Impacts of subsurface heat storage on aquifer hydrogeochemistry

The use of shallow aquifers for subsurface heat storage in terms of energy management and building climatisation can lead to a temperature rise in the aquifer to 70 °C and above. The influence of temperature changes on individual mineral and sorption equilibria, reaction kinetics and microbial activity is largely known. However, the impact of heating to temperatures as high as 70 °C on the aquifer overall system has not been quantified yet. Temperature-related changes in sediment ion exchange behaviour, dimension and rates of mineral dissolution and precipitation as well as microbially enhanced redox processes were studied in column experiments using aquifer sediment and tap water at 10, 25, 40, and 70 °C. At 70 °C, a change in sediment sorption behaviour for cations and organic acids was postulated based on temporal changes in pH, magnesium, and potassium concentration in the experimental solution. No clear changes of pH, TIC and major cations were found at 10–40 °C. Redox zoning shifted from oxic conditions towards nitrate and iron(III) reducing conditions at 25 and 40 °C and sulphate reducing conditions at 70 °C. This was attributed to (a) a temperature-related increase in microbial reduction activity, and (b) three times higher release of organic carbon from the sediment at 70 °C compared to the lower temperatures. The findings of this study predict that a temperature increase in the subsurface up to 25 °C and above can impair the usability of ground water as drinking and process water, by reducing metal oxides and thus possibly releasing heavy metals from the sediment. Generally, at 70 °C, where clear cation and organic carbon desorption processes were observed and sulphate reducing conditions could be achieved, a site-specific assessment of temperature effects is required, especially for long-term operations of subsurface heat storage facilities.     

Effects of thermal energy storage on shallow aerobic aquifer systems: temporary increase in abundance and activity of sulfate-reducing and sulfur-oxidizing bacteria

Aquifer thermal energy storage may result in increases in the groundwater temperature up to 70 °C and more. This may lead to geochemical and microbiological alterations in the aquifer. To study the temperature effects on the indigenous microbial community composition, sediment column experiments at four different temperatures were carried out and the effluents were characterized geochemically and microbiologically. After an equilibrium phase at groundwater temperature of 10 °C for 136 days, one column was kept at 10 °C as a reference and the others were heated to 25, 40 and 70 °C. Genetic fingerprinting and quantitative PCR revealed a change in the bacterial community composition and abundance due to the temperature increase. While at 25 °C only slight changes in geochemical composition and gene copy numbers for bacteria were observed, increasing concentrations of total organic carbon in the 40 °C column were followed by a strong increase in bacterial abundance. Thermophilic bacteria became dominant at 70 °C. Temporary sulfate reduction took place at 40 and 70 °C and this correlated with an increased abundance of sulfate-reducing bacteria (SRB). Furthermore, a coexistence of SRB and sulfur-oxidizing bacteria (SOB) at all temperatures indicated an interaction of these physiological groups in the sediments. The results show that increased temperatures led to significant shifts in the microbial community composition due to the altered availability of electron donors and acceptors. The interplay of SRB and SOB in sedimentary biofilms facilitated closed sulfur cycling and diminished harmful sulfur species.     

Methane oxidation capacity of methanotrophs isolated from different soil ecosystems

Methane is one of the potential greenhouse gases contributing to global climate change, with a global warming potential of about 25 times than that of carbon dioxide. Aerobic methane oxidation (methanotrophy) is the key process that counteracts emission of methane to atmosphere. In this study, methane oxidation capacity of different methane-oxidizing bacteria (methanotrophs) isolated from six different ecosystems was investigated. Methanotrophic consortium isolated from dumpsite proved to be most effective in oxidizing methane. Initially, methane oxidation rate was found to be 0.72 ± 0.036 mM/day; in course of the study consortium M5 showed an increase in methane oxidation rate up to 1.7 ± 0.016 mM/day. A maximum of 0.78 mol of CO₂ production was found during methane oxidation in methanotrophs from dumpsite (M5). While varying temperatures, methane oxidation rate was in the range of 1.3–1.7 mM/day which has been found in the temperature range of 30–40 °C. Even at higher temperature (50 °C), 0.076 ± 0.14 mM of the methane was utilized per day. Methane oxidation was assessed by Michaelis–Menten kinetics. By varying the methane concentration, methane oxidation was studied and kinetic parameters such as V _max and K _m were derived using Lineweaver–Burk plot and found to be 1.497 mM/day and 2.23 mM, respectively. In methane mitigation approach, Methane soil sink is very essential because a balance between methane production by methanogens and consumption by methanotrophs plays an important role in methane emission reduction. Enhancing the methane soil sink will be a cost-effective method to cut down methane emission.     

