and 5D, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr isotopic data on present‐day deep formation waters to determine their origin and possible relationship to the Zn‐Pb mineralizing palaeofluids.

The present‐day Canning Basin formation waters have salinity ranging from typically less than 5000 mg/L up to 250 000 mg/L locally. The brines are mixtures of highly saline water, formed by seawater which evaporated beyond halite saturation (bittern water), with meteoric water ranging in salinity from low (<5000 mg/L) to hypersaline water (up to about 50 000 mg/L) formed by re‐solution of halite and calcium sulphate minerals. The original marine chemical composition of the bittern‐dominated brines was changed to that of a Na‐Ca‐Cl water by addition of Ca and removal of Mg and SO₄, initially by bacterial sulphate reduction and later by dolomitization of carbonate. Other reactions with terrigenous components of the sediment have provided additional Ca and Sr, including a small proportion of ⁸⁷Sr‐rich material. The δ³⁴S values of the bittern‐containing waters are within the range over which marine sulphate has fluctuated from the Ordovician to the Holocene, although one of the hypersaline waters has a value of +6.8%, indicating SO₄ of non‐marine origin. The pH of the bittern‐containing waters is low (about 5) and they contain significant concentrations of dissolved Fe (up to 120 mg/L).

The Canning Basin bitterns appear similar in origin and chemical composition to highly saline marine brines in the Mississippi Salt Dome Basin, USA, which are known to be either metal or sulphide‐rich depending on the organic content of the host rock. In the Canning Basin, mixing of the bittern water with the various types of meteoric water has resulted in decreases in salinity, Na, Ca, Mg, K, Sr, Li and Fe, and increases in HCO₃, SO₄ and pH.

Mixing of the bitterns with other types of metalliferous fluids and/or with sulphate‐containing hypersaline meteoric waters formed from the same marine evaporite sequence should produce ore‐precipitating fluids which are relatively hot and saline, and the resulting ore deposit should be of high grade and contain abundant sulphate minerals. In the southern Canning Basin, this type of mixing and the corresponding style of ore deposit is evident in the evaporite‐associated areas of Zn‐Pb mineralization near the Admiral Bay Fault. If the bitterns mix with low salinity HCO₃‐waters in near‐surface environments, then the ore‐precipitating fluids should have relatively low salinities and carbonate minerals would precipitate during later stages of mixing. In the Lennard Shelf, the present‐day formation waters, the style of the Zn‐Pb deposits, and range of salinity and temperature of the ore‐forming palaeofluids are consistent with this type of mixing.     

Sources of elevated salinity in the Mississippi River Alluvial Aquifer, south-central Louisiana, USA

Salinization is a process impacting groundwater quality and availability across much of southern Louisiana, USA. However, a broad divergence of opinion exists regarding the causes of this elevated salinity: updip-migrating marine waters from the Gulf of Mexico, saline fluids migrating up fault planes, movement of water from salt domes, and/or remnant seawater from the last major marine transgression. The Mississippi River Alluvial Aquifer (MRAA) in south-central Louisiana is recharged by the Mississippi River, and there are discharge zones to the west and east. Recharge waters from the Mississippi River are fresh, but Cl⁻ levels in the western portions of the aquifer are as high as 1000 mg/L. The aquifer is an important source of water for several municipalities and industries, but prior to this study the source(s) of the elevated salinity or whether the salinization can be remediated had not been determined.The low Br/Cl ratios in the groundwaters are consistent with a saline endmember produced by subsurface dissolution of salt domes, not a marine source. The H and O isotopic systematics of the aquifer waters indicate meteoric sources for the H₂O, not marine waters or diagenetically-altered deep brines. The westward salinization of aquifer water represents a broad regional process, instead of contamination by point sources. Mapping of spatial variations in salinity has permitted the identification of specific salt domes whose subsurface dissolution is producing waters of elevated salinity in the aquifer. These include the Bayou Choctaw and St. Gabriel domes, and possibly the Bayou Blue dome. Salinization is a natural, on-going process, and the potential for remediation or control is slight, if not non-existent.     

