A hitherto unrecognised band in the Raman spectra of silica rocks: influence of hydroxylated Si–O bonds (silanole) on the Raman moganite band in chalcedony and flint (SiO<Subscript>2</Subscript>)

Chalcedony is a spatial arrangement of hydroxylated nanometre-sized α-quartz (SiO₂) crystallites that are often found in association with the silica mineral moganite (SiO₂). A supplementary Raman band at 501 cm⁻¹ in the chalcedony spectrum, attributed to moganite, has been used for the evaluation of the quartz/moganite ratio in silica rocks. Its frequency lies at 503 cm⁻¹ in sedimentary chalcedony, representing a 2 cm⁻¹ difference with its position in pure moganite. We present a study of the 503 cm⁻¹ band’s behaviour upon heat treatment, showing its gradual disappearance upon heating to temperatures above 300 °C. Infrared spectroscopic measurements of the silanole (SiOH) content in the samples as a function of annealing temperature show a good correlation between the disappearance of the 503 cm⁻¹ Raman band and the decrease of structural hydroxyl. Thermogravimetric analyses reveal a significant weight loss that can be correlated with the decreasing of this Raman band. X-ray powder diffraction data suggest the moganite content in the samples to remain stable. We propose therefore the existence of a hitherto unknown Raman band at 503 cm⁻¹ in chalcedony, assigned to ‘free’ Si–O vibrations of non-bridging Si–OH that oscillate with a higher natural frequency than bridging Si–O–Si (at 464 cm⁻¹). A similar phenomenon was recently observed in the infrared spectra of chalcedony. The position of this Si–OH-related band is nearly the same as the Raman moganite band and the two bands may interfere. The actually observed Raman band in silica rocks might therefore be a convolution of a silanole and a moganite vibration. These findings have broad implications for future Raman spectroscopic studies of moganite, for the assessment of the quartz/moganite ratio, using this band, must take into account the contribution from silanole that are present in chalcedony and moganite.     

A proposed mechanism for the growth of chalcedony

The structural disparities that distinguish chalcedony from macrocrystalline quartz suggest that different crystallization mechanisms are operative during the growth of these two forms of silica. Although the paragenesis of chalcedony has provoked marked disagreement among researchers, a review of previous studies supports the idea that chalcedony can precipitate from slightly saturated aqueous solutions at relatively low temperatures (<100° C). These conditions for deposition suggest a model for chalcedony crystallization that involves the assembly of short-chain linear polymers via bridging silica monomers. This assembly occurs through a spiral growth mechanism activated by a screw dislocation withb=n/2 [110], wheren is an integer. The proposed model can account for a number of peculiarities that have been observed in chalcedony at the microstructural scale, such as: (1) the direction of fiber elongation along [110] rather than [001]; (2) the periodic twisting of chalcedony fibers about [110]; (3) the high density of Brazil twin composition planes; (4) the common intergrowth of moganite within chalcedony.     

Structural defects in microcrystalline silica

The structure of the microcrystalline silica varieties chalcedony, flint, moganite, opal-C and -CT is characterized by X-ray powder diffractometry and transmission electron microscopy (TEM). The role of impurities is investigated by infrared spectroscopy and chemical analysis. Microcrystalline opal, chalcedony and flint have a disordered intergrowth structure composed of cristobalite and tridymite domains in opal, and quartz and moganite domains in chalcedony and flint. Each constituent phase has different cell dimensions and symmetry. The main impurity is water which is enriched at the intergrowth interfaces. Density and refractive indices of microcrystalline silica depend on the water content.     

Mineralogical and textural variation of silica minerals in hydrothermal flow-through experiments: Implications for quartz vein formation

We conducted hydrothermal flow-through experiments at 430 °C and 31 MPa to investigate the mechanism of silica precipitation on granite under crustal conditions. Two experiments were performed using different input solutions: a single-component Si solution, and a multi-component solution with minor Al, Na, and K. The degree of supersaturation with respect to quartz, Ω = C_Si/C_Si,Qtz,eq, where C_Si and C_Si,Qtz,eq indicate Si concentration in solutions and the solubility of quartz within water, respectively, decreased from 3-3.5 to <1.1 along the flow path. A variety of silica minerals formed during the experiments (opal-A, opal-C, chalcedony, and quartz), and their occurrences and modal abundances changed in response to Ω and the presence of additives in the solution.For near-equilibrium solutions (Ω < ∼1.2), silica precipitation occurred in a simple way in both experiments, being restricted to overgrowths on pre-existing quartz surfaces in the granite. At higher saturation levels (Ω > ∼1.2), silica minerals were deposited on other surfaces in addition to quartz. In the single-component experiment, the dominant silica minerals changed in the order of opal-A → opal-C → quartz with decreasing Si concentration along the flow path. In contrast, in the multi-component experiment, quartz and minor chalcedony formed throughout the entire reaction vessel. This finding indicates that impurities (Na, K, and Al) in the solutions inhibited the precipitation of opal and enhanced the direct nucleation of quartz. The systematic appearance of metastable silica minerals were examined by nucleation processes and macroscopic precipitation kinetics. Our experimental results indicate that different precipitation mechanisms yield contrasting textures, which in turn suggests that vein textures can be used as indicators of solution chemistry within the fracture.     

