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 and hydrogeological characterization of thermal springs in Western Sicily, Italy

Thermal and cold waters from Castellammare–Alcamo (Western Sicily-Italy) were collected between May 1994 and May 1995 and studied for their chemical and isotopic composition. During the same period, mean monthly samples of meteoric water were also collected and measured for their isotopic composition. The main purpose of this study was the characterization of the acquifers and, if possible, of their recharge areas. According to the results obtained, the acquifers were divided into three main groups: (a) selenitic waters, (b) cold carbonatic waters, and (c) deep thermal waters resulting from the mixing of the other two types. Besides a mixing process between carbonatic and selenitic waters, contamination processes of thermal waters by seawater take place during their ascent. The water temperature of the acquifer feeding the thermal springs was estimated by means of various geothermometers to range between 60°C and 97°C. Isotope data on rainwater samples show a wide seasonal variation of both δ and δD values. The fairly constant values of thermal waters through time and the lack of an apparent correlation with the isotopic values of rainwater suggest the existence of a deep circuit determining an almost complete homogenisation of the seasonal variations of the isotopic values.     

Geochemical evidence of hydrothermal recharge in Lake Baringo,central Kenya Rift Valley

Lake Baringo, a freshwater lake in the central Kenya Rift Valley, is fed by perennial and ephemeral rivers, direct rainfall, and hot springs on Ol Kokwe Island near the centre of the lake. The lake has no surface outlet, but despite high evaporation rates it maintains dilute waters by subsurface seepage through permeable sediments and faulted lavas. New geochemical analyses (major ions, trace elements) of the river, lake, and hot spring waters and the suspended sediments have been made to determine the main controls of lake water quality. The results show that evaporative concentration and the binary mixing between two end members (rivers and thermal waters) can explain the hydrochemistry of the lake waters. Two zones are recognized from water composition. The southern part of the lake near sites of perennial river inflow is weakly influenced by evaporation, has low total dissolved species (TDS), and has a seasonally variable load of mainly detrital suspended sediments. In contrast, waters of the northern part of the lake show evidence for strong evaporation (TDS of up to eight times inflow). Authigenic clay minerals and calcite may be precipitating from those more concentrated fluids. The subaerial hot‐spring waters have a distinctive chemistry and are enriched in some elements that are also present in the lake water. Comparison of the chemical composition of the inflowing surface waters and lake water shows (1) an enrichment of some species (HCO₃^?, Cl, SO₄^2?, F, Na, B, V, Cr, As, Mo, Ba and U) in the lake, (2) a depletion in SiO₂ in the lake, and (3) a possible hydrothermal origin for most F. The rare earth element distribution and the F/Cl and Na/Cl ratios give valuable information on the rate of mixing of the river and hydrothermal fluids in the lake water. Calculations imply that thermal fluids may be seeping upward locally into the lake through grid‐faulted lavas, particularly south of Ol Kokwe Island. Copyright © 2006 John Wiley & Sons, Ltd.     

Petroleum hydrocarbons in zooplankton faecal pellets from the Sargasso Sea

Analysis of hexane-extractable hydrocarbons in zooplankton collected off Bermuda in August 1979, and their faecal pellets, gave an estimated removal rate of hydrocarbons from surface waters by ‘grazing’ of 16–46 μg m^?2 for a 4 h period. With a number of assumptions, this can be translated to 8–23 mg m^?2 yr^?1. When compared to the annual input due to petroleum discharge in the currents feeding the Sargasso Sea (18–70 mg m^?2 yr^?1 hexane-extractable hydrocarbons), this result implies that zooplankton are an important factor in the short-term removal of petroleum residues from open ocean surface waters.     