Origin of groundwater salinity (current seawater vs. saline deep water) in a coastal karst aquifer based on Sr and Cl isotopes. Case study of the La Clape massif (southern France)

In this study a typical coastal karst aquifer, developed in lower Cretaceous limestones, on the western Mediterranean seashore (La Clape massif, southern France) was investigated. A combination of geochemical and isotopic approaches was used to investigate the origin of salinity in the aquifer. Water samples were collected between 2009 and 2011. Three groundwater groups (A, B and C) were identified based on the hydrogeological setting and on the Cl⁻ concentrations. Average and maximum Cl⁻ concentrations in the recharge waters were calculated (Cl_Ref. and Cl_Ref.Max) to be 0.51 and 2.85 mmol/L, respectively). Group A includes spring waters with Cl⁻ concentrations that are within the same order of magnitude as the Cl_Ref concentration. Group B includes groundwater with Cl⁻ concentrations that range between the Cl_Ref and Cl_Ref.Max concentrations. Group C includes brackish groundwater with Cl⁻ concentrations that are significantly greater than the Cl_Ref.Max concentration. Overall, the chemistry of the La Clape groundwater evolves from dominantly Ca–HCO₃ to NaCl type. On binary diagrams of the major ions vs. Cl, most of the La Clape waters plot along mixing lines. The mixing end-members include spring waters and a saline component (current seawater or fossil saline water). Based on the Br/Cl_molar ratio, the hypothesis of halite dissolution from Triassic evaporites is rejected to explain the origin of salinity in the brackish groundwater.Groundwaters display ⁸⁷Sr/⁸⁶Sr ratios intermediate between those of the limestone aquifer matrix and current Mediterranean seawater. On a Sr mixing diagram, most of the La Clape waters plot on a mixing line. The end-members include the La Clape spring waters and saline waters, which are similar to the deep geothermal waters that were identified at the nearby Balaruc site. The ³⁶Cl/Cl ratios of a few groundwater samples from group C are in agreement with the mixing hypothesis of local recharge water with deep saline water at secular equilibrium within a carbonate matrix. Finally, PHREEQC modelling was run based on calcite dissolution in an open system prior to mixing with the Balaruc type saline waters. Modelled data are consistent with the observed data that were obtained from the group C groundwater. Based on several tracers (i.e. concentrations and isotopic compositions of Cl and Sr), calculated ratios of deep saline water in the mixture are coherent and range from 3% to 16% and 0% to 3% for groundwater of groups C and B, respectively.With regard to the La Clape karst aquifer, the extension of a lithospheric fault in the study area may favour the rise of deep saline water. Such rises occur at the nearby geothermal Balaruc site along another lithospheric fault. At the regional scale, several coastal karst aquifers are located along the Gulf of Lion and occur in Mezosoic limestones of similar ages. The ⁸⁷Sr/⁸⁶Sr ratios of these aquifers tend toward values of 0.708557, which suggests a general mixing process of shallow karst waters with deep saline fossil waters. The occurrence of these fossil saline waters may be related to the introduction of seawater during and after the Flandrian transgression, when the highly karstified massifs invaded by seawater, formed islands and peninsulas along the Mediterranean coast.     

Evolution of saline waters and brines in the Benue-Trough,Nigeria

Hydrogeochemical assessment of 40 saline waters and brines from 20 locations within the lower (southern) and middle regions of the Benue-Trough, Nigeria are presented and discussed in terms of genesis of the primary salinity and subsequent hydrochemical evolution. The total dissolved ions range from 5263 to 88,800 mg/L and 5148 to 47,145 mg/L in the lower and middle region, respectively.The saline waters and brines are characteristically Na–Cl type enriched in Ca and Sr on the one hand and depleted in Mg and SO₄ on the other, relative to the seawater evaporation trend. Ionic ratios, Na–Cl–Br systematic and divalent cations suggest two likely sources of primary salinity: a fossil seawater source and dissolution of halite. However, water–rock interaction involving Mg uptake by clay minerals and possibly dolomitization during diagenesis appear to be responsible for further modification of the primary chemistry. A conceptualized hydrogeological/flow model for the brines is presented.     

