Chemical composition of thermal springs, cold springs, streams, and gas vents in the Mt. Amiata geothermal region (Tuscany, Italy)

A geochemical study of thermal and cold springs, stream waters and gas emissions has been carried out in the Mt. Amiata geothermal region.The cold springs and stream waters do not seem to have received significant contribution from hot deep fluids. On the contrary, the thermal springs present complex and not clearly quantifiable interactions with the hot fluids of the main geothermal reservoir.The liquid-dominated systems in the Mt. Amiata area, like most of the high-enthalpy geothermal fields in the world, are characterized by saline, NaCl fluids. The nature of the reservoir rock (carbonatic and anhydritic), and its widespread occurrence in central Italy, favor a regional circulation of “Ca-sulfate” thermal waters, which discharge from its outcrop areas. Waters of this kind, which have been considered recharge waters of the known geothermal fields, dilute, disperse and react with the deep geothermal fluids in the Mt. Amiata area, preventing the use of the main chemical geothermometers for prospecting purposes. The temperatures obtained from the chemical geothermometers vary widely and are generally cooler than temperatures measured in producing wells.Other thermal anomalies in central Italy, apart from those already known, might be masked by the above-mentioned circulation. A better knowledge of deep-fluid chemistry could contribute to the calibration of specific geothermometers for waters from reservoirs in carbonatic rocks.     

Hydrogeochemistry and strontium isotopes in the Arno River Basin (Tuscany, Italy): Constraints on natural controls by statistical modeling

In this paper the chemistry of major and trace elements and, for the first time, strontium isotopic ratios measured in running waters from the Arno River Basin (Tuscany, central-northern Italy) and thermal springs discharging in the same hydrographic system are presented and discussed. Classical graphical methods (e.g. mixing diagrams) have here been improved to identify, in a correct statistical sample space, extreme chemical compositions attributable to the action of geochemical processes and/or inherited from specific lithologies (namely contributions or components 1, 2 and 3) to be used in inverse modeling procedures, due to the absence of clear end-members. A linear least squares problem, with non-negativity constraints and distances, as required for compositional data (convex linear mixing) was solved by considering the contribution of the most discriminant variables given by the ⁸⁷Sr/⁸⁶Sr isotopic ratios and the concentration of Ca²⁺, Mg²⁺, Sr and Rb. Following such approach, it can be assumed (p < 0.05) that component 1, characterized by a Ca²⁺(Mg²⁺)– radiogenic-rich (⁸⁷Sr/⁸⁶Sr = 0.71274; Rb/Sr = 0.039), represents a dominant feature at basin scale, with a weight ranging from 69% to 100%. Much lower percentages are related to component 2, represented by a Ca²⁺(Mg²⁺)– facies with intermediate ⁸⁷Sr/⁸⁶Sr (0.70874) and low Rb/Sr (2.8 × 10⁻⁴) ratios and component 3, identified by Ca²⁺– facies with less radiogenic ⁸⁷Sr/⁸⁶Sr (0.70827) and low Mg²⁺/Ca²⁺ (0.011) ratios. These components are mainly dominated by the dissolution of evaporitic rocks and/or mixing with thermal waters in the southern part of the Arno River Basin and by dissolution of the carbonatic fraction, kinetically favored with respect to that of the silicatic minerals, in the upper reaches of the main course and its tributaries, respectively.     

Geochemistry, geothermics and relationship to active tectonics of Gujarat and Rajasthan thermal discharges, India