Thermochemistry of the new silica polymorph moganite

Samples of microcrystalline silica varieties containing variable amounts of the new silica polymorph moganite (up to R~82 wt.%) have been studied by a combination of high temperature solution calorimetry using lead borate (2 PbO · B₂O₃) solvent and transposed temperature drop calorimetry near 977 K, in order to investigate the thermochemical stability of this new silica mineral. The enthalpy of solution at 977 K and the heat content (H₉₇₇ — H₂₉₈) of “pure” moganite phase were estimated to be -7.16 ± 0.35 kJ/mol and 43.62 ± 0.50 kJ/mol, respectively. The standard molar enthalpy of formation is-907.3 ± 1.2 kJ/mol. Thus, calorimetry strongly supports results of previous X-ray and Raman spectroscopic studies that moganite is a distinct silica polymorph. Its thermochemical instability relative to quartz at 298 K of 3.4 ± 0.7 kJ/mol is marginally higher than those of cristobalite and tridymite. Structurally, this instability may be related to the presence of distorted 4-membered rings of SiO₄ tetrahedra, which are not found in the quartz structure. The metastability relative to quartz may also explain the apparent scarcity of moganite in altered rocks and in rocks that are older than 130 my.     

Characterization of the Sündikendağı deposit of moganite-rich,blue chalcedony nodules,Mayıslar–Sarıcakaya (Eskişehir), Turkey

Blue chalcedony nodules have been mined from the Sündikendağı deposit in the Mayıslar–Sarıcakaya (Eskişehir) region of north-central Turkey since ancient times; however, no modern geological study of this deposit has yet been published. Although ancient and current mining production have both taken place in an area of complex geology, our study and analyses of the deposit suggests a simple model of sedimentary deposition for its origin. The repeated episodes of tectonic activity, accompanied by brittle deformation, metamorphism, and hydrothermal activity, which characterize this part of the Anatolian Peninsula with its complex junction of tectonic plates, appear to have had little influence on the blue chalcedony nodules that make the deposit valuable other than perhaps to influence their trace-element composition.The physical nature of the nodules as revealed by polarized-light microscopy and XRD—they are composed only of fibrous length-fast quartz (chalcedony) and fibrous length-slow quartz (moganite), but contain neither platy opal-CT nor opal-C—is consistent with a sedimentary origin as are their overall shape and strata-bound occurrence in a sandstone (arkose).The relatively high concentrations of some trace elements in the nodules revealed by ICP-AES, suggest involvement of hydrothermal fluids during the direct epigenetic formation of chalcedony concretions during diagenesis of the enclosing sandstone or by alteration of diagenetic concretions of another composition. Sources could include upwardly moving hydrothermal fluids entering the sedimentary basin from underlying older Sarıcakaya intrusive rocks or sea-floor hydrothermal vents in the vicinity during diagenesis in the Palaeocene and Eocene (65–37.8 Ma) periods.Oxygen isotope analyses (SMOW) (using EA-IRMS) of both the blue chalcedony nodules (δ¹⁸O = + 28.2‰ to + 30.8‰) and the enclosing sandstone (δ¹⁸O = + 11.3‰ to + 13.2‰) suggest that the nodules formed during diagenesis at a low temperature of around 55 °C, although they are encased in sandstone whose grains came from rocks that formed at significantly higher temperature, perhaps above 100 °C.The unbanded Sündikendağı chalcedony nodules are similar in occurrence to the banded Fairburn agates of South Dakota, USA and the Dryhead agates of Montana, USA, which formed in Palaeozoic limestones, except that the blue chalcedony is hosted in sandstone. Other sedimentary agates are generally believed to have formed by the alteration of diagenetic concretions from the outside, inward. No other agates or chalcedonies hosted in sandstone are known for comparison with this deposit. Thus, the deposit appears to be unique. It is possible that the Sündikendağı unbanded blue chalcedony formed as epigenetic concretions during diagenesis of the sandstone—a mechanism previously shown for large crystals of other minerals found in sandstones.     