A stratigraphic and geophysical approach to studying the deep-circulating groundwater and thermal springs, and their recharge areas, in Cimini Mountains–Viterbo area, central Italy

The stratigraphic and structural setting of the Cimini Mountains and Viterbo area of Italy has been reconstructed. The architecture of the tectonic edifice, below the Pleistocene Cimino and Vicano volcanic districts cover, is characterized by the Mesozoic–Cenozoic Tuscan Nappe and the similar Umbria-Marche Succession; both are capped by the overthrusted Ligurian Late Cretaceous–Eocene Tolfa Flysch. A shallow unconfined volcanic aquifer is separated, by a thick aquiclude, from the deep confined carbonate aquifer consisting of the Tuscan Nappe and the Umbria-Marche Succession. The volcanic aquifer hosts cold waters, whilst the carbonate aquifer hosts hot sulphate–alkaline earth waters that emerge in the thermal area of Viterbo with a temperature of 30–60°C. The recharge area of cold waters is located in the Cimini Mountains. Thermal waters of the Viterbo hot springs are derived from a circuit of waters that emerge along the River Nera near Narni (about 34 km ENE of Viterbo), with a high salinity, a temperature of 16–18°C, a sulphate–alkaline earth composition, and a discharge of 13 m³/sec, whose recharge area is located in the central pre-Apennines reliefs.     

Preservation of thermophilic mixed culture for anaerobic palm oil mill effluent treatment by convective drying methods

The generation of huge amount of liquid waste known as palm oil mill effluent is a major problem in oil palm industry. Meanwhile, anaerobic biodegradation of such organic effluent at thermophilic condition is a promising treatment technology due to its high efficiency. However, storage and transportation of thermophilic mixed culture sludge are challenging due to constant biogas generation and heating requirement. Hence, drying of thermophilic sludge was conducted to obtain dormant thermophiles and thus enables easier handling. In this study, thermophilic sludge was dried using heat pump at 22 and 32 °C as well as hot air oven at 40, 50, 60, and 70 °C. Subsequently, quality of dried sludge was examined based on most probable number enumeration, chemical oxygen demand, and methane yield. Average drying rate was found to increase from 3.21 to 17.84 g H₂O/m² min as drying temperatures increases while average moisture diffusivity values ranges from 5.07 × 10^?9 to 4.34 × 10^?8 m²/s. Oven drying of thermophilic mixed culture resulted in highest chemical oxygen demand removal and lowest log reduction of anaerobes at 53.41% and 2.16, respectively, while heat pump drying resulted in the highest methane yield and lowest log reduction of methanogens at 53.4 ml CH₄/g COD and 2.09, respectively. To conclude, heat pump at 22 °C was most suitable drying technique for thermophilic mixed culture as the original methane-producing capability was largely retained after drying, at a slightly lower yet still comparable chemical oxygen demand removal when palm oil mill effluent was treated with the rehydrated culture.     

Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes

Fluid inclusion studies in combination with hydrogen, oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst-bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul, Brazil. Monophase liquid inclusions in colourless quartz, amethyst, calcite, barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice-melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I, celadonite, chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low δ³⁴S_V-CDT values of pyrite (?25 to ?32?‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst, goethite and anhydrite), III (early subhedral calcite) and IV (barite, late subhedral calcite and gypsum), the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3, 3.4 and 0.3 wt% NaCl-equivalent characterise the mineralisation stages II, III and IV, respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in δ¹⁸O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80–90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C, while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst-precipitating fluid in combination with δD values of amethyst-hosted fluid inclusions (?59 to ?51?‰) show a significant ¹⁸O-shift from the meteoric water line. This ¹⁸O-shift, high salinities of the fluid inclusions with chloride-sulphate composition, and high δ³⁴S values of anhydrite and barite (7.5 to 9.9?‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation.     