The behavior of lithium and its isotopes in oilfield brines: evidence from the Heletz-Kokhav field, Israel

Twenty-four brine samples from the Heletz-Kokhav oilfield, Israel, have been analyzed for chemical composition and Li isotope ratios. The chemical composition of the brines, together with geological evidence, suggests derivation from (Messinian) seawater by evaporation that proceeded well into the gypsum stability field but failed to reach the stage of halite crystallization. The present salinity of the samples (18-47 g Cl/L) was achieved by dilution of the original evaporitic brine by local fresh waters. Like brines from other sedimentary basins, the Li/Cl ratios in the Heletz-Kokhav samples show a prominent Li enrichment (five-fold to eight-fold) relative to modern seawater. The isotopic ratios of Li, expressed in the δ ⁶Li notation, vary from −26.3 to −17.9‰, all values being significantly higher than that of modern seawater (−32‰) irrespective of their corresponding Li concentration (1.0-2.3 mg/L). The isotopic composition of Li and the Li/Cl ratio in the oilfield brines were acquired in two stages: (a) The original evaporated seawater gained isotopically light Li during the diagenetic interaction between the interstitial Messinian brine and the basin sediments. A parent brine with an elevated Li/Cl ratio was formed. The brine was later diluted in the oilfields. (b) The δ ⁶Li values of the final brines were determined during epigenetic interaction with the Heletz-Kokhav aquifer rocks. At the same time, the Li/Cl ratio inherited from stage (a) remained largely unchanged. This work represents the first use of lithium isotopic composition to elucidate the origin and evolution of formation waters in sedimentary basins.     

Origin of boron from a complex aquifer in southeast of Spain

A study of the boron content alongside Cl ^-, SO ₄ ^2-, and NO ₃ ^- ions has enabled the factors that determine its origin to be distinguished. In carbonate rocks, with their higher saline content, boron is associated with marine intrusion. In the Plioquaternary aquifer, its origin is complex and is associated with three processes: marine intrusion, where there is a high Cl ^- content and the B/Cl ^- ratio is close to that of seawater; anthropogenic pollution, at points with high B and NO ₃ ^- concentrations and where the B/Cl ^- ratio is higher than that of seawater; and the dissolution of evaporite deposits present in the Plioquaternary strata, at a series of sampling points where the SO ₄ ^2-/Cl ^- ratio is elevated and B content is high.     

Origin of salinity of deep groundwater in crystalline rocks

Deep groundwater in fractured crystalline basement has been reported from deep mines and from scientific deep wells. Highly saline brines have been described from several km depth in the continental basement of the Canadian, Fennoscandian and Ukrainian shields and elsewhere in the world. The origin of salinity is unknown and many different possibilities have been presented. We compare the compositional evolution of deep waters in the Black Forest basement, SW Germany, with those of other deep crystalline waters, and use halogen systematics (e.g. Cl/Br ratios) and other parameters of the waters to deduce the origin of their salinity. In the Black Forest the composition of deep thermal waters results from chemical interaction of surface water with the rock matrix (mainly weathering of plagioclase and mica) and from mixing of the reacted water with stagnant saline deep water. Here we show by Na/TDS-and Cl/TDS-investigations, by molality-ratios of the Na and Cl concentrations, and by Cl/Br systematics that these deep saline waters have a marine origin. The Cl/Br ratios in deep crystalline waters are very close to normal marine ratios (Cl/Br = 288 ppm basis). In contrast, Cl/Br ratios of other possible sources of salinity show distinctly different Cl/Br ratios: water derived from dissolved Tertiary halite deposits of the rift valley is in the order of Cl/Br = 2400 and water from dissolved Muschelkalk halite deposits has values of about Cl/Br = 9900. Leaching experiments on crystalline rocks, on the other hand, show that the average Cl/Br ratio of crystalline rocks is far below Cl/Br = 100.     