Isotope–geochemical characterization and geothermometrical modeling of Uttarakhand geothermal field,India

Uttarakhand geothermal area, located in the central belt of the Himalayan geothermal province, is one of the important high temperature geothermal fields in India. In this study, the chemical characteristics of the thermal waters are investigated to identify the main geochemical processes affecting the composition of thermal waters during its ascent toward the surface as well as to determine the subsurface temperature of the feeding reservoir. The thermal waters are mainly Ca–Mg–HCO₃ type with moderate silica and TDS concentrations. Mineral saturation states calculated from PHREEQC geochemical code indicate that thermal waters are supersaturated with respect to calcite, dolomite, aragonite, chalcedony, quartz (SI > 0), and undersaturated with respect to gypsum, anhydrite, and amorphous silica (SI < 0). XRD study of the spring deposit samples fairly corroborates the predicted mineral saturation state of the thermal waters. Stable isotopes (δ¹⁸O, δ²H) data confirm the meteoric origin of the thermal waters with no oxygen-18 shift. The mixing phenomenon between thermal water with shallow ground water is substantiated using tritium (³H) and chemical data. The extent of dilution is quantified using tritium content of thermal springs and non-thermal waters. Classical geothermometers, mixing model, and multicomponent fluid geothermometry modeling (GeoT) have been applied to estimate the subsurface reservoir temperature. Among different classical geothermometers, only quartz geothermometer provide somewhat reliable estimation (96–140 °C) of the reservoir temperature. GeoT modeling results suggest that thermal waters have attained simultaneous equilibrium with respect to minerals like calcite, quartz, chalcedony, brucite, tridymite, cristobalite, talc, at the temperature 130 ± 5 °C which is in good agreement with the result obtained from the mixing model.     

Opal and chalcedony speleothems on quartz sandstones in the Sydney region,southeastern Australia

Speleothems of silica are far rarer than those of calcite but occur in a range of types including stalactites, stalagmites and flowstones. This study has found a wider range and far greater number of silica speleothems on the quartz sandstones of the Sydney region than the small number of previous accounts had suggested. Speleothems on the Sydney region sandstones are composed of multiple layers of amorphous opal‐A and cryptocrystalline chalcedony. Silica slowly dissolved from detrital and diagenetic quartz and kaolinite clays of the host arenites is redeposited as opal‐A at the sandstone surface when groundwater evaporates. This amorphous silica converts over time by Ostwald‐type paragenesis to the cryptocrystalline form, but the expected intermediate opal‐CT phase has not been detected. The crystallisation of chalcedony at earth‐surface temperatures is generally believed to take an extremely long time and its presence makes these speleothems very significant, especially as it is reported in only a small number of silica speleothems elsewhere. Furthermore, a similar paragenetic silica‐‘ripening’ mechanism may also be involved in the low‐temperature earth‐surface formation of other crystalline silica deposits such as silcrete duricrusts and pedogenic quartz. Additional closely coupled laboratory and field investigations into the processes that control silica paragenesis under earth‐surface conditions are sorely needed.     

The nature of water in chalcedony and opal-C from brazilian agate geodes

The water species (H₂O_(SiOH) and H₂O_(mol)) of length-fast chalcedony and opal-C in Brazilian agates were studied with thermoanalytical, chemical and infrared absorption methods. Specific surfaces were measured with the BET nitrogen adsorption method and the specific densities were determined. Chalcedony and opal-C have fully hydrated crystal surfaces at the open porosity. They contain additional water at inner surfaces, which are closed micropores in the case of opal-C and regions of accumulated defects (e.g. twinlamellae boundaries) in chalcedony. All surfaces are covered with silanole groups, hydrogen-bonded to molecular water. Additional hydroxyl groups, weakly hydrogen bonded to the structural framework within the crystallites, are located at structural point defects. Wall-lining chalcedony ranges from translucent gray to milky white bands corresponding with decreasing total water content, the H₂O_(SiOH)/H₂O_(mol)-ratio, BET-surfaces and increasing density. The H₂O_(SiOH)/H₂O_(mol)-ratio is sensitive to subsequent hydrothermal treatment and indicates a low temperature formation of chalcedony.     

Crystallization of quartz dioritic magmas at 2 and 1 kbar: experimental results

Crystallization experiments were performed on quartz diorite (~55 wt.% SiO₂, 3.1–8.4 wt.% MgO) from the G?siniec Intrusion (Bohemian Massif, SW Poland) at 1?2 kbar, 750–850°C, various mole fractions of water and with fO₂ buffered by the NNO buffer. The two natural quartz diorites (leucocratic poikilitic quartz diorite - ‘LPD’ and melanocratic quartz diorite - ‘MD’) differ in whole rock and mineral composition with MD being richer in MgO and poorer in CaO than LPD, probably due to accumulation of mafic minerals or melt removal in MD. LPD represents melt composition and is used to reconstruct crystallization conditions in the G?siniec Intrusion. The crystallization history of LPD magma, deduced from experimental and natural mineral compositions, includes a higher pressure stage probably followed by emplacement at ~2 kbar of partly crystallized magma at temperatures ~850?800°C and quick cooling. The mineral assemblage present in LPD requires water contents in the magma of at least 5 wt% and oxygen fugacity below that controlled by the NNO buffer. The compositions of mafic minerals in the MD composition were equilibrated at temperatures below 775°C and at subsolidus conditions. The equilibration was probably due to the reaction between water-rich, oxidizing residual melt and the cumulatic-restitic mineral assemblage. MD is characterized by occurrence of the euhedral cummingtonite and increasing anorthite content in the rims of plagioclase. A similar reaction was reproduced experimentally in both LPD and MD compositions indicating that cummingtonite may be a late magmatic phase in quartz dioritic systems, crystallizing very close to solidus and only from water saturated magma.     