Most thermal spring discharges of Rajasthan and Gujarat in northwestern India have been sampled and analysed for major and trace elements in both the liquid and associated gas phase, and for ¹⁸O/¹⁶O, D/H (in water), ³He/⁴He and ¹³C/¹²C in CO₂ (in gas) isotopic ratios. Most thermal springs in Rajasthan are tightly associated to the several regional NE–SW strike-slip faults bordering NE–SW ridges formed by Archaean rocks at the contact with Quaternary alluvial and aeolian sedimentary deposits of the Rajasthan desert. Their Ca–HCO₃ immature character and isotopic composition reveals: (1) meteoric origin, (2) relatively shallow circulation inside the crystalline Archaean formations, (3) very fast rise along faults, and (4) deep storage temperatures of the same order of magnitude as discharging temperatures (50–90°C). Thermal spring discharges in Gujarat are spread over a larger area than in Rajasthan and are associated both with the NNW–SSE fault systems bordering the Cambay basin and the ENE–WSW strike-slip fault systems in the Saurashtra province, west of the Cambay basin. Chemical and isotopic compositions of springs in both areas suggest a meteoric origin of deep thermal waters. They mix with fresh or fossil seawater entering the thermal paths of the spring systems through both the fault systems bordering the Cambay basin, as well as faults and fractures occurring inside the permeable Deccan Basalt Trap in the Saurashtra province. The associated gas phase, at all sampled sites, shows similar features: (1) it is dominated by the presence of atmospheric components (N₂ and Ar), (2) it has high crustal ⁴He enrichment, (3) it shows crustal ³He/⁴He signature, (4) it has low CO₂ concentration, and (5) the only analysed sample for ¹³C/¹²C isotopic ratio in CO₂ suggests that CO₂ has a strong, isotopically light organic imprint. All these features and chemical geothermometer estimates of spring waters suggest that any active deep hydrothermal system at the base of the Cambay basin (about 2000–3000 m) has low-to-medium enthalpy characteristics, with maximum deep temperature in the storage zone of about 150°C. In a regional overview, both thermal emergences of Rajasthan and Gujarat could be controlled by the counter-clockwise rotation of India.     

Thermal springs,fumaroles and gas vents of continental Yemen: Their relation with active tectonics,regional hydrology and the country’s geothermal potential

Most thermal springs of continental Yemen (about 65 emergences at 48 sampling sites) and a couple of fumaroles and boiling water pools have been sampled and analyzed for chemical and isotopic composition in the liquid phase and the associated free-gas phase. Whatever the emergence, all the water discharges have an isotopic signature of meteoric origin. Springs seeping out from high altitudes in the central volcanic plateau show a prevalent Na–HCO₃-composition, clearly affected by an anomalous flux of deep CO₂ deriving from active hydrothermal systems located in the Jurassic Amran Group limestone sequence and/or the Cretaceous Tawilah Group, likely underlying the 2000–3000 m thick volcanic suite. At lower elevations, CO₂ also affects the composition of some springs emerging at the borders of the central volcanic plateau.     

Geochemistry of water and gas discharges from the Mt. Amiata silicic complex and surrounding areas (central Italy)

The Mt. Amiata volcano in central Italy is intimately related to the post-orogenic magmatic activity which started in Pliocene times. Major, trace elements, and isotopic composition of thermal and cold spring waters and gas manifestations indicate the occurrence of three main reservoir of the thermal and cold waters in the Mt. Amiata region. The deepest one is located in an extensive carbonate reservoir buried by thick sequences of low-permeability allochthonous and neo-autochthonous formations. Thermal spring waters discharging from this aquifer have a neutral Ca-SO₄ composition due to the presence of anhydrite layers at the base of the carbonate series and, possibly, to absorption of deep-derived H₂S with subsequent oxidation to SO₄²⁻ in a system where pH is buffered by the calcite–anhydrite pair (Marini and Chiodini, 1994). Isotopic signature of these springs and N₂-rich composition of associated gas phases suggest a clear local meteoric origin of the feeding waters, and atmospheric O₂ may be responsible for the oxidation of H₂S. The two shallower aquifers have different chemical features. One is Ca-HCO₃ in composition and located in several sedimentary formations above the Mesozoic carbonates. The other one has a Na-Cl composition and is hosted in marine sediments filling many post-orogenic NW–SE-trending basins. Strontium, Ba, F, and Br contents have been used to group waters associated with each aquifer. Although circulating to some extent in the same carbonate reservoir, the deep geothermal fluids at Latera and Mt. Amiata and thermal springs discharging from their outcropping areas have different composition: Na-Cl and Ca-SO₄ type, respectively. Considering the high permeability of the reservoir rock, the meteoric origin of thermal springs and the two different composition of the thermal waters, self-sealed barriers must be present at the boundaries of the geothermal systems. The complex hydrology of the reservoir rocks greatly affects the reliability of geothermometers in liquid phase, which understimate the real temperatures of the discovered geothermal fields. More reliable temperatures are envisaged by using gas composition-based geothermometers. Bulk composition of the 67 gas samples studied seems to be the result of a continuous mixing between a N₂-rich component of meteoric origin related to the Ca-SO₄ aquifer and a deep CO₂-rich component rising largely along the boundaries of the geothermal systems. Nitrogen-rich gas samples have nearly atmospheric N₂/Ar (=83) and