Experimental and numerical simulation study of the mineral sequestration mechanism of the Shiqianfeng saline aquifers in the Ordos Basin,Northwest China

This study focused on typical injection layers of deep saline aquifers in the Shiqianfeng Formation used in the Carbon Capture and Sequestration Demonstration Projects in the Ordos Basin, Northwest China. The study employed experiments and numerical simulations to investigate the mechanism of CO₂ mineral sequestration in these deep saline aquifers. The experimental results showed that the dissolved minerals are plagioclase, hematite, illite–smectite mixed layer clay and illite, whereas the precipitated minerals are quartz (at 55, and 70 °C) and kaolinite (at 70 °C). There are rare carbonate mineral precipitations at the experimental time scale, while the precipitation of quartz as a product of the dissolution of silicate minerals and some intermediate minerals rich in K and Mg that transform to clay minerals, reveals the possibility of carbonate precipitation at the longer time scale. These results are consistent with some results previously reported in the literature. We calibrated the kinetic parameters of mineral dissolution and precipitation by these experimental results and then simulated the CO₂ mineral sequestration under deep saline aquifer conditions. The simulation results showed that the dissolved minerals are albite, anorthite and minor hematite, whereas the precipitated minerals are calcite, kaolinite and smectite at 55 and 70 °C. The geochemical reaction of illite is more complex. At 55 °C, illite is dissolved at the relatively lag time and transformed to dawsonite; at 70 °C, illite is precipitated in the early reaction period and then transformed to kaolinite. Based on this research, sequestrated CO₂ minerals, which are mainly related to the temperature of deep saline aquifers in Shiqianfeng Fm., are calcite and dawsonite at lower temperature, and calcite at higher temperature. The simulation results also establish that calcite could precipitate over a time scale of thousands of years, and the higher the temperature the sooner such a process would occur due to increased reaction rates. These characteristics are conducive, not only to the earlier occurrence of mineral sequestration, but also increase the sequestration capacity of the same mineral components. For a sequestration period of 10,000 years, we determined that the mineral sequestration capacity is 0.786 kg/m³ at 55 °C, and 2.180 kg/m³ at 70 °C. Furthermore, the occurrence of mineral sequestration indirectly increases the solubility of CO₂ in the early reaction period, but this decreases with the increase in temperature.     

Biotransformation potential of hexavalent chromium by Bacillus pumilus-S4, Pseudomonas doudoroffii-S5 and Exiguobacterium-S8 in association with hydrophytes

Three chromium-resistant bacteria Bacillus pumilus-S4, Pseudomonas doudoroffii-S5 and Exiguobacterium-S8 were isolated from chromium-contaminated wastewater/soil and could resist very high concentrations of potassium chromate in Luria agar (up to 25 mg ml^?1) and acetate minimal medium (2 mg ml^?1). The strains showed growth at diverse pH and temperatures and could resist multiple heavy metals. Pseudomonas doudoroffii-S5 reduced (8.27 mg hexavalent chromium 24 h^?1) at a lower initial potassium chromate concentration (100 μg ml^?1), but overall more chromate (28.4 mg hexavalent chromium 24 h^?1) was reduced at a higher initial concentration (1,000 μg ml^?1). The addition of various heavy metals (zinc sulphate, copper sulphate, and manganese sulphate at 50 μg ml^?1) in the chromium reduction media did not significantly affect the hexavalent chromium reduction potential of these isolates. The chromium removal/detoxification potential of these strains increased when used in conjunction with hydrophytes Eichornia crassipes and Pistia stratiotes. Interestingly, the whole process runs automatically with less energy input, that is, the bacterial strains support the growth of plant while in turn the plant releases exudates that help bacterial growth.     