Natural tracers for identifying the origin of the thermal fluids emerging along the Aegean Volcanic arc (Greece): Evidence of Arc-Type Magmatic Water (ATMW) participation

The Aegean volcanic arc is the result of a lithosphere subduction process during the Quaternary time. Starting from the Soussaki area, from west to east, the arc proceeds through the islands of Egina, Methana, Milos, Santorini, the Columbus Bank, Kos and Nisyros. Volcano-tectonic activities are still pronounced at Santorini and Nisyros in form of seismic activity, craters of hydrothermal explosions, hot fumaroles and thermal springs. A significant number of cold water springs emerge in the vicinity of hot waters on these islands.Chemical and isotopic analyses were applied on water and fumaroles samples collected in different areas of the volcanic arc in order to attempt the assessment of these fluids. Stable isotopes of water and carbon have been used to evaluate the origin of cold and thermal water and CO₂.Chemical solute concentrations and isotopic contents of waters show that the fluids emerging in Egina, Soussaki, Methana and Kos areas represent geothermal systems in their waning stage, while the fluids from Milos, Santorini and Nisyros proceed from active geothermal systems.The δ²H–δ¹⁸O–Cl^? relationships suggest that the parent hydrothermal liquids of Nisyros and Milos are produced through mixing of seawater and Arc-Type Magmatic Water (ATMW), with negligible to nil contribution of local ground waters and with very high participation of the magmatic component, which is close to 70% in both sites. A very high magmatic contribution to the deep geothermal system could occur at Santorini as well, perhaps with a percentage similar to Nisyros and Milos, but it cannot be calculated because of steam condensation heavily affecting the fumarolic fluids of Nea Kameni before the surface discharge.The parent hydrothermal liquid at Methana originates through mixing of local groundwaters, seawater and ATMW, with a magmatic participation close to 19%. All in all, the contribution of ATMW is higher in the central–eastern part of the Aegean volcanic arc than in the western sector. This difference, which is spotted in the variable isotopic composition of the sampled fluids from west to east along the arc, is probably due to several causes, including the tectonic regime, the depth of the deep reservoir below sea level, the age of volcanic activity and in general the geomorphologic state of each island.     

Dependence of the chemical composition of thermal waters upon seismic activity

Changes in the chemical composition of the hot springs of Mendeleev Volcano (Kunashir Island) as for Cl^?, SO ₄ ^2? , CO₂, NH ₄ ⁺ and Cl^?/SO ₄ ^2? are given in function of the 1965–66 and 1973 (in part) seismic activity in the South Kurile islands.     

Chemical and isotopic assessment in volcanic thermal waters: Cases of Ischia (Italy) and São Miguel (Azores,Portugal)

Isotopic fractionation of ¹⁰B/¹¹B provides a sound tool for identifying hydrogeochemical processes in complex areas, owing to its ability to discriminate between various scenarios. In addition, the occurrence of boron as a minor element in areas of active volcanism allows its use in comparison with concentrations of other conservative or non‐conservative ions. This allows the detection of water mixtures of diverse origin and temperature, deep or shallow, including fresh water, seawater and even brines. This tool was applied in studies of the volcanic islands of Ischia and São Miguel, across widely differing geographical and climatic contexts. Five groups of waters have been identified in Ischia Island: marine, transition, hot carbonated, cold carbonated and fresh waters. For São Miguel Island the identified groups are cold carbonic, hot carbonic, boiling and acidic boiling waters. Copyright © 2008 John Wiley & Sons, Ltd.     

Radioactive elements in sediments and altered rocks of the Kikhpinych long-lived volcanic center

Data on the concentration of radioactive elements in mineral sediments and hydrothermally altered rocks of the long-lived Kikhpinych volcanic center are presented. High concentrations of uranium (up to 31 g/t) and thorium (up to 46 g/t) relative to the average values for the dacites of Kamchatka and the Uzon-Geyser depression are found in white kaolinite clays of mud pots and in dacites of the Yuzhnoe Kikhpinych thermal field transformed into kaolinite clays. In this field and in the Severnoe thermal field (in the crater of Staryi Kikhpinych Volcano) high values of volume radon activity (VA Rn > 1000 kBq/m³) were recorded in subsoil air. These high concentrations of uranium and thorium in fresh mineral sediments and anomalous values of VA Rn in subsoil air of hydrothermally altered rocks are considered to have resulted from the mass transfer of radioactive elements by fluid flows of the hydrothermal system.     