Crystal structure and growth fabric of length-fast chalcedony

Chalcedony from Brazilian agates, has been investigated by using transmission-electron microscopy, X-ray-diffraction, thermogravimetry and optical techniques. The quartz fibers of length-fast chalcedony are composed of submicroscopical polysynthetic, lamellar-twinned right- and lefthanded crystals, according to the Brazil law. This very narrow twinning causes 3 systems of diffuse diffraction streaks (corresponding to the three-fold symmetry) parallel to 〈10.1〉, very frequently possessing an intensity maximum at h±1/2, k, l±1/2. These extra reflections were detected both in electron- and X-ray-diffraction patterns. Wall-lining chalcedony is parallel fibrous consisting of smaller crystallites with a higher total water content (0.06±0.01 μm and 1.2±0.1 wt %) than spherulitic chalcedony in horizontal agate bands (ca. 0.1 μm and 0.7±0.1 wt%).     

TEM characterisation and interpretation of fabric and structural degree of order in microcrystalline SiO2 phases

Representative samples of the two fabric varieties of microcrystalline quartz, chalcedony and quartzine, from agates of different origin were investigated by transmission electron microscopy (TEM). Both varieties contain lamellar admixtures of the SiO₂ mineral moganite. The transitions from quartz to moganite within the fabric differ in a characteristic way. Whereas in quartzine the gradient between the structures is steep, the transition is more continuous in chalcedony. The morphology of moganite in chalcedony and quartzine is determined by the (101)-face; in pure moganite from Gran Canaria it is governed by the (110)-face.     

Hydrogeochemical investigations of thermal waters in the northeastern part of Morocco

Northeastern Morocco is characterised by a large number of surface geothermal manifestations. Thermal waters are hosted within sedimentary rocks, and in particular the Liassic dolomitic limestones act as a reservoir. The presence of geothermal waters is closely related to important fault systems. Meteoric water infiltrates along those fractures and faults, gets heated, and then returns to the surface through hydrothermal conduits. Most of the thermal waters are of Na–Cl and Ca–Mg–HCO₃ types. In this paper different geochemical approaches were applied to infer the reservoir temperature. Na–K–Mg^1/2 ternary diagram points to temperatures ranging from 100 to 180 °C. Cation geothermometers suggest an average reservoir temperature of about 100 °C. Mineral solution equilibria analysis yields temperatures ranging from 50 to 185 °C. The silica enthalpy mixture model gives an average value (about 110 °C) higher than that inferred from cation geothermometers.     

Occurrence and distribution of “moganite” in agate/chalcedony: a combined micro-Raman, Rietveld, and cathodoluminescence study

Agate/chalcedony samples of different origin were investigated by performing Raman, X-ray diffraction (using Rietveld refinement), and cathodoluminescence measurements. These analyses were performed to measure the content and spatial distribution of the silica polymorph moganite, which is considered to represent periodic Brazil-law twinning of α-quartz at the unit-cell scale in agate/chalcedonies. Homogeneous standard samples including the nearly α-quartz free moganite type material from Gran Canaria were analysed in order to compare results of the X-ray diffractometry and Raman spectroscopy techniques and to provide a calibration curve for the Raman results. However, due to the different length scales analysed by the two techniques, the “moganite content” in microcrystalline SiO₂ samples measured by Raman spectroscopy (short-range order) was found to be considerably higher than the “moganite content” measured by X-ray diffractometry (long-range order). The difference is explained by the presence of moganite nanocrystals, nano-range moganite lamellae, and single Brazil-law twin-planes that are detected by vibrational spectroscopy but that are not large enough (in the sense of coherently scattering lattice domains) to be detected by X-ray diffractometry. High resolution Raman analysis provides a measure of the moganite content and its spatial variation in microcrystalline silica samples with a lateral resolution in the μm-range. Variations in the moganite-to-quartz ratio are revealed by varying intensity ratios of the main symmetric stretching-bending vibrations (A₁ modes) of α-quartz (465 cm⁻¹) and moganite (502 cm⁻¹), respectