Hydrothermal Water Research Articles

Distribution and behaviour of reduced sulfur substances in the oligotrophic and hydrothermal waters of the Western Tropical South Pacific

Reduced sulfur species (RSS) are involved in essential biological and chemical processes, including metal complexation, yet little is known about their occurrence and behaviour in marine systems. Here, we present a quantitative and qualitative data set of species-specific RSS in open ocean samples collected during the GEOTRACES Tonga GPpr14 cruise. The cruise traversed differing biogeochemical provinces, from the mesotrophic Melanesian waters and the North Fiji Basin, through the hydrothermally active Lau Basin, eastward to the oligotrophic South Pacific Gyre. Using cathodic stripping voltammetry in acidified samples (pH 2), we measured the concentration of two RSS, with peak potentials of -0.18 and -0.09 V in equivalents of thioacetamide (TA) and glutathione (GSH) respectively. GSH-like compounds were only present in the upper 200 m at concentrations up to 6.2 nM eq. GSH, consistent with other cathodic stripping voltammetry as well as chromatography-based studies. In contrast, RSS−0.18 V2 compounds were detected at all depths at concentrations ranging from 48 nM to 980 nM eq. TA. Both RSS−0.18 V2 and GSH-like compounds were present at higher levels in the hydrothermally-impacted region of the Lau Basin relative to other stations. The highest levels, along with high sulfide concentrations, were detected in a hydrothermal plume sample, indicating that hydrothermal vents are a direct or indirect source of these compounds. Elevated levels of RSS−0.18 V2 compounds were detected throughout almost the entire water column at a station located in the North Fiji Basin. We also employed the qualitative technique of cathodic pseudopolarography on unbuffered samples (pH ~ 8.5). Pseudopolarograms of marine RSS were compared to sulfide, GSH and TA standards. Pseudopolarography supports the presence of GSH in marine samples. However, while a compound that is electrochemically similar to TA is often detected in marine samples, TA itself is not thought to be naturally present. This is supported by our pseudopolarograms of RSS−0.52 V8.5 which often lacked the characteristic TA reduction wave but suggested the presence of other unidentified RSS compounds.

Silica solubility and molecular speciation in water vapor at 400–800 °C

Silica solubility and molecular speciation in hydrothermal water vapor have been determined through quartz solubility experiments at 400–800 °C and 50–270 bar using a novel U-tube flow-through reactor system and theoretical calculations. The results demonstrate that silica concentrations are low in water vapor (mSi,tot = 0.11–4.56 mmol/kg or xSi,tot = 8.21 × 10−5–1.98 × 10−6 mol/mol) increase with both temperature and pressure, which is attributed to the dissolution of quartz according to the reaction:SiO2(s) + (n + 2)H2O(g) ⇋ Si(OH)4·(H2O)n(g)Thermodynamic modeling and theoretical calculations employing density functional theory (B3LYP-D3), and MP2 ab initio calculations reveal the stable structures to be Si(OH)4(g), Si(OH)4·(H2O)2(g), Si(OH)4·(H2O)4(g) and Si(OH)4·(H2O)7(g) (n = 0, 2, 4, 7) under the temperature and pressure conditions of interest, with higher-order hydrated structures also present at the lowest temperatures and highest pressures. Various isomers of the gaseous silica species were identified, with the number of energetically favorable structures increasing with hydration level and the motifs shifting from silanol-water bonds to complex water-water networks. Over the temperature range of interest, the logarithm of the quartz equilibrium solubility constant (logKn) rises from −7.40 to −6.55 and −12.23 to −11.65 at 400 to 800 °C for the formation of Si(OH)4(g) and Si(OH)4·(H2O)2(g), respectively, and decreases from −16.20 to −19.15 and –22.61 to −28.74 for Si(OH)4·(H2O)4(g) and Si(OH)4·(H2O)7(g) at the same temperature range, respectively. Standard thermodynamic properties were derived based on the experimental results, revealing temperature-independent enthalpy (ΔHn,ro), entropy (ΔSn,ro) and heat capacity (ΔCp,n,ro) of reaction for each gaseous silica species. The enthalpy of the reaction is nearly constant, whereas the entropy and heat capacity decrease with increasing hydration, resulting in higher-level hydrated species becoming less important with increasing temperature. Our quartz solubility results are in good agreement with previous experimental data and thermodynamic equations, as well as the thermodynamic properties of Si(OH)4(g) at 25 °C and 1 bar.