Numerical investigation on the implications of spring temperature and discharge rate with respect to the geothermal background in a fault zone

Geothermal springs are some of the most obvious indicators of the existence of high-temperature geothermal resources in the subsurface. However, geothermal springs can also occur in areas of low average subsurface temperatures, which makes it difficult to assess exploitable zones. To address this problem, this study quantitatively analyzes the conditions associated with the formation of geothermal springs in fault zones, and numerically investigates the implications that outflow temperature and discharge rate from geothermal springs have on the geothermal background in the subsurface. It is concluded that the temperature of geothermal springs in fault zones is mainly controlled by the recharge rate from the country rock and the hydraulic conductivity in the fault damage zone. Importantly, the topography of the fault trace on the land surface plays an important role in determining the thermal temperature. In fault zones with a permeability higher than 1 mD and a lateral recharge rate from the country rock higher than 1 m³/day, convection plays a dominant role in the heat transport rather than thermal conduction. The geothermal springs do not necessarily occur in the place having an abnormal geothermal background (with the temperature at certain depth exceeding the temperature inferred by the global average continental geothermal gradient of 30 °C/km). Assuming a constant temperature (90 °C here, to represent a normal geothermal background in the subsurface at a depth of 3,000 m), the conditions required for the occurrence of geothermal springs were quantitatively determined.     

Alteration of fluid properties during the initial operation of a geothermal plant: results from in situ measurements in Groß Schönebeck

Recently, the thermal fluid loop has been established and continuosly operated for 7 days at the geothermal in situ laboratory in Groß Schönebeck (North German Basin). During this initial phase of fluid production, the fluid temperature, measured at the surface, continuously increased until a stable value of about 98 °C was established. Fluid physicochemical properties (pH, redox, density, temperature, and pressure) were measured online and in situ with a newly developed fluid monitoring system (FluMo). Additionally, fluid samples have been collected at various temperatures (in 5–10 °C steps) directly at the production well at about 10 bar pressure. From the pressurized sampling tool, the fluid was directly transferred into a heated autoclave, which allowed filtration (0.2 μm) in the absence of oxygen. Physicochemical parameters [pH, redox, electric conductivity, total dissolved solids (TDS)] as well as acid capacity (K _S 4.3) of these samples have been measured onsite at atmospheric conditions. Concentrations of anions, total organic carbon, and metals were analyzed later in the laboratory. Both, measurements in collected samples or in situ (FluMo) analysis of most the parameters density, electric conductivity, or TDS indicated relatively constant values over the whole production time (1.17–1.18 g · cm^?3, 215–221 mS · cm^?1, 241–260 g · L^?1, respectively). Good correlation was also found for pH values (pH = 6.6–6.9), whereas the redox values varied between ?1 and 46 mV when determined at 25 °C and decreased strongly when measured in situ with increasing temperature (?110 mV at 90 °C). The elemental composition of collected samples remained also relatively constant for most compounds and was clearly higher as compared with samples collected in 2011. Results of this study demonstrate that realistic, comprehensive, and time-resolved physicochemical data can be obtained by FluMo. These detailed data sets can be crucial to understand the complex geochemical processes in a thermal water loop and eventually to take required measures on time.     

Determination of radon exhalation from granite, dolerite and marbles decorative stones of the Azad Kashmir area, Pakistan

Extensive export quality reserves of granite, dolerite and marbles which are used for interior decorations as wall facing, paving floors, kitchen counter tops, etc., are available in Azad Kashmir. Since these stones contain radium in trace amounts, therefore, its use as a building material may be a potential source of indoor radon. In order to assess health hazards due to the use of these stones as a building material, samples were collected from different mining sites. After processing, these samples were placed in plastic containers and box type radon detectors were installed in it at the height of 25 cm above the surface of the samples. The containers were then hermetically sealed. After 60 days of exposure to radon, CR-39 detectors were etched in 6 M NaOH at 70 °C for 9 h and measured track densities were related to radon concentration. Radon exhalation rate form the studied granites, marble and dolerite samples varied from 87 ± 26 to 353 ± 36 mBq m^?2h^?1, 79 ± 25 to 650 ± 42 mBq m^?2h^?1 and 90 ± 26 to 324 ± 36 mBq m^?2h^?1, respectively. These decorative stones are therefore used in buildings and for export purposes as the observed radon exhalation values are smaller than that of the EPA recommended-action level.     

