The relationship between surface and subsurface waters: water quality aspects in areas of low precipitation / Rapport entre les eaux de surface et les eaux souterraines: aspects des propriétés caractéristiques de l'eau dans les zones à précipitation faible

Abstract

In the temperate and semiarid environment the salinity of both surface and subsurface (meteoric) waters is dominated by the weathering products of soil and aquifer minerals, since even surface waters have a history of subsurface flow. In the desert environment, in contrast, surface flows are more superficial and their chemistry dominated by the aeolian salinity. This has both a marine input and a contribution from recycled salinity from surface accumulation of evaporitic minerals. Both these sources have chloride (and to a lesser extent sulphate) as the dominant anion.     

Groundwater problems in the karstic aquifers of the Dobrich region,northeastern Bulgaria

Abstract

In the Dobrich region, with an area of a little over 4000 km², two important aquifer systems can be differentiated, which we have named the Upper and Deep Aquifers. The hydrodynamic and hydrogeochemical characteristics of these two aquifers are different. Agricultural activities, livestock units, and urban waste waters and solid wastes constitute the principal sources of contamination of the Upper Aquifer. Furthermore, signs of marine intrusion in some coastal zones have been detected. The Deep Aquifer is found to be affected by hydrogeochemical processes related to hydrocarbons that generate elevated concentrations of H₂S and NO₂ (which may exceed 10 mg 1^?1). This aquifer has numerous deep overflowing boreholes that lack appropriate capping, with the consequent loss of resource, draining in the order of 4 m³ s^?1 of thermal and sulphurous waters.     

Hydrogeochemistry of thermal and mineral water springs of the Azores archipelago (Portugal)

Mineral and thermal water chemistry from the Azores archipelago was investigated in order to discriminate among hydrochemical facies and isotopic groups and identify the major geochemical processes that affect water composition. A systematic geochemical survey of mineral and thermal water chemistry was carried out, incorporating new data as well as results from the literature. The Azores are a volcanic archipelago consisting of nine islands and samples were collected at São Miguel, Graciosa, Faial, São Jorge, Pico and Flores islands. Hydrothermal manifestations show the effects of active volcanism on several islands. Discharges are mainly related to active Quaternary central volcanoes, of basaltic to trachytic composition, but also some springs are related to older dormant or extinct volcanoes.Multivariate analysis – principal component and cluster analysis – enables classification of water compositions into 4 groups and interpretation of processes affecting water compositions. Groups 1 and 2 discharge from perched-water bodies, and mostly correspond to Na–HCO₃ and Na–HCO₃–Cl type waters. These groups comprise of cold, thermal (27 °C–75 °C) and boiling waters (92.2 °C–93.2 °C), with a wide TDS range (77.3–27, 145.7 mg/L). Group 3 is made of samples of dominated Na–SO₄ from very acid boiling pools (pH range of 2.02–2.27) which are fed by steam-heated perched-water bodies. Group 4 is representative of springs from the basal aquifer system and corresponds to Na–Cl type fluids, with compositions dominated by seawater.Results are used to further develop a conceptual model characterizing the geochemical evolution of the studied waters. Mineral and thermal waters discharging from perched-water bodies are of meteoric origin and chemically evolve by absorption of magmatic volatiles (CO₂) and by a limited degree of rock leaching. Existing data also suggest mixture between cold waters and thermal water. Water chemistry from springs that discharge from the basal aquifer system evolves by mixing with seawater; although, processes such as absorption of magmatic volatiles (CO₂), rock leaching and mixture with hydrothermal waters are not excluded by the data because the actual composition of these waters deviates from that expected considering only conservative mixing between fresh and seawater.     

Geochemical mapping of magmatic gas–water–rock interactions in the aquifer of Mount Etna volcano