Hydrothermal Karstification of the Pre-Messinian Eonile Canyon: Geomorphological and Geochemical Evidences for Hypogene Speleogenesis in the Middle Nile Valley of Egypt

The surface and subsurface karst features of the Eocene limestone plateaus along the Middle Nile Valley in Egypt were formerly believed to be epigene in origin and to have developed during post-Eocene pluvial periods. However, the morphology of the caves and their restriction to particular stratigraphic intervals suggests that they are hypogene. The geochemistry and mineralogy of the soft, thick-bedded, brown/black cave infills shows that these sediments originated from hydrothermal processes, as evidenced by their Fe, Mn, Co, Ni, and Cu concentrations. Thus, the karst features are hypogene and probably formed during the opening of the Red Sea Rift at the end of the Oligocene and early Miocene. At this time, there was abundant volcanic activity, as shown by basalt lavas ~70 km northwest of Assiut; this triggered the release of large amounts of CO2 that made the hydrothermal waters acidic and dissolved the caves.

Hydrothermal Hot Isostatic Pressing (HHIP)-Experimental Proof of Concept.

A new hydrothermal hot isostatic pressing (HHIP) approach, involving hydrothermal water conditions and no usage of inert gas, was hypothesized and tested on 3D-printed Al-10%Si-0.3%Mg (%Wt) parts. The aluminum-based metal was practically inert at the applied HHIPing conditions of 300-350 MPa and 250-350 °C, which enabled the employment of a long (6-24 h) HHIP treatment with hardly any loss of material (the overall loss due to corrosion was mostly <0.5% w/w). Applying the new approach on the above-mentioned samples resulted in an 85.7% reduction in the AM micro-pores, along with a 90.8% reduction in the pores' surface area at a temperature of 350 °C, which is much lower than the 500-520 °C applied in common argon-based aluminum HIPing treatments, while practically maintaining the as-recieved microstructure. These results show that better mechanical properties can be expected when using the suggested treatment without affecting the material fatigue resistance due to grain growth. The proof of concept presented in this work can pave the way to applying the new HHIPing approach to other AM metal parts.

Hot spring oases in the periglacial desert as the Last Glacial Maximum refugia for temperate trees in Central Europe.

Northern glacial refugia are a hotly debated concept. The idea that many temperate organisms survived the Last Glacial Maximum (LGM; ~26.5 to 19 thousand years) in several sites across central and northern Europe stems from phylogeographic analyses, yet direct fossil evidence has thus far been missing. Here, we present the first unequivocal proof that thermophilous trees such as oak (Quercus), linden (Tilia), and common ash (Fraxinus excelsior) survived the LGM in Central Europe. The persistence of the refugium was promoted by a steady influx of hydrothermal waters that locally maintained a humid and warm microclimate. We reconstructed the geological and palaeohydrological factors responsible for the emergence of hot springs during the LGM and argue that refugia of this type, allowing the long-term survival and rapid post-LGM dispersal of temperate elements, were not exceptional in the European periglacial zone.

Polycladomyces zharkentensis sp. nov., a novel thermophilic cellulose- and starch-degrading member of the Bacillota from a geothermal aquifer in Kazakhstan.