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(δ=0‰) ratios whereas CO₂-rich samples show anomalously high

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values (up to +6.13 ‰), likely related to N₂ from metamorphic schists lying below the carbonate formations. On the basis of average

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isotopic ratio (

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around 0‰), CO₂ seems to originate mainly from thermometamorphic reactions in the carbonate reservoir and/or in carbonate layers embedded in the underlying metamorphic basement. Distribution of

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isotopic ratios indicates a radiogenic origin of helium in a tectonic environment that, in spite of the presence of many post-orogenic basins and mantle-derived magmatics, can presently be considered in a compressive phase.     

Geochemical evolution of southern Red Sea and Yemen flood volcanism: evidence for mantle heterogeneity

The Red Sea is part of the Afro-Arabian rift system, the world’s largest active continental rift system. The early opening phases of the Red Sea Rift were accompanied by continental flood magmatism. Large volumes of flood basalts emplaced in the Oligocene through to the present time at discrete eruptive centres along the western margin of the Arabian plate. Some of these rocks, in Southern Yemen, were investigated by geochemistry and K/Ar whole rock (WR) geochronology. In addition, the Jabal At-Tair (JAT) volcano, in the Red Sea trough, was investigated by geochemistry, with particular concern to the lavas of the last eruption of September 2007. The magmatism of Yemen is divided in: Oligocene–Early Miocene trap series (YOM), Tertiary intrusive rocks, and Late Miocene–recent volcanic series (YMR). YOM and Tertiary intrusions yielded K/Ar WR ages mostly in the range 31.6–16.6 Ma. Three older ages of 34.6, 35.4 and 49.0 Ma, if confirmed by further investigation, could suggest an Eocenic pre-trap phase of magmatic activity. YMR samples yielded K/Ar WR ages between 2.52 and 8.14 Ma. Both YOM and YMR basalts are alkaline, but YMR tend to be richer in alkalis than YOM. JAT basalts have subalkaline tholeiitic character, are geochemically homogeneous, and in the hygromagmaphile element spidergrams display increasing normalised concentrations from Cs to Ta, then decreasing up to Lu, with negative spikes of Nb, K and Pb. YOM have patterns almost identical to those of JAT, whereas YMR have higher normalized concentrations of all trace elements, but REE. The geochemical characteristics of JAT, YOM and YMR, framed in the broader context of the Red Sea Rift, are mostly consistent with a model of continental uplift and magmatism occurring across a linear, north–south axis of mantle upwelling, which intersects the Red Sea axis at the initiation site of axial seafloor spreading. The symmetrical propagation of the rift system to opposite sides of the N–S lineament, along the Red Sea axis, resulted in the observed symmetrical distribution of geochemical signatures of the Red Sea basalts and Yemen continental magmas.     

Karst springs as “natural” pluviometers: Constraints on the isotopic composition of rainfall in the Apennines of central Italy

This paper describes an indirect method to calculate the isotopic composition of rainfall by using the isotopic composition of karst springs fed by waters circulating in the most important regional aquifer of central Italy, i.e. the Mesozoic limestone sequence that forms the backbone of the Apennines. By using δ¹⁸O and δD data and the δ¹⁸O (and/or δD) average gradient for elevation, evaluated through the use of literature rainfall data and new measurements from a typical Alpine valley in northern Italy, the altitude of precipitation of their parent water has been re-calculated. Vertical descents of more than 2000 m, from recharge to discharge, have been assessed in some high flow-rate cold springs in the morphologically steep Adriatic sector of central Italy. A clear correlation between the vertical descents and more negative isotopic compositions at their relative emergence elevations is highlighted. In contrast, in the Tyrrhenian sector lower karstic drops (generally lower than 500 m) correlate with less negative isotopic composition of recharge areas.The δ¹⁸O iso-contour map of the “recalculated” parent rainfall in central Italy is more detailed than any possible isotopic map of rainfall made using pluviometers, unless large number of rainfall collectors were deployed on mountaintops. The data also show that the isotopic composition of rainfall depends on the source of the storm water. In particular, precipitation is isotopically heavier when originating in the Mediterranean Sea, and lighter when formed in the Atlantic Ocean. Consequently, the collision between air masses with such a different isotopic signature results in a relatively small latitudinal fractionation effect. The peninsular part of central Italy is very narrow, with several mountains and massifs more that 2000 m high, and any latitudinal variation in the isotopic composition between rainfall sourced in the Atlantic Ocean and in the Mediterranean Sea is much lower than that due to the isotopic fractionation due to elevation.     