Systematic analysis of major and minor elements in groundwaters from springs and wells on the slopes of Mt. Etna in 1995–1998 provides a detailed geochemical mapping of the aquifer of the volcano and of the interactions between magmatic gas, water bodies and their host rocks. Strong spatial correlations between the largest anomalies in pCO₂ (pH and alkalinity) K, Rb, Mg, Ca and Sr suggest a dominating control by magmatic gas (CO₂) and consequent basalt leaching by acidified waters of the shallow (meteoric) Etnean aquifer. Most groundwaters displaying this magmatic-type interaction discharge within active faulted zones on the S–SW and E lower flanks of the volcanic pile, but also in a newly recognised area on the northern flank, possibly tracking a main N–S volcano-tectonic structure. In the same time, the spatial distribution of T°C, TDS, Na, Li, Cl and B allows us to identify the existence of a deeper thermal brine with high salinity, high content of B, Cl and gases (CO₂, H₂S, CH₄) and low K/Na ratio, which is likely hosted in the sedimentary basement. This hot brine reaches the surface only at the periphery of the volcano near the Village of Paternò, where it gives rise to mud volcanoes called “Salinelle di Paternò”. However, the contribution of similar brines to shallower groundwaters is also detected in other sectors to the W (Bronte, Maletto), SW (Adrano) and SE (Acireale), suggesting its possible widespread occurrence beneath Etna. This thermal brine is also closely associated with hydrocarbon fields all around the volcano and its rise, generally masked by the high outflow of the shallow aquifer, may be driven by the ascent of mixed sedimentary–magmatic gases through the main faults cutting the sedimentary basement.     

Chemical and isotopic compositions of thermal springs,fumaroles and bubbling gases at Tacaná Volcano (Mexico–Guatemala): implications for volcanic surveillance

This study presents baseline data for future geochemical monitoring of the active Tacaná volcano–hydrothermal system (Mexico–Guatemala). Seven groups of thermal springs, related to a NW/SE-oriented fault scarp cutting the summit area (4,100m a.s.l.), discharge at the northwest foot of the volcano (1,500–2,000m a.s.l.); another one on the southern ends of Tacaná (La Calera). The near-neutral (pH from 5.8 to 6.9) thermal (T from 25.7°C to 63.0°C) HCO₃–SO₄ waters are thought to have formed by the absorption of a H₂S/SO₂–CO₂-enriched steam into a Cl-rich geothermal aquifer, afterwards mixed by Na/HCO₃-enriched meteoric waters originating from the higher elevations of the volcano as stated by the isotopic composition (δD and δ¹⁸O) of meteoric and spring waters. Boiling temperature fumaroles (89°C at ~3,600m a.s.l. NW of the summit), formed after the May 1986 phreatic explosion, emit isotopically light vapour (δD and δ¹⁸O as low as −128 and −19.9‰, respectively) resulting from steam separation from the summit aquifer. Fumarolic as well as bubbling gases at five springs are CO₂-dominated. The δ¹³C_CO2 for all gases show typical magmatic values of −3.6 ± 1.3‰ vs V-PDB. The large range in ³He/⁴He ratios for bubbling, dissolved and fumarolic gases [from 1.3 to 6.9 atmospheric ³He/⁴He ratio (R _A)] is ascribed to a different degree of near-surface boiling processes inside a heterogeneous aquifer at the contact between the volcanic edifice and the crystalline basement (⁴He source). Tacaná volcano offers a unique opportunity to give insight into shallow hydrothermal and deep magmatic processes affecting the CO₂/³He ratio of gases: bubbling springs with lower gas/water ratios show higher ³He/⁴He ratios and consequently lower CO₂/³He ratios (e.g. Zarco spring). Typical Central American CO₂/³He and ³He/⁴He ratios are found for the fumarolic Agua Caliente and Zarco gases (3.1 ± 1.6 × 10¹⁰ and 6.0 ± 0.9 R _A, respectively). The L/S (5.9 ± 0.5) and (L + S)/M ratios (9.2 ± 0.7) for the same gases are almost identical to the ones calculated for gases in El Salvador, suggesting an enhanced slab contribution as far as the northern extreme of the Central American Volcanic Arc, Tacaná.     

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.     

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.     

Deciphering groundwater flow between the Complex Terminal and Plio-Quaternary aquifers in Chott Gharsa plain (southwestern Tunisia) using isotopic and chemical tools