A thermophilic, aerobic and heterotrophic filamentous bacterium, designated strain ZKZ2T, was isolated from a pipeline producing hydrothermal water originating from a >2.3 km deep subsurface geothermal source in Zharkent, Almaty region, Kazakhstan. The isolate was Gram-stain-positive, non-motile, heat-resistant and capable of producing a variety of extracellular hydrolases. Growth occurred at temperatures between 55 and 75 °C, with an optimum around 70 °C, and at pH values between 5.5 and 9.0, with an optimum at pH 7.0-7.5 with the formation of aerial mycelia; endospores were produced along the aerial mycelium. The isolate was able to utilize the following substrates for growth: glycerol, l-arabinose, ribose, d-xylose, d-glucose, d-fructose, d-mannose, rhamnose, d-mannitol, methyl-d-glucopyranoside, aesculin, salicin, cellobiose, maltose, melibiose, sucrose, trehalose, melezitose, raffinose, starch, turanose and 5-keto-gluconate. Furthermore, it was able to hydrolyse carboxymethylcellulose, starch, skimmed milk, Tween 60 and Tween 80. The major cellular fatty acids were iso-C15 : 0, iso-C17 : 0, iso-C16 : 0 and C16 : 0. Our 16S rRNA gene sequence analysis placed ZKZ2T within the genus Polycladomyces, family Thermoactinomycetaceae, with the highest similarity to the type species Polycladomyces abyssicola JIR-001T (99.18 % sequence identity). Our draft genome sequence analysis revealed a genome size of 3.3 Mbp with a G+C value of 52.5 mol%. The orthologous average nucleotide identity value as compared to that of its closest relative, P. abyssicola JIR-001T, was 90.23 %, with an in silico DNA-DNA hybridization value of 40.7 %, indicating that ZKZ2T represents a separate genome species. Based on the phenotypic and genome sequence differences from the other two Polycladomyces species, we propose that strain ZKZ2T represents a novel species, for which we propose the name Polycladomyces zharkentensis sp. nov. The type strain is ZKZ2T (=CECT 30708T=KCTC 43421T).

Carbonate production and reef building under ferruginous seawater conditions in the Cambrian rift branches of the Avalon Zone, Newfoundland

AbstractThe characterization of carbonate production on rift basins is critical for understanding the nucleation and demise of reefs in tectonically active areas. A new petrographic and mineralogical analysis of Cambrian strata from the Avalon Zone in Newfoundland, based on scanning electron microscopy – back‐scattered electron detector and Raman spectrometer analyses, facilitates recognition of several episodes of Terreneuvian–Miaolingian carbonate production and associated precipitation of ironstone and phosphorite. These distinct units mainly developed on uplifted rift shoulders and basaltic lava palaeoreliefs, and reflect amalgamated high‐energy events, interrupted by scouring discontinuities (diastems) commonly lined by phosphatized and ferruginized microbial crusts. Mud‐mounds, in contrast, nucleated under calm conditions episodically punctuated by high‐energy episodes, where scattered thromboid structures occur as both clotted textures and distinct calcimicrobes. Precipitation of hematite/goethite versus chamosite couplets, both occluding primary porosities and replacing interlaminae and cortices of oncoids and coated aggregates, point to marine substrates close to the Fe‐redox boundary. Upwelling of phosphate‐rich ferruginous hydrothermal waters contributed to the precipitation of ironstone and phosphate interbeds. Ferruginous waters related to penecontemporaneous hydrothermal activity, reflected by the record of synsedimentary fissuring and stockwork ore bodies, were delivered to confined rift‐related horst‐and‐graben settings, largely controlled by the development of specific Cambrian carbonate and associated ironstone facies. The influence of ferruginous waters necessarily affected the record of climatically sensitive evaporitic pseudomorphs, reefs/mounds and phosphorites, which are then not suitable criteria to discriminate palaeolatitude, as demonstrated by a comparison of low‐latitude to middle‐latitude margins fringing Baltica, and the Avalonian and Atlas – Ossa‐Morena – Northarmorican rift transects of West Gondwana.