Origin and migration of brines from Paleozoic strata in Central Tarim,China: constraints from 87Sr/86Sr, δD, δ18O and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, and δ¹⁸O of oilfield waters, and ⁸⁷Sr/⁸⁶Sr of whole rock were measured from Paleozoic strata in the Central Tarim basin, NW China. The aim is to elucidate the origin and migration of formation water and its relation to petroleum migration. High salinity oilfield waters in Carboniferous, Silurian and Ordovician reservoirs have maintained the same Na/Cl ratio as seawater, indicative of subaerially evaporated seawater. Two possible sources of evaporitic water are Carboniferous (C_II) and Cambrian, both of which contain evaporitic sediments. Geographic and stratigraphic trends in water chemistry suggest that most of the high salinity water is from the Cambrian. Strontium, H and O isotopes as well as ion chemistry indicate at least 3 end member waters in the basin. High-salinity Cambrian evaporitic water was expelled upward into Ordovician, Silurian and Carboniferous reservoirs along faults and fractures during compaction and burial. Meteoric water has likely invaded the section throughout its history as uplift created subaerial unconformities. Meteoric water certainly infiltrated Silurian and older strata during development of the C_III unconformity and again in recent times. Modern meteoric water enters Carboniferous strata from the west and flows eastward, mixing with the high salinity Cambrian water and to a lesser degree with paleometeoric water. The third end member is highly radiogenic, shale-derived water which has migrated eastward from the Awati Depression to the west. Enrichment of Ca and Sr and depletion of K, Mg, and SO₄ relative to the seawater evaporation trajectory suggest waters were affected by albitization of feldspars, dolomitization, illitization of smectite, and SO₄ reduction. The mixing of meteoric water occurred subsequently to seawater evaporation, main water-rock interactions, and brine migration. The direction of brine migration is consistent with that of petroleum migration, suggesting water and petroleum have followed the same migration pathways.     

Halogen concentrations in pore waters and sediments of the Nankai Trough,Japan: Implications for the origin of gas hydrates

Presented here are halogen concentrations (Cl, Br and I) in pore waters and sediments from three deep cores in gas hydrate fields of the Nankai Trough area. The three cores were drilled between 1999 and 2004 in different geologic regions of the northeastern Nankai Trough hydrate zone. Iodine concentrations in all three cores increase rapidly with depth from seawater concentrations (0.00043 mmol/L) to values of up to 0.45 mmol/L. The chemical form of I was identified as I⁻, in accordance with the anaerobic conditions in marine sediments below the SO₄ reduction depth. The increase in I is accompanied by a parallel, although lesser increase in Br concentrations, while Cl concentrations are close to seawater values throughout most of the profiles. Large concentration fluctuations of the three halogens in pore waters were found close to the lower boundary of the hydrate stability zone, related to processes of formation and dissociation of hydrates in this zone. Generally low concentrations of I and Br in sediments and the lack of correlation between sediment and pore water profiles speak against derivation of I and Br from local sediments and suggest transport of halogen rich fluids into the gas hydrate fields. Differences in the concentration profiles between the three cores indicate that modes of transportation shifted from an essentially vertical pattern in a sedimentary basin location to more horizontal patterns in accretionary ridge settings. Because of the close association between organic material and I and the similarity of transport behavior for I⁻ and CH₄, the results suggest that the CH₄ in the gas hydrates also was transported by aqueous fluids from older sediments into the present layers.     

Hydrochemistry in coastal aquifer of southwest Bangladesh: origin of salinity

In the coastal region of Bangladesh, groundwater is mainly used for domestic and agricultural purposes, but salinization of many groundwater resources limits its suitability for human consumption and practical application. This paper reports the results of a study that has mapped the salinity distribution in different aquifer layers up to a depth of 300 m in a region bordering the Bay of Bengal based on the main hydrochemistry and has investigated the origin of the salinity using Cl/Br ratios of the samples. The subsurface consists of a sequence of deltaic sediments with an alternation of more sandy and clayey sections in which several aquifer layers can be recognized. The main hydrochemistry shows different main water types in the different aquifers, indicating varying stages of freshening or salinization processes. The most freshwater, soft NaHCO₃-type water with Cl concentrations mostly below 100 mg/l, is found in the deepest aquifer at 200–300 m below ground level (b.g.l.), in which the fresh/saltwater interface is pushed far to the south. Salinity is a main problem in the shallow aquifer systems, where Cl concentrations rise to nearly 8000 mg/l and the groundwater is mostly brackish NaCl water. Investigation of the Cl/Br ratios has shown that the source of the salinity in the deep aquifer is mixing with old connate seawater and that the saline waters in the more shallow aquifers do not originate from old connate water or direct seawater intrusion, but are derived from the dissolution of evaporite salts. These must have been formed in a tidal flat under influence of a strong seasonal precipitation pattern. Long dry seasons with high evaporation rates have evaporated seawater from inundated gullies and depressions, leading to salt precipitation, while subsequent heavy monsoon rains have dissolved the formed salts, and the solution has infiltrated in the subsoil, recharging groundwater.     