Fluid geochemistry of the Mondragone hydrothermal systems (southern Italy): water and gas compositions vs. geostructural setting

International Journal of Earth Sciences - The geochemistry of natural thermal fluids discharging in the Mondragone Plain has been investigated. Thermal spring emergences are located along the...     

Geochemistry of Quaternary travertines in the region north of Rome (Italy): structural, hydrologic and paleoclimatic implications

In the Tyrrhenian region of central Italy, late Quaternary fossil travertines are widespread along two major regional structures: the Tiber Valley and the Ancona-Anzio line. The origin and transport of spring waters from which travertines precipitate are elucidated by chemical and isotopic studies of the travertines and associated thermal springs and gas vents. There are consistent differences in the geochemical and isotopic signatures of thermal spring waters, gas vents and present and fossil travertines between east and west of the Tiber Valley. West of the Tiber Valley, δ¹³C of CO₂ discharged from gas vents and δ¹³C of fossil travertines are higher than those to the east. To the west the travertines have higher strontium contents, and gases emitted from vents have higher ³He/⁴He ratios and lower N₂ contents, than to the east. Fossil travertines to the west have characteristics typical of thermogene (thermal spring) origin, whereas those to the east have meteogene (low-temperature) characteristics (including abundant plant casts and organic impurities). The regional geochemical differences in travertines and fluid compositions across the Tiber Valley are interpreted with a model of regional fluid flow. The regional Mesozoic limestone aquifer is recharged in the main axis of the Apennine chain, and the groundwater flows westward and is discharged at springs. The travertine-precipitating waters east of the Tiber Valley have shallower flow paths than those to the west. Because of the comparatively short fluid flow paths and low (normal) heat flow, the groundwaters to the east of the Tiber Valley are cold and have CO₂ isotopic signatures, indicating a significant biogenic contribution acquired from soils in the recharge area and limited deeply derived CO₂. In contrast, spring waters west of the Tiber Valley have been conductively heated during transit in these high heat-flow areas and have incorporated a comparatively large quantity of CO₂ derived from decarbonation of limestone. The elevated strontium content of the thermal spring water west of the Tiber Valley is attributed to deep circulation and dissolution of a Triassic evaporite unit that is stratigraphically beneath the Mesozoic limestone. U-series age dates of fossil travertines indicate three main periods of travertine formation (ka): 220-240, 120-140 and 60-70. Based on the regional flow model correlating travertine deposition at thermal springs and precipitation in the recharge area, we suggest that pluvial activity was enhanced during these periods. Our study suggests that travertines preserve a valuable record of paleofluid composition and paleoprecipitation and are thus useful for reconstructing paleohydrology and paleoclimate.     

Chemistry of thermal springs in the Larderello-Travale geothermal region, southern Tuscany, Italy

Thirty-two thermal spring, eleven cold spring and six steam condensates in the Larderello-Travale geothermal region have been studied from a geochemical point of view. The aim of this work was to delineate the relation between the chemical composition of the natural thermal manifestations and the thermal anomaly, which is among the best known in the world.The Larderello spring, both hot and cold, are characterized by low salinity (total dissolved solids generally lower than 1000 mg/kg), and alkaline-earth bicarbonate composition. In contrast, an alkaline-earth sulfate composition characterizes the thermal springs of the Travale area. This difference is due to the fact that the underground pathways of the Larderello hot springs are only in shallow flyschoid caprock formations, whereas at Travale the paths are longer and in carbonate-anhydritic Mesozoic rocks, which constitute the main reservoir formations in both the Larderello and Travale areas.The thermal character of Larderello springs is, therefore, mainly due to rock conduction, whereas in Travale it is mostly due to inflows of hot fluid phases from the geothermal reservoir. Comparison between ammonia, Li and B in fluid phases (both steam condensates and hot springs) in the Larderello area suggests that in some of them, their temperatures might be partly due to direct vapor inflows.