Hydrogeochemical and geothermal features of thermal springs along the Ganzi-Yushu fault, eastern Tibetan Plateau and its geological implications

Important fault zone processes can be discerned from the hydrothermal fluid circulation associated with active seismic sources. This study focused on the geochemical and isotopic features of the thermal waters along the Ganzi-Yushu fault (GZYSF) located in the eastern Tibetan Plateau. 22 spring samples were collected to characterize the chemical compositions and calculate the geothermal reservoir temperatures. The hydrothermal waters are mainly recharged by meteoric water based on the δ18O and δ2H values. Immature waters with a Na + -HCO3- or Ca2+(Mg2+)-HCO3- composition were recognized in the study area, combined with the poor correlation between K+, Na+, Mg2+, HCO3− and Cl− suggesting a shallow hydrothermal fluid source. The 87Sr/86Sr ratios and high concentrations of B (from 20.3 to 9445 μg/L) and Li (from 3.04 to 2380 μg/L) show a dissolution of silicate minerals containing calcium and magnesium during fluid circulation. The geothermometry in the silicon-enthalpy system suggested equilibrium temperatures up to 146 °C, whereas most are low temperatures. The shallow geothermal fields along GZYSF show that most large earthquakes (M＞5) were distributed in the transitional zone between high-value area and low-value area of the shallow geothermal field, suggesting a potential genetic link between geothermal field structure and earthquake nucleation along active faults. In conclusion, we proposed a conceptual model to portray the fluid circulation process. Such work can provide insights into the potential geothermal resource in Tibetan Plateau, and also investigate the processes controlling the fluid chemistry and the correlation with occurrence of earthquakes in the region.

Investigating the processes and rate of iodide ion and compound oxidation in subterranean hydrothermal waters

Studies using physico-chemical methods have been conducted to evaluate the oxidative characteristics of various reagents for the technological extraction of iodine from groundwater and sufficient data have been obtained. According to the research results, iodine is predominantly present in the form of molecular iodine (85.6%), iodide ions (3.2%), iodate (9.1%) and iodine chloride (2.1%) were detected. Preserving all forms of iodine in solution at the same time is possible only in an alkaline environment, where the oxidizing properties of iodates are sharply reduced. This information is important for choosing a method for purifying iodine paste using various physical and chemical methods. From experiments in research, the beginning of the release of elemental iodine was noted at a voltage above 0.250 V and a pH of 5-3 or less. In this case, the solution usually becomes dark red with a reddish or brownish tint, which indicates the formation of complex compounds of iodine with other ions in the solution.

Chironomids of thermal and karst springs of the Bolshezemelskaya tundra

Pymvashor Creek is the northernmost in continental Europe hydrothermal system (Bolshezemelskaya tundra, Northeast of European Russian Arctic). Our study aimed to investigate the taxonomic composition and abundance of chironomids and to evaluate the relationship of these parameters with the water temperature along the thermal gradient in the arctic Pymvashor Creek thermal system. The greatest taxonomic richness and abundance of chironomids were found in tepid waters (25 chironomid taxa), where Orthocladiinae dominated chironomid communities. Eurybiotic Chironomus Meigen, 1803 species dominated thermal springs. Cold stenotherm Pseudodiamesa (Pseudodiamesa) nivosa (Goetghebuer, 1928) and Eukiefferiella claripennis (Lundbeck, 1898) prevailed in cold karst springs. The chironomid faunas of thermal, tepid, and cold parts of the Pymvashor Creek hydrothermal water system differ statistically significantly.

Lithology Of Geothermal Potential Areas Using The Electrical Resistivity Tomography (ERT) Method

The rock lithology of the potential hydrothermal area has been studied using Electrical Resistivity Tomography (ERT) in Pungguk Pedaro Village, Bingin Kuning District, Lebong Regency. Field data acquisition uses a stretch length of 480 meters with the MAE X612-EM Geoelectric tool that forms a straight line. ERT method, using Res2dinvx64 software. This study aims to determine the subsurface conditions of the potential hydrothermal area and the characteristics of the rocks that make up the hydrothermal area. The results of this study can be concluded that Pungguk Pedaro Village is dominated by Clay, Sandstone, Sandy Gravel, Andesite, Basalt, and Granite rocks. Line 1 has no potential for hydrothermal distribution because there has been a mixture of hydrothermal water with mountain water, so only groundwater is obtained on this line.

The dynamic influence of subsurface geological processes on the assembly and diversification of thermophilic microbial communities in continental hydrothermal systems

An accepted paradigm of hydrothermal systems is the process of phase separation, or boiling, of a deep, homogeneous hydrothermal fluid as it ascends through the subsurface resulting in gas rich and gas poor fluids. While phase separation helps to explain first-order patterns in the chemistry and biology of a hot spring’s surficial expression, we know little about the subsurface architecture beneath “phase-separated” pools and the timescales over which phase separation processes occur. Essentially, we have a two-dimensional understanding of a four-dimensional process. By combining geophysical, geochemical, isotopic, and microbiological measurements of two adjacent phase-separated hot springs in Norris Geyser Basin, Yellowstone National Park, we provide a four-dimensional assessment of phase separation processes and their biological manifestation. We uniquely show that Yellowstone’s hydrothermal waters originate from a deep sedimentary aquifer and that both meteoric recharge and shallow reactive transport processes are required to establish the geobiological feedbacks that drive bimodal distributions in the geochemical and microbial composition of hot springs. Specifically, over periods of tens of years, gas-enriched fluids containing volcanic sulfide mix with meteoric waters resulting in microbially-mediated production of sulfuric acid by thermoacidophilic Archaea in the near subsurface. In contrast, over periods of hundreds of years, anoxic residual liquid rises to the surface where it is infused with atmospheric gas fostering Archaea and Bacteria that are largely dependent on oxygen. As such, our results provide formative insight into the causative links between subsurface geological processes, the development of geochemical fluids, and the assembly and diversification of thermophilic microbial communities in hydrothermal systems.

Water and Sediments of an Acidic Hot Spring—Distinct Differentiation with Regard to the Microbial Community Composition and Functions

Over the last half-century, microbial communities of the Kamchatka hot springs have been largely studied using molecular, radioisotopic, and cultural approaches. Generally, these results were obtained for mixed samples of water with sediments, for only hydrothermal water, or for only sediment samples. Simultaneous comparative analysis of the microbial communities of water and sediments was performed for only one Kamchatka hot spring with circumneutral pH. Here, the microbial communities of both sediments and water (separately) of hot spring #4229 (the Uzon Caldera, Kamchatka) with a temperature of 50–56 °C and pH of 3.2 were analyzed by 16S rRNA gene V4 fragment amplicon sequencing. It was revealed that the microbial community of sediments was represented by uncultured phylogenetically deep-branching lineages of archaea, such as ARK-15 within Thermoplasmatota and ‘Ca. Marsarchaeales’ from the Thermoproteota phyla. Metagenome analysis showed that these archaea most probably carried out the degradation of organic matter. The microbial community of the hot water is represented by thermoacidophilic, (micro)aerobic, chemolithoautotrophic, hydrogen- and sulfur-oxidizing bacteria of the genera Hydrogenobaculum (phylum Aquificota) and Acidithiobacillus (phylum Pseudomonadota). Radioisotopic tracing and DNA-stable-isotope probing techniques proved their role as primary producers in the hot spring. The experiment revealed significant differences in the composition and functions of the microbial communities of sediments and water through the example of a typical acidic hot spring in Kamchatka.

Decadal Monitoring of the Hydrothermal System of Stromboli Volcano, Italy

AbstractIn active volcanoes, magmatic fluids rising toward the surface may interact with shallow waters, thereby forming hydrothermal systems that record variations in magma dynamics at depth. Here, we report on a data set comprising the chemical and isotopic composition of thermal waters and dissolved gases from Stromboli Island (Aeolian Volcanic Arc, Southern Italy) that spans 14 years (2004–2018) of continuous observations. We show that the shallow thermal aquifer of Stromboli results from variable mixing between meteoric water, seawater and magmatic fluids. Gas‐water‐rock interactions occur, which induce a large spectrum of variation in both water and gas chemistry. These shallow processes do not affect the 3He/4He of helium dissolved in thermal waters, which records a magmatic signature that varies in response to changes in magma supply at depth. We show that in periods of more intense volcanic activity, the helium isotopic composition of thermal waters approaches that of the gas emitted from the magma residing at 7–10 km depth. Investigation of hydrothermal waters at active volcanoes is a promising tool to examine magmatic fluids and their shallow circulation, as well as to evaluate the state of activity of a volcano, particularly when summit areas are inaccessible.