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.     

Geochemical Constraints on the Origin and Evolution of Spring Waters in the Changdu‐Lanping‐Simao Basin,Southwestern China

Chemical and isotopic data were measured for 51 leached brine springs in the Changdu-Lanping-Simao Basin (CD-LP-SM), China. The predominance of Cl and Na, saturation indices of carbonate minerals, and Na/Cl and Ca/SO4 ratios of ~1 suggest that halite, sulphate, and carbonate are the solute sources. Integration of geochemical, δ18O, and δD values suggests that springs are mainly derived from meteoric water, ice-snow melt, and water-rock interactions. B concentrations range from 0.18 to 11.9 mg/L, with δ11B values of ?4.37‰ to +32.39‰, indicating a terrestrial source. The δ11B-B relationships suggest B sources of crustal origin (marine carbonates with minor crust-derived volcanics); we did not identify a marine or deep mantle origin. The δ11B values of saline springs (+4.61‰ to +32.39‰) exceed those of hot (?4.37‰ to +4.53‰) and cold (?3.47‰ to +14.84‰) springs; this has contributed to strong water-rock interactions and strong saturation of dissolved carbonates. Conversely, the global geothermal δ11B-Cl/B relationship suggests mixing of marine and non-marine sources. The δ11B-Cl/B relationships of the CD-LP-SM are similar to those of the Tibet geothermal belt and the Nangqen Basin, indicating the same B origin. These differ from thermal waters controlled by magmatic fluids and seawater, suggesting that B in CD-LP-SM springs has a crustal origin.     

Origin of brine in the Kangan gasfield: isotopic and hydrogeochemical approaches

The Kangan Permo-Triassic brine aquifer and the overlying gas reservoir in the southern Iran are located in Kangan and Dalan Formations, consisting dominantly of limestone, dolomite, and to a lesser extent, shale and anhydrite. The gasfield, 2,900 m in depth and is exploited by 36 wells, some of which produce high salinity water. The produced water gradually changed from fresh to saline, causing severe corrosion in the pipelines and well head facilities. The present research aims to identify the origin of this saline water (brine), as a vital step to manage saline water issues. The major and minor ions, as well as δ²H, δ¹⁸O and δ³⁷Cl isotopes were measured in the Kangan aquifer water and/or the saline produced waters. The potential processes causing salinity can be halite dissolution, membrane filtration, and evaporation of water. The potential sources of water may be meteoric, present or paleo-seawater. The Na/Cl and I/Cl ratios versus Cl^? concentration preclude halite dissolution. Concentrations of Cl, Na, and total dissolved solid were compared with Br concentration, indicating that the evaporated ancient seawater trapped in the structure is the cause of salinization. δ¹⁸O isotope enrichment in the Kangan aquifer water is due to both seawater evaporation and interaction with carbonate rocks. The δ³⁷Cl isotope content also supports the idea of evaporated ancient seawater as the origin of salinity. Membrane filtration is rejected as a possible source of salinity based on the hydrochemistry data, the δ¹⁸O value, and incapability of this process to dramatically enhance salinity up to the observed value of 330,000 mg/L. The overlaying impermeable formations, high pressure in the gas reservoir, and the presence of a cap rock above the Kangan gasfield, all prevent the downward flow of meteoric and Persian Gulf waters into the Kangan aquifer. The evaporated ancient seawater is autochthonous, because the Kangan brine aquifer was formed by entrapment of brine seawater during the deposition of carbonates, gypsum, and minor clastic rocks in a lagoon and sabkha environment. The reliability of determining the source of salinity in a deep complicated inaccessible high-pressure aquifer can be improved by combining various methods of hydrochemistry, isotope, hydrodynamics, hydrogeology and geological settings.     