Characterization of the subsurface urban heat island and its sources in the Milan city area,Italy

Urban areas are major contributors to the alteration of the local atmospheric and groundwater environment. The impact of such changes on the groundwater thermal regime is documented worldwide by elevated groundwater temperature in city centers with respect to the surrounding rural areas. This study investigates the subsurface urban heat island (SUHI) in the aquifers beneath the Milan city area in northern Italy, and assesses the natural and anthropogenic controls on groundwater temperatures within the urban area by analyzing groundwater head and temperature records acquired in the 2016–2020 period. This analysis demonstrates the occurrence of a SUHI with up to 3 °C intensity and reveals a correlation between the density of building/subsurface infrastructures and the mean annual groundwater temperature. Vertical heat fluxes to the aquifer are strongly related to the depth of the groundwater and the density of surface structures and infrastructures. The heat accumulation in the subsurface is reflected by a constant groundwater warming trend between +0.1 and?+?0.4 °C/year that leads to a gain of 25 MJ/m² of thermal energy per year in the shallow aquifer inside the SUHI area. Future monitoring of groundwater temperatures, combined with numerical modeling of coupled groundwater flow and heat transport, will be essential to reveal what this trend is controlled by and to make predictions on the lateral and vertical extent of the groundwater SUHI in the study area.

     

Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure

We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between ?194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm^?1 display a small frequency lowering (<4 cm^?1) and a moderate broadening (<10 cm^?1) as temperature is increased from ?194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm^?1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm^?1 respectively) and broadening (~30 cm^?1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm^?1, three broad bands are identified at 3,151, 3,178 and 3,217 cm^?1, at ?194 °C. They exhibit significant frequency increase (~20 cm^?1) and broadening (~70 cm^?1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)_Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm^?1 (type (2); 3,550 cm^?1 at room temperature). The contribution of OH bands of type (3), associated to (2H)_Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.     

Past methane release events and environmental conditions at the upper continental slope of the South China Sea: constraints by seep carbonates

Authigenic carbonates and seep biota are archives of seepage history and record paleo-environmental conditions at seep sites. We obtained the timing of past methane release events at the northeastern slope of the South China Sea based on U/Th dating of seep carbonates and seep bivalve fragments from three sites located at 22°02′–22°09′N, 118°43′–118°52′E (water depths from 473 to 785 m). Also, we were able to reconstruct the paleo-bottom water temperatures by calculating the equilibrium temperature using the ages, the corresponding past δ¹⁸O of seawater (δ¹⁸O_sw) and the δ¹⁸O of the selected samples formed in contact with bottom seawater with negligible deep fluid influence. A criterion consists of mineralogy, redox-sensitive trace elements and U/Th-isotope systematics is proposed to identify whether the samples were formed from pore water or have been influenced by deep fluid. Our results show that all methane release events occurred between 11.5 ± 0.2 and 144.5 ± 12.7 ka, when sea level was about 62–104 m lower than today. Enhanced methane release during low sea-level stands seems to be modulated by reduced hydrostatic pressure, increased incision of canyons and increased sediment loads. The calculated past bottom water temperature at one site (Site 3; water depth: 767–771 m) during low sea-level stands 11.5 and 65 ka ago ranges from 3.3 to 4.0 °C, i.e., 1.3 to 2.2 °C colder than at present. The reliability of δ¹⁸O of seep carbonates and bivalve shells as a proxy for bottom water temperatures is critically assessed in light of ¹⁸O-enriched fluids that might be emitted from gas hydrate and/or clay dehydration. Our approach provides for the first time an independent estimate of past bottom water temperatures of the upper continental slope of the South China Sea.     