Geothermal carbonate reservoirs and their sustainability: what can natural hydrothermal systems tell us?

Minerals that make up carbonate rocks (i.e. calcite) have very high chemical reactivity, allowing for various types of porosity-altering deformation processes such as dissolution and recrystallization (e.g. dolomitization, silicification), that produce secondary porosity. Even though water enriched with CO2 may quickly equilibrate by dissolving calcite, carbonate is also very dynamic, and cemented veins may still act as planes of weakness compared to the host rock allowing fluids to open up and then seal these fractures again. Therefore, natural carbonate rocks often show not only the numerous deformation stages overprinting one another, but also the same veins opening up again and again forming crack-seal structures.Natural fossil hydrothermal systems were investigated within outcrops at Nowa Wioska, Czatkowice, Pomorzan, Trzebionka, Orzel Bialy mines, Dziura cave and Hucianski Klin crest in the south of Poland to evaluate the influence of hydrothermal activities on the rock pore evolution. We present in more detail the Triassic carbonate sequence near Nowa Wioska village in the Silesian-Kraków region, where hydrothermal water had been flowing through an open fault zone, forming various hydrothermal products: secondary intercrystalline pores, vugs, breccias, metal ore and mineral precipitates. The impact of these products on the permeability of the geothermal system was analyzed in comparison with the adjacent host rock unaffected by tectonic and hydrothermal processes. We observed that at least three successive episodes of fracturing occurred during the Tertiary demonstrating that fluids were introduced episodically in the Triassic rocks. Fracture- and vug-filling calcite, saddle dolomite, pyrite, sphalerite, galena, quartz and clays were preferentially observed on the downthrown side of the fault that underwent a more intense tectonic deformation that had a decisive influence on the migration of mineralizing hydrothermal solutions. Even though mineral and metal-ore precipitates, sediments and solution / collapse breccias fill most of these karsts and fractures, the porosity and permeability of the hydrothermally altered rocks remain quite high compared to the host rock. Moreover, secondary dissolution forming vugs increase this porosity and permeability even further. The studied examples suggest that once geothermal system has been active, it stays as a preferential zone for the following deformation events, making it sustainable for tens of thousands or even millions of years.

Caracterización geoquímica de salmueras con litio de Guaranda, Ecuador

Lithium is considered a critical metal for its technological use. It was proposed to carry out the geochemical prospecting study in favorable environments to host possible lithium mineralization, in specific sectors of Ecuador. This would be important, as no anomalies of economic interest have been discovered to date. The content of Li in solid samples and hydrothermal waters in brines in the Guaranda sector, Bolívar province, was evaluated. Likewise, a mineralogical analysis of the solid samples and a multivariate statistical analysis of the data was carried out. The values of sub-anomalies of Li (median 222.46 mgL-1 in brines and Li in solids from Guaranda (median 201.5 ppm), may be comparable to exploitable Li deposits worldwide, which is interesting for its possible economic use. Based on the multivariate statistical analysis, chemical and mineralogical results, Li is associated with Be, and Na mainly in the solids analyzed, this is evidenced by the detection of aponite and fluoroferroleakeite. The chemical composition of the sampled waters could be the result of several processes that include: the dissolution of minerals by water-rock interaction, hydrothermal fluids related to active volcanism and/or recharge by meteoric waters.