Hydrogeochemical characteristics and genetic implications of Edipsos thermal springs, north Euboea, Greece

Edipsos area, situated in northern Euboea, has been well known since ancient times for the existence of thermal springs. In order to assess the hydrogeochemical conditions, thermal and cold water samples were collected and analyzed by ICP method for major and trace elements. The results revealed the direct impact of seawater, a process which is strongly related to the major tectonic structures of the area. Seawater impact was confirmed by the Cl/Br and Na/Cl ionic ratios, as well as from statistical processing and graphical interpretation of the analytical results, which classified the sampled waters into three groups (two for cold waters and one for the thermal ones). Trace element ranges for thermal waters are: As (44–84 ppb), Pb (23–154 ppb), Ag (1–2 ppb), Mn (31–680 ppb), Cu (61–97 ppb), Cs (66–244 ppb), Se (0–76 ppb), Li (732–3269 ppb), Fe (0–1126 ppb), Sr (14000–34100 ppb), B (4300–9600 ppb). Compared with the chemical composition of other thermal springs from the Hellenic Volcanic Arc, Edipsos thermal waters are enriched in Ca²⁺, Na⁺, Cl^?, SO₄ ^2?, Li, B and K⁺, reflecting the influence from seawater. Cold waters are free of heavy metals compared with other natural waters and are characterized by good quality based on the major element chemistry. Finally, several geothermometers were applied in order to assess the reservoir temperatures, but none of them appear to be applicable, mainly due to the impact of seawater on the initial hydrogeochemistry of the geothermal fluids.     

Study of shallow groundwater quality evolution under saline intrusion with environmental isotopes and geochemistry

Evolution of the shallow groundwater quality under saline intrusion in porous aquifer system has been studied with environmental isotopes and geochemistry in the Laizhou Bay area, China. Two campaigns of water sampling from various sources were carried out in spring and winter for environmental isotopic and chemical analyses. The origin of groundwater salinity from intrusion of both modern seawater and deep brine water was identified by analysing the correlations between ¹⁸O, D, T, Cl⁻, SO₄²⁻ and electrical conductivity. The results indicate that the brine is originated from evaporating and concentrating of intruded seawater and its δD and δ¹⁸O are different from modern seawater but similar to those of mixture of seawater with fresh groundwater. It is hard to distinguish the salinity origin in this area by the δD–δ¹⁸O relationship alone. The relations between δ¹⁸O and conductivity, Cl⁻ and SO₄²⁻ have been used to identify the salinity origin due to the distinct difference in salinity between the brine and seawater, conjunctively with use of T. A threshold of T = 12 TU was adopted to identify the origin of saline groundwater.     

Identifying sources of salinization using hydrochemical and isotopic techniques, Konarsiah, Iran

Konarsiah salt diapir is situated in the Simply Folded Zone of the Zagros Mountain, south Iran. Eight small permanent brine springs emerge from the Konarsiah salt body, with average total dissolved solids of 326.7 g/L. There are numerous brackish to saline springs emerging from the alluvial and karst aquifers adjacent to the diapir. Concerning emergence of Konarsiah diapir in the study area, halite dissolution is the most probable source of salinity in the adjacent aquifers. However, other sources including evaporation and deep brines through deep Mangerak Fault are possible. The water samples of the study area were classified based on their water-type, salinity, and the trend of the ions concentration curves. The result of this classification is in agreement with the hydrogeological setting of the study area. The hydrochemical and isotopic evaluations show that the groundwater samples are the result of mixing of four end members; Gachsaran sulfate water, Sarvak and Asmari carbonate fresh waters, and diapir brine. The molar ratios of Na/Cl, Li/Cl, Br/Cl, and SO₄/Cl; and isotopic signature of the mixed samples justify a groundwater mixing model for the aquifers adjacent to the salt diapir. The share of brine in each adjacent aquifer was calculated using Cl mass balance. In addition, concentrations of 34 trace elements were determined to characterize the diapir brine and to identify the possible tracers of salinity sources in the mixed water samples. B, Mn, Rb, Sr, Cs, Tl, and Te were identified as trace elements evidencing contact of groundwater with the salt diapir.