Abstract

The Complex Terminal (CT) and Plio-Quaternary (P-Q) aquifers in the Chott Gharsa plain in southwestern Tunisia have been investigated with the aid of chemical and isotopic tools. It has been demonstrated that groundwater from the CT is mainly of palaeo-origin, especially in the western and central parts of the plain where the most negative values of δ¹⁸O and δ²H were observed (between??8.1 and??7.6‰ for δ¹⁸O, and??60 to??57‰ for δ²H), combined with low concentrations of radiocarbon (6.8–7.5 pmc) and absence of tritium. Modern recharge of the aquifer occurs only in the eastern part of the system where younger waters were observed, as indicated by their stable isotope composition, relatively high radiocarbon content and presence of tritium. Groundwater from the P-Q multi-layer aquifer represents mixtures of ascending deep CT waters and modern water recharging the P-Q aquifer system. Isotope mass balance was used to quantify mixing proportions. The calculations showed that the contribution of deep CT groundwater to the P-Q aquifer system reaches about 75% in the western and central parts of the plain where the CT aquifer remains strongly artesian. This contribution decreases to about 15% towards the eastern part of the plain, as a consequence of significant reduction of artesian pressure in this area of the CT aquifer. Chemical data suggest that mineralization of the studied groundwater systems is controlled mainly by dissolution of evaporative minerals (halite, anhydrite and gypsum) and cation exchange reactions with the matrix, possibly enhanced by recent anthropogenic disturbance of the system caused by lowering of the water table due to heavy exploitation and return flow of saline irrigation water into the P-Q aquifer.

Editor D. Koutsoyiannis; Associate editor E. Custodio

Citation Yangui, H., Abidi, I., Zouari, K., and Rozanski, K., 2012. Deciphering groundwater flow between the Complex Terminal and Plio-Quaternary aquifers in Chott Gharsa plain (southwestern Tunisia) using isotopic and chemical tools. Hydrological Sciences Journal, 57 (5), 967–984.     

Variations in surface manifestations at vulcano (Aeolian Islands,Italy) as a possible evidence of deep processes

Five years of geochemical surveillance at Vulcano have shown interesting changes in the physico-chemical characters of the fumaroles at the crater and of the phreatic waters in the surrounding area. In particular, 1) The maximum temperature of the fumaroles, which had been of about 200°C for at least 30 years, rose suddenly to above 300°C: after a period of rather constant values, a decreasing trend has recently been observed; 2) An increase of CO₂, S compounds and HF with respect to HCl, B, Br occurred in the gas composition contemporaneous to the rise in temperature. This increase is now gradually declining; 3) Higher concentrations of sulphate ion and silica in phreatic waters accompanied the thermal changes observed at the fumaroles. According to a model previously proposed (Martini et al., 1980), the increase in the above mentioned factors would reflect an increasing magmatic contribution to the volcanic system, which might be due to an increased permeability to fluids at depth. Because a sensible seismic shock occurred in the area a few months after the first chemical and thermal variations had been observed, such variations may be regarded as forerunners of the seismic event, and may be used to forecast some months in advance changes occurring at depth. The work was carried out within the research programme of C.N.R. Centro di Studio per la Mineralogia e la Geochimica dei Sedimenti, Florence, Italy.     

Acquisition de salinité et qualité des eaux d’une nappe profonde en Tunisie: approche statistique et géochimique

Abstract

The multi-layered Jeffara de Gabes aquifer system is greatly influenced by tectonics. This system is limited at the base and laterally by evaporite layers and has lateral contacts with the sebkhas (salt flats). The groundwater in this aquifer is characterized by high salinity (3–10 g L^-1). Multivariate statistical analysis and a geochemical approach were applied to determine the influence of the evaporite layers and sebkhas on the hydrochemical quality of the Jeffara de Gabes aquifer, and to understand the processes governing its salinity. According to these methods, and based in part on the Sr²⁺/Ca²⁺ ratio, it is demonstrated that the strong salinity of the groundwater is due to interactions between water and the evaporite layers that act as a substratum of this aquifer, as well as saltwater intrusion from the sebkhas. Moreover, the medium- to poor-quality groundwaters are characterized by geochemical interactions: cationic exchange and the precipitation/dissolution process of minerals in the aquifer formations.

Editeur Z.W. Kundzewicz

Citation Ben Alaya, M., Zemni, T., Mamou, A. et Zargouni, F., 2014. Acquisition de salinité et qualité des eaux d’une nappe profonde, Tunisie: approche statistique et géochimique. Hydrological Sciences Journal, 59 (2), 395–419.     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

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.     

Groundwater composition and recharge origin in the shallow aquifer of the Djerid oases,southern Tunisia: implications of return flow

Abstract

Major ions and stable isotopes in groundwaters of the Plio-Quaternary shallow aquifer of the Djerid oases, southern Tunisia, were investigated to elucidate the origin of groundwater recharge and the mineralization processes. It has been demonstrated that the groundwater composition is mainly controlled by the water–rock interaction, the encroachment of brines from the Chotts and the return flow of irrigation waters. The isotopically depleted groundwater samples suggest that the recharge waters derive from an old palaeoclimatic origin. However, the enriched groundwater samples reflect the presence of evaporated recharge water. Furthermore, the large negative deuterium-excess values indicate the effect of secondary evaporation processes, probably related to the return flow of irrigation waters pumped from the underlying aquifer.