Triple oxygen isotopes in intertrappean fossil woods: Evidence of higher tropical rainfall during Deccan volcanism

Despite several attempts, the effects of volcanism and greenhouse gas emission on climate (e.g., rainfall) over India across the Cretaceous/Palaeogene Boundary (66.1 ± 0.01 Ma) remain a contentious issue. Inferences from conventional isotopic, palaeosol, floral analysis, and palaeoclimate models are contradictory ranging from much lower- to higher-than-today rainfall during this high CO2 atmosphere. To resolve this, robust tracer of triple oxygen isotopic ratios (ẟ18O-∆′17O) of silicified fossil woods from Deccan intertrappean lacustrine sediments, central India were analysed for retrieving the silicification temperature and ambient fluid (water) isotopic composition. Under certain assumptions and uncertainty, triple oxygen isotope data indicate that the fluids were derived from a mixture of meteoric and hydrothermal water. The meteoric water end member possibly had a low ẟ18OVSMOW value (∼− 12 ± 2‰) compared to the modern mean monsoon rainwater (∼− 5‰) which implies a substantially higher rainfall than today (∼1760 ± 200 to 1860 ± 200 mm/year) in the terminal Cretaceous India. This result supports the prediction of elevated precipitation by the recent new generation of global coupled models that consider various feedbacks and ocean dynamics, at a high CO2 atmosphere. It is also consistent with the paleo-botanical evidence but far exceeds the amount predicted by the older paleoclimate models pertaining to the Cretaceous period.

An integrated geochemical spatial and temporal survey of thermal springs to characterize the geothermal resource of a volcano (Piton des Neiges, Réunion Island)

Geothermal exploration can be challenging in the absence of obvious surface indicators of a high enthalpy geothermal resource such as geysers, fumaroles or thermal springs with temperatures near 100 °C. This is the case at the Piton des Neiges volcano (Réunion Island), which displays evidence of hydrothermal activity mostly as thermal springs with temperatures not exceeding 50 °C, affected by mixing and reequilibration, and emerging in a complex geological framework, resulting from the polygenic history of this dormant volcano. Yet, these thermal springs keep a partial record of the reservoir geochemistry. Here, we propose an exploration method to set this thermal signature apart from the contribution of other processes and trace back the equilibrium conditions, enabling us to locate thermal fluid circulations, and evaluate their temperature and availability. We report its application at Piton des Neiges volcano. We led an extensive geochemical survey which nearly doubled the number of thermal springs reported on the volcano and dramatically extended the existing geochemical database in space and time. In tandem, we also monitored δ18O and δD values in rainwaters and thermal springs over two years to compare their temporal variations.Our surveys show that the repartition of thermal springs is controlled by only one of the volcanic rift zones (the N30°E axis), which is thus identified as the heat source of hydrothermal circulations. This N30°E rift zone is also a preferential pathway for the degassing of mantellic CO2. In addition, the composition of thermal waters is influenced by syenite intrusions along the rim of the caldera, acting as drains for the uprise of hydrothermal waters. O, H and Sr isotopic signatures of springs show that the geothermal resource of Piton des Neiges is in fact made of two independent and unconnected hydrothermal systems on the northern and southern circular depressions of the volcano (the cirques of Salazie and Cilaos, respectively). Their recharge is meteoric, multi-year, and mostly achieved by cyclonic events. Thermal waters experience reequilibration during their ascent and various degrees of CO2 input or degassing. Last equilibrium temperatures of water/rock interaction, estimated by multicomponent geothermometry, reach up to 125 ± 6 °C in the cirque of Salazie, and up to 141 ± 15 °C in the cirque of Cilaos, with possibility for hotter waters before reequilibration. Taken together, our results suggest that the most promising target for future exploration is located in the cirque of Cilaos, along the caldera rim, and in proximity of syenite intrusions.With a thorough prospecting of thermal springs, a comprehensive geochemical study and a geochemical monitoring of the different water reservoirs, we improved our understanding of the geothermal resource and identified future exploration targets at Piton des Neiges volcano.A separation scheme for strontium and light rare earth elements and its application to the isotopic analysis of strontium and neodymium in silicate rocks are presented. This method benefits from the selectivity and high capacity of two newly introduced extraction Chromatographic materials, referred to as Sr.Spec and TRU.Spec, respectively. These afford a straightforward separation of Sr and Sm + Nd with high yield, good purity and satisfactory blank levels, on very small (0.25 ml) columns using small volumes of solutions of a single mineral acid, HNO3. The validity of the method is illustrated by the measurement of 87Sr/ 86Sr and 143Nd/144Nd ratios in twelve international standard reference materials.