Relationship between pelagic tar,fluorescence and biological markers in the South Atlantic Ocean

Surface pelagic tar concentrations in the equatorial South Atlantic Ocean were low (< 0.001 to 14.6 mg m^?2). With one exception, concentrations were less than 0.5 mg m^?2. The tars were characterized by gravimetry, carbon isotopic composition, molecular compositions (gas chromatographically), sulphur content, total fluorescence spectra, and biological marker fingerprints. Most tars exhibited significant amounts of degradation. A total fluorescence technique was used to group the tars into two basic types. One type occurred at low concentrations and appeared to be due to chronic long-term oil pollution in the South Atlantic Ocean. The second group occurred at much higher concentrations and was associated with more coastal-influenced waters. Biological marker (triterpanes and steranes) fingerprints confirmed the fluorescence groupings. Carbon isotopic composition and pristane/phytane ratios exhibited few geographical trends.     

Factors controlling the chemical evolution of travertine‐depositing rivers of the Barkly karst,northern Australia

Groundwaters feeding travertine‐depositing rivers of the northeastern segment of the Barkly karst (NW Queensland, Australia) are of comparable chemical composition, allowing a detailed investigation of how the rate of downstream chemical evolution varies from river to river. The discharge, pH, temperature, conductivity and major‐ion concentrations of five rivers were determined by standard field and laboratory techniques. The results show that each river experiences similar patterns of downstream chemical evolution, with CO₂ outgassing driving the waters to high levels of calcite supersaturation, which in turn leads to widespread calcium carbonate deposition. However, the rate at which the waters evolve, measured as the loss of CaCO₃ per kilometre, varies from river to river, and depends primarily upon discharge at the time of sampling and stream gradient. For example, Louie Creek (Q = 0·11 m³ s^?1) and Carl Creek (Q = 0·50 m³ s^?1) have identical stream gradients, but the loss of CaCO₃ per kilometre for Louie Creek is twice that of Carl Creek. The Gregory River (Q = 3·07 m³ s^?1), O'Shanassy River (Q = 0·57 m³ s^?1) and Lawn Hill Creek (Q = 0·72 m³ s^?1) have very similar gradients, but the rate of hydrochemical evolution of the Gregory River is significantly less than either of the other two systems. The results have major implications for travertine deposition: the stream reach required for waters to evolve to critical levels of calcite supersaturation will, all others things being equal, increase with increasing discharge, and the length of reach over which travertine is deposited will also increase with increasing discharge. This implies that fossil travertine deposits preserved well downstream of modern deposition limits are likely to have been formed under higher discharge regimes. Copyright © 2002 John Wiley & Sons, Ltd.     

Estimating groundwater discharge to surface waters using heat as a tracer in low flux environments: the role of thermal conductivity

Analytical modelling of heat transport was used to address effects of uncertainty in thermal conductivity on groundwater–surface water exchange. In situ thermal conductivities and temperature profiles were measured in a coastal lagoon bed where groundwater is known to discharge. The field site could be divided into three sediment zones where significant spatial changes in thermal conductivity on metre to centimetre scale show that spatial variability connected to the sediment properties must be considered. The application of a literature‐based bulk thermal conductivity of 1.84 Wm^?1 °C^?1, instead of field data that ranged from 0.62 to 2.19 W m^?1 °C^?1, produced a mean overestimation of 2.33 cm d^?1 that, considering the low fluxes of the study area, represents an 89% increase and up to a factor of 3 in the most extreme cases. Incorporating the uncertainty due to sediment heterogeneities leads to an irregular trend of the flux distribution from the shore towards the lagoon. The natural variability of the thermal conductivity associated with changes in the sediment composition resulted in a mean variation of ±0.66 cm d^?1 in fluxes corresponding to a change of ±25.4%. The presence of organic matter in the sediments, a common situation in the near‐shore areas of surface water bodies, is responsible for the decrease of thermal conductivity. The results show that the natural variability of sediment thermal conductivity is a parameter to be considered for low flux environments, and it contributes to a better understanding of groundwater–surface water interactions in natural environments. Copyright © 2015 John Wiley & Sons, Ltd.     