Editor D. Koutsoyiannis; Associate editor E. Custodio

Citation Tarki, M., Dassi, L. and Jedoui, Y., 2012. Groundwater composition and recharge origin in the shallow aquifer of the Djerid oases, southern Tunisia: implications of return flow. Hydrological Sciences Journal, 57 (4), 790–804.     

The hydrothermal system of Volcan Puracé, Colombia

This paper presents chemical and isotopic data for thermal waters, gases and S deposits from Volcan Puracé (summit elevation 4600 m) in SW Colombia. Hot gas discharges from fumaroles in and around the summit crater, and thermal waters discharge from three areas on its flanks. The waters from all areas have D values of-75±1, indicating a single recharge area at high elevation on the volcano. Aircorrected values of³He/⁴He in thermal waters range from 3.8 to 6.7 R_A, and approach those for crater fumarole gas (6.1–7.1 R_A), indicating widespread addition of magmatic volatiles. An economic S deposit (El Vinagre) is being mined in the Rio Vinagre fault zone at 3600 m elevation. Sulfur isotopic data are consistent with a magmatic origin for S species in thermal waters and gases, and for the S ore deposit. Isotopic equilibration between S species may have occurred at 220±40°C, which overlaps possible equilibration temperatures (170±40°C) determined by a variety of other geothermometers for neutral thermal waters. Apparent CH₄–CO₂ equilibration temperatures for gases from thermal springs (400±50°C) and crater fumaroles (520±60°C) reflect higher temperatures deeper in the system. Hot magmatic gas ascending through the Rio Vinagre fault zone is though to have precipitated S and generated thermal waters by interaction with descending meteoric waters.     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

Isotopic tracing for conceptual models of groundwater hydrodynamics in multilayer aquifer systems of central and southern Tunisia

Abstract

New and previously published data sets including stable and radiogenic isotope measurements (¹⁸O, ²H, ³H, ¹³C and ¹⁴C) were used to investigate, conceptualize and compare groundwater hydrodynamics within three major multilayer aquifer systems located in central and southern Tunisia. It has been demonstrated that the investigated aquifer systems contain modern and palaeoclimatic waters. Modern groundwaters, which refer to contemporaneous and post-nuclear recharge waters, are characterized by enriched stable isotope contents, high carbon-14 activities and high to moderate tritium concentration. While palaeoclimatic groundwaters, which refer to Late Pleistocene and Early Holocene recharge waters, are distinguished by their depleted stable isotope contents, low carbon-14 activities and insignificant tritium concentrations. Established conceptual models have elucidated the groundwater hydrodynamics within the studied aquifer systems. They show that groundwater mixing occurs between end-members from the shallow and deep aquifers that migrate by downward and upward leakage towards the intermediate aquifer.

Editor D. Koutsoyiannis; Associate editor S. Faye

Citation Dassi, L. and Tarki, M., 2014. Isotopic tracing for conceptual models of groundwater hydrodynamics in multilayer aquifer systems of central and southern Tunisia. Hydrological Sciences Journal, 59 (6), 1240–1258. http://dx.doi.org/10.1080/02626667.2014.892206     

Geothermal assessment of the island of ischia (southern Italy) from isotopic and chemical composition of the delivered fluids