Multi-parametric observations of intermittent hydrothermal water discharge in West Crater of Iwo-Yama volcano, Kirishima Volcanic Complex, Japan

From April to July 2021, West Crater at Iwo-Yama, Kirishima Volcanic Complex, Japan, was repeatedly filled with hydrothermal water and subsequently evacuated. The overall cycle lasted 14–70 h, and the course of a single cycle followed this sequence of phases: (i) steam effusion disappeared 20–40 min before hydrothermal water discharge; (ii) hydrothermal water discharge occurred, generating a hydrothermal water pool; (iii) steam effusion resumed and gradually increased; and (iv) drain-back (evacuation) of the hydrothermal water occurred 1–1.5 h before the onset of the next hydrothermal water discharge. We used multi-parametric observations (optical camera, thermometer, electric self-potential (SP) electrodes, seismometer, acoustic sensor, and tiltmeter) to investigate the cause of the cyclic hydrothermal water discharge. A change in SP data occurred approximately 2 h before the onset of hydrothermal water discharge. However, the change in SP was small when hydrothermal water discharge did not occur. The temporal change in SP is inferred to have been caused by groundwater flow through the region below West Crater, implying that groundwater flow was occurring 2 h before hydrothermal water discharge. The polarity of SP change suggests that groundwater flowed toward the region underlying the vents. Seismic signals in the frequency range of < 20 Hz decreased 15–45 min after the onset of change in SP. This seismic signal pattern is inferred to have been caused by bubble activity in boiling fluid. We interpret that the inflow of cold groundwater inhibited boiling activity in the conduit, which in turn caused the cessation of both steam effusion and seismic activity. SP data suggest that the inflow of cold groundwater gradually decreased before hydrothermal water discharge. Pressurization sufficient to force the water in the upper part of the conduit to ascend could have built up in the lower part of the conduit owing to a decrease in the input of groundwater into the upper part of the conduit and the continuing supply of steam bubbles and hot water. This increase in pressure finally led to hydrothermal water discharge at the surface. We suggest that the inflow of cold groundwater into the geyser conduit was the key control on the occurrence and cyclicity of hydrothermal water discharge in West Crater at Iwo-Yama.Graphical

Diatom assemblages from different environments of the Acoculco Caldera associated to hydrothermal and anthropogenic activity.

The use of diatoms as indicators of water quality has been studied worldwide; however, the use of diatoms as indicators of thermic anomalies has received less attention. The objective of this study is not only to provide a record on algal communities, but also to investigate the relationship between the diversity in diatom species and the physicochemical conditions of water. Evaluating its temporal variability in a caldera with low permeability and cold acid hydrothermal anomalies. Diatom assemblages were identified at 11 sites. Species composition was compared between seasons (dry and wet) in different environments, as streams, ponds and pools within the caldera. The physicochemical and environmental differences are very specific, which allowed the diatom identification from geothermal and anthropogenic sources without finding mixtures. The results show that the main diatom flora of the Acoculco caldera consists of 15 dominant species. Sulphite-rich acidic hydrothermal waters are characterized by the presence of Eunotia exigua, Eunotia bilunaris, and Pinnularia brauniana. In non-hydrothermal streams, Planothidium, Achnanthidium, and Humidophila species are the most common taxa. Other diatoms from acidic environments were Frustulia saxonica, Surirella, and Stenopterobia. The assemblages are clearly different from those of alkaline environments. Epithemia, Planothidium, and Ulnaria are present in the streams and are not associated with thermalism. Ordination of diatom assemblages showed that pH, conductivity, and nutrient concentrations, some of which are influenced by anthropogenic activities, were the main factors influencing the distribution of diatom composition.