Geochemical weathering at the bed of Haut Glacier d'Arolla,Switzerland—a new model

Waters were sampled from 17 boreholes at Haut Glacier d'Arolla during the 1993 and 1994 ablation seasons. Three types of concentrated subglacial water were identified, based on the relative proportions of Ca²⁺, HCO₃^? and SO₄^2? to Si. Type A waters are the most solute rich and have the lowest relative proportion of Si. They are believed to form in hydrologically inefficient areas of a distributed drainage system. Most solute is obtained from coupled sulphide oxidation and carbonate dissolution (SO–CD). It is possible that there is a subglacial source of O₂, perhaps from gas bubbles released during regelation, because the high SO₄^2? levels found (up to 1200 µeq/L) are greater than could be achieved if sulphides are oxidized by oxygen in saturated water at 0 °C (c.414 µeq/L). A more likely alternative is that sulphide is oxidized by Fe³⁺ in anoxic environments. If this is the case, exchange reactions involving Fe^III and Fe^II from silicates are possible. These have the potential to generate relatively high concentrations of HCO₃^? with respect to SO₄^2?. Formation of secondary weathering products, such as clays, may explain the low Si concentrations of Type A waters. Type B waters were the most frequently sampled subglacial water. They are believed to be representative of waters flowing in more efficient parts of a distributed drainage system. Residence time and reaction kinetics help determine the solute composition of these waters. The initial water–rock reactions are carbonate and silicate hydrolysis, and there is exchange of divalent cations from solution for monovalent cations held on surface exchange sites. Hydrolysis is followed by SO–CD. The SO₄^2? concentrations usually are <414 µeq/L, although some range up to 580 µeq/L, which suggests that elements of the distributed drainage system may become anoxic. Type C waters were the most dilute, yet they were very turbid. Their chemical composition is characterized by low SO₄^2? : HCO₃^? ratios and high pH. Type C waters were usually artefacts of the borehole chemical weathering environment. True Type C waters are believed to flow through sulphide‐poor basal debris, particularly in the channel marginal zone. The composition of bulk runoff was most similar to diluted Type B waters at high discharge, and was similar to a mixture of Type B and C waters at lower discharge. These observations suggest that some supraglacial meltwaters input to the bed are stored temporarily in the channel marginal zone during rising discharge and are released during declining flow. Little of the subglacial chemical weathering we infer is associated with the sequestration of atmospheric CO₂. The progression of reactions is from carbonate and silicate hydrolysis, through sulphide oxidation by first oxygen and then Fe^III, which drives further carbonate and silicate weathering. A crude estimate of the ratio of carbonate to silicate weathering following hydrolysis is 4 : 1. We speculate that microbial oxidation of organic carbon also may occur. Both sulphide oxidation and microbial oxidation of organic carbon are likely to drive the bed towards suboxic conditions. Hence, we believe that subglacial chemical weathering does not sequester significant quantities of atmospheric CO₂ and that one of the key controls on the rate and magnitude of solute acquisition is microbial activity, which catalyses the reduction of Fe^III and the oxidation of FeS₂. Copyright © 2002 John Wiley & Sons, Ltd.     

Depth of origin of the gas content in thermal waters

The gas composition of recent thermal waters is in perfect conformity with their geologictectonic positions. The composition of gas-liquid inclusions in the basic-hyperbasic xenoliths of basaltoid lavas depends on the depth from which xenoliths are supplied. (The depth is determined by using the methods of geological thermobarometers). By comparing available data we came to the conchision that the gas compositions of thermal waters reflect the depth of generation of deep fluid which heats them and depends on the penetration depth of the fluid-conducting fissure zones.     

An iron-rich deposit from the Northeast Pacific

An iron-rich deposit dredged from the upper flank of Dellwood Seamount in the Northeast Pacific has been analyzed for major and trace elements, rare-earth contents and uranium isotopic composition. In terms of mineralogy and overall chemical composition, the deposit resembles other iron-rich deposits variously attributed to volcanic hydrothermal activity. Both the relative concentrations of the rare-earth elements and the isotopic composition of uranium rule out seawater as the sole source of elements in this deposit. The rare-earth element pattern indicates that these elements were derived from the underlying basalt. The²³⁴U/²³⁸U ratio is significantly higher than in seawater and can best be explained by preferential leaching of²³⁴U generated by decay from its parent²³⁸U in the underlying rock and subsequent redeposition of the excess²³⁴U together with the Fe and minor metals. These data are consistent with a model for the origin of submarine metal-rich solutions involving mobilization of elements from the interior of slowly cooling basalts by circulating seawater.     