The Ischia geothermal system is hosted by silicic rocks of the Quaternary Potassic Roman Province, in southern Italy. Exploration drilling down to 1156 m depth in the mid-1950s provided information on boiling profiles (up to 250°C) and on the depth and permeability of the potential reservoirs. Discharge fluid samples were collected and analyzed to define the inflow of surrounding seawater (C1 ranges from 2.5 to 20 g/kg) into the system.Analyses of samples from surface manifestations and shallow wells collected during 1983 and 1988 point to the existence of three distinct mixing regimes, involving three water components. A dishomogeneous body of diluted water (Cl less than 2.5 g/kg), that occurs at depths > 700 m and reequilibrates at 240°C at least, is overlain by an aquifer of groundwater variably mixed with variably seawater (Cl from 4 to 10 g/kg), which tends to reequilibrate at 160°C. Steam-heated waters locally develop and act as dilutants of the rising geothermal fluids.Dilution, mixing, and evaporation of the ascending chloride fluids are supported by oxygen and hydrogen isotopic data the thermal waters being enriched in ¹⁸O and D with respect to local meteoric water by up to 7 and 30‰, respectively. The relative composition of the major cations in thermal solutions was used to discriminate the two main groups of thermal waters, the reservoir temperatures of which are estimated from the Na/K-gethermometer. K-Mg geothermometer indicates reequilibration in near-surface conditions.The isotopic composition of the fumarolic steam varies from −7 to −12‰ in ∂⁸O and from − 35 to − 70‰ in ∂D, in agreement with a deep mixed fluid that boils adiabatically from 240 to 80°C. The deuterium content of the H₂O-H₂ pair gives enrichment factor of about 830‰, corresponding to equilibrium temperature conditions slightly higher than the surface boiling temperatures. The ∂¹³C of CO₂is almost constant at −4.5‰ (1δ=0.4), suggesting an important magmatic contribution, and the ∂¹⁸O values of CO₂appears to in equilibrium with accompanying steam at the measured temperatures.The CO₂/Ar and H₂/Ar chemical ratios have been used to derive aquifer temperatures, the values obtained being consistent with those of solute geothermometers.     

Hydrogeochemistry of the Simav geothermal field, western Anatolia, Turkey

Thermal waters hosted by Menderes metamorphic rocks emerge along fault lineaments in the Simav geothermal area. Thermal springs and drilled wells are located in the Eynal, Çitgöl and Na a locations, which are part of the Simav geothermal field. Studies were carried out to obtain the main chemical and physical characteristics of thermal waters. These waters are used for heating of residences and greenhouses and for balneological purposes. Bottom temperatures of the drilled wells reach 163°C with total dissolved solids around 2225 mg/kg. Surface temperatures of thermal springs vary between 51°C and 90°C. All the thermal waters belong to Na–HCO₃–SO₄ facies. The cold groundwaters are Ca–Mg–HCO₃ type. Dissolution of host rock and ion-exchange reactions in the reservoir of the geothermal system shift the Ca–Mg–HCO₃ type cold groundwaters to the Na–HCO₃–SO₄ type thermal waters. Thermal waters are oversaturated at discharge temperatures for aragonite, calcite, quartz, chalcedony, magnesite and dolomite minerals giving rise to a carbonate-rich scale. Gypsum and anhydrite minerals are undersaturated with all of the thermal waters. Boiling during ascent of the thermal fluids produces steam and liquid waters resulting in an increase of the concentrations of the constituents in discharge waters. Steam fraction, y, of the thermal waters of which temperatures are above 100°C is between 0.075 and 0.119. Reservoir pH is much lower than pH measured in the liquid phase separated at atmospheric conditions, since the latter experienced heavy loss of acid gases, mainly CO₂. Assessment of the various empirical chemical geothermometers and geochemical modelling suggest that reservoir temperatures vary between 175°C and 200°C.     

Inorganic carbon dynamics during northern California coastal upwelling

Coastal upwelling events in the California Current System can transport subsurface waters with high levels of carbon dioxide (CO₂) to the sea surface near shore. As these waters age and are advected offshore, CO₂ levels decrease dramatically, falling well below the atmospheric concentration beyond the continental shelf break. In May 2007 we observed an upwelling event off the coast of northern California. During the upwelling event subsurface respiration along the upwelling path added ∼35 μmol kg⁻¹ of dissolved inorganic carbon (DIC) to the water as it transited toward shore causing the waters to become undersaturated with respect to Aragonite. Within the mixed layer, pCO₂ levels were reduced by the biological uptake of DIC (up to 70%), gas exchange (up to 44%), and the addition of total alkalinity through CaCO₃ dissolution in the undersaturated waters (up to 23%). The percentage contribution of each of these processes was dependent on distance from shore. At the time of measurement, a phytoplankton bloom was just beginning to develop over the continental shelf. A box model was used to project the evolution of the water chemistry as the bloom developed. The biological utilization of available nitrate resulted in a DIC decrease of ∼200 μmol kg⁻¹, sea surface pCO₂ near ∼200 ppm, and an aragonite saturation state of ∼3. These results suggest that respiration processes along the upwelling path generally increase the acidification of the waters that are being upwelled, but once the waters reach the surface biological productivity and gas exchange reduce that acidification over time.     

Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.