Local climate change induced by groundwater overexploitation in a high Andean arid watershed,Laguna Lagunillas basin,northern Chile

The Laguna Lagunillas basin in the arid Andes of northern Chile exhibits a shallow aquifer and is exposed to extreme air temperature variations from 20 to ?25 °C. Between 1991 and 2012, groundwater levels in the Pampa Lagunillas aquifer fell from near-surface to ~15 m below ground level (bgl) due to severe overexploitation. In the same period, local mean monthly minimum temperatures started a declining trend, dropping by 3–8 °C relative to a nearby reference station. Meanwhile, mean monthly maximum summer temperatures shifted abruptly upwards by 2.7 °C on average in around 1996. The observed air temperature downturns and upturns are in accordance with detected anomalies in land-surface temperature imagery. Two major factors may be causing the local climate change. One is related to a water-table decline below the evaporative energy potential extinction depth of ~2 m bgl, which causes an up-heating of the bare soil surface and, in turn, influences the lower atmosphere. At the same time, the removal of near-surface groundwater reduces the thermal conductivity of the upper sedimentary layer, which consequently diminishes the heat exchange between the aquifer (constant heat source of ~10 °C) and the lower atmosphere during nights, leading to a severe dropping of minimum air temperatures. The observed critical water-level drawdown was 2–3 m bgl. Future and existing water-production projects in arid high Andean basins with shallow groundwater should avoid a decline of near-surface groundwater below 2 m bgl and take groundwater-climate interactions into account when identifying and monitoring potential environmental impacts.     

Geochemical heterogeneity and isotope geochemistry of natural attenuation processes in a gasoline-contaminated aquifer at the Hnevice site,Czech Republic

The geochemical processes, water–rock interactions and stable isotopes distribution (δ¹³C of DIC and δ¹⁸O and δ³⁴S of \({\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} \)) were investigated in the gasoline-contaminated aquifer at the Hnevice site, 50  km northwest of Prague, Czech Republic. Diesel, gasoline and oil leaks originate from a large fuel storage area causing heavy contamination of the saturated and unsaturated zones in an area of about 0.7  km². Groundwater investigations were conducted using five multilevel sampler wells with emphasis on redox parameters and degradation by-products and a solid-phase study focused on iron speciation and determination of principal and secondary minerals. Based on the study of groundwater and solid-phase geochemistry, four different geochemical zones were described. Zone I is thought to be background consisting of an aerobic aquifer and the absence of reduced species in significant concentrations. Zone II is situated in the plume core with methanogenic, sulphate and iron-reducing conditions accompanied by ankerite and kutnahorite precipitates and significant depletion of the oxidation capacity of the aquifer. Zone III is a mixing (corona) zone, situated at the fringe of the plume with high biodegradation rates and Fe(III)-precipitants. In zone IV, reoxidation of Fe(II) minerals (with e.g. the occurrence of psilomelane and cornelite) is typical.     

Properties of geothermal resources in Kebilli region, Southwestern Tunisia

The Kebilli region is located in the Southwestern part of Tunisia, and is characterized by the presence of deep and shallow geothermal systems (continental intercalary and complex terminal). Chemical and isotopic contents are used to classify the type and determine the origin of thermal water. An evaluation of reservoir temperature and a possible geothermal fluid mixing are also carried out. Both continental intercalary-deep aquifer and complex terminal-shallow aquifer are of Na–(Ca)–Cl–(SO₄) mixed water type. The use of different geothermometers and the computation of saturation indexes for different solid phases suggests that the thermal reservoir temperature of the continental intercalary is between 92 and 105 °C, while the fluid temperature from the shallow complex terminal aquifer ranges from 50 to 75 °C. Also, the isotopic data indicates the old origin of all groundwater of Southwestern Tunisia. Mixing effects characterizing the continental intercalary and the complex terminal aquifers were identified using δ²H and δ¹⁸O relationship. It appears that the upward movement of thermal water from the deep aquifer to shallow ones is probably due to the abundant fractures in the research area.     