Ce anomalies in Gough Island lavas — Trace element characteristics of a recycled sediment component

High precision trace element data obtained by inductively coupled plasma mass spectrometry and Sr–Nd isotope analyses are presented for mafic volcanic rocks from Gough Island, South Atlantic. The new data reveal negative Ce anomalies, with Ce/Ce^? values in Gough lavas extending down to ～ 0.92. Ce is only fractionated from other rare earth elements (REE) due to formation of Ce⁴⁺ under oxidizing conditions of near-surface environments while other REE remain trivalent. Ce anomalies in convergent margin magmas have been shown to indicate a contribution of a subducted sediment component. In contrast, Ce anomalies in intra-plate basalts have been attributed to weathering processes, but can be excluded here based on element–element systematics indicating magmatic trends rather than weathering-induced element mobility. Shallow-level contamination by local marine sediments with negative Ce anomaly inherited from seawater can be excluded because Gough lavas with increasingly negative Ce anomalies do not trend towards low Ce/Pb ratios characterizing such sediments. Rather, it is argued that the negative Ce anomalies in Gough Island lavas are consistent with variable amounts of a sediment component in the mantle plume source. Mixtures between estimates of subducting sediment columns with negative Ce anomaly and mantle capable of giving rise to Gough Island magmas without Ce anomalies reproduce the Gough compositional array with the exception of highly fluid-mobile elements. The calculated trace element composition of the deeply recycled sediment in the Gough plume source is depleted in fluid-mobile elements such as Ba and Pb relative to the composition of some present-day subducting sediments. This loss is attributed to the dehydration or flushing of sediment in the subduction factory, consistent with constraints from arc magmas.     

The use of radon as tracer in environmental sciences

Radon can be used as a naturally occurring tracer for environmental processes. By means of grab-sampling or continuous monitoring of radon concentration, it is possible to assess several types of dynamic phenomena in air and water. We present a review of the use of radon and its progeny at the University of Cantabria. Radon can be an atmospheric dynamics indicator related with air mass interchange near land-sea discontinuities as well as for the study of vertical variations of air parameters (average values of different types of stability: 131–580 Bq m^?3). Concerning indoor gas, we present some results obtained at Altamira Cave (Spain): from 222 to 6549 Bq m^?3 (Hall) and from 999 to 6697 Bq m^?3 (Paintings Room). Finally, variations of radon concentration in soil (0.3 to 9.1 kBq m^?3) and underground water (values up to 500 Bq l^?1) provide relevant information about different geophysical phenomena.     

The effect of interstitial gaseous pressure on the thermal conductivity of a simulated Apollo 12 lunar soil sample

The thermal conductivity of a simulated Apollo 12 lunar soil sample was measured with a needle probe under vacuum. The result showed that the sample, with bulk densities of 1.70–1.85 g cm^?3 held in a vertical cylinder (2.54 cm in diameter and 6.99 cm long) has a thermal conductivity ranging from 8.8 to 10.9 mW m^?1 K^?1. This is comparable to the lunar regolith's thermal conductivity as determined in situ. Besides the dense packing of the soil particles, an enhanced intergranular thermal contact, due to the self-compression of the sample, is necessary to raise the sample's thermal conductivity from the level of loose soil (< 5 mW m^?1 K^?1) to that of the lunar regolith deeper than 35 cm (～ 10 mW m^?1 K^?1). A model of the lunar regolith, a thin layer of loose soil resting on a compacted self-compressed substratum, is consistent with the lunar regolith's surface structure as deduced from an observation of the lunar surface's brightness temperature. Martian regolith surface structure is similar, except that its surface layer may be missing in places because of aeolian activity. Measurements of thermal conductivity under simulated martian surface conditions showed that the thermal properties of loose and compacted soils agreed with the two peak values of the martian surface's thermal inertia as observed from “Viking” orbiters, suggesting that drifted loose soil and exposed compacted soil are responsible for the bimodal distribution of the martian surface's thermal inertia near zero elevation. For compacted soil exposed to the martian surface to have the same thermal conductivity as that buried under the surface layer, a cohesion of the soil particles must be assumed.     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.