Effects of experimental reheating of natural basaltic ash at different temperatures and redox conditions

A set of experiments have been performed on volcanic materials from Etna, Stromboli and Vesuvius in order to evaluate how the exposure to thermal and redox conditions close to that of active craters affects the texture and composition of juvenile pyroclasts. Selected samples were placed within a quartz tube, in presence of air or under vacuum, and kept at T between 700 and 1,130 °C, for variable time (40 min to 12 h). Results show that reheating reactivates the melt, which, through processes of chemical and thermal diffusion, reaches new equilibrium conditions. In all the experiments performed at T = 700–750 °C, a large number of crystal nuclei and spherulites grows in the groundmass, suggesting conditions of high undercooling. This process creates textural heterogeneities at the scale of few microns but only limited changes of groundmass composition, which remains clustered around that of the natural glasses. Reheating at T = 1,000–1,050 °C promotes massive groundmass crystallization, with a different mineral assemblage as a function of the redox conditions. Morphological modifications of clasts, from softening to sintering as temperature increases, occur under these conditions, accompanied by progressive smoothing of external surfaces, and a reduction in size and abundance of vesicles, until the complete obliteration of the pre-existing vesicularity. The transition from sintering to welding, characteristic of high temperature, is influenced by redox conditions. Experiments at T = 1,100–1,130 °C and under vacuum produce groundmass textures and glass compositions similar to that of the respective starting material. Collapse and welding of the clasts cause significant densification of the whole charge. At the same temperature, but in presence of air, experimental products at least result sintered and show holocrystalline groundmass. In all experiments, sublimates grow on the external surfaces of the clasts or form a lining on the bubble walls. Their shape and composition is a function of temperature and fO₂ and the abundance of sublimates shows a peak at 1,000 °C. The identification of the features recorded by pyroclasts during complex heating–cooling cycles allows reconstructing the complete clasts history before their final emplacement, during weakly explosive volcanic activity. This has a strong implication on the characterization of primary juvenile material and on the interpretation of eruption dynamics.     

Shallow groundwater temperature in the Turin area (NW Italy): vertical distribution and anthropogenic effects

This study investigated the thermal regime of shallow groundwater in the Turin area (NW Italy), where the large energy demand has motivated a new interest for renewable sources, such as the use of ground-source heat pumps for domestic heating and cooling. The vertical variability of the groundwater temperature between the ground surface and 10–20 m was detected: deeper temperatures were higher than shallow temperatures in spring, while a decrease with depth occurred in autumn. These variations are connected with the heating and cooling cycles of the ground surface due to the seasonal temperature oscillation. Variations below the seasonal oscillation are likely to be connected with the presence of advective heat transport due to the groundwater flow, according to the hydraulic features of a shallow aquifer. Temperature values mostly ranged between 12 and 14 °C in rural areas, while the values were between 14 and 16 °C below the Turin city. This groundwater warming is attributed to a widespread urban heat island phenomenon linked to warmer land surface temperatures in Turin city. Sparse warm outliers are connected with point heat sources and site-specific conditions of land and subsurface use, which may cause the aquifer temperature to rise. A relatively stable temperature below the seasonal fluctuation zone combined with high productivity and legislated limits for deeper groundwater use represent favourable conditions for a large-scale diffusion of groundwater heat pumps within the shallow aquifer. Moreover, this heat surplus should be regarded as a resource for future geothermal installations.     

Improvement of anaerobic biodegradability of organic fraction of municipal solid waste by mechanical and thermochemical pretreatments

The effect of particle size of the organic fraction of municipal solid waste on methane potentiel was investigated and tested at different substrate-to-inoculum ratios (0.1, 0.5 and 1.0). The highest methane yield was obtained with particle size fraction > 3 mm at S/I of 0.1. Thermo-alkali and thermo-acid methods were also tested as pretreatment to increase the organic matter solubilization and subsequently methane production. The results indicated that maximum variation (63.6%) of soluble chemical oxygen demand was obtained by thermo-acid method. Optimum conditions of thermo-alkali pretreatment were pH 10, time reaction of 30 min and temperature of 105 °C. Soluble chemical oxygen demand and reducing sugar variations reached, respectively, 40 and 69% under these conditions. The methane yield of untreated and thermochemical pretreated OFMSW was determined in batch condition. The highest methane yield (260.9 L/kg VS) was obtained with thermo-alkali pretreatment, which was 21% higher than that of raw substrate. This study may pave a new way for industrial application of dealing with the organic fraction of municipal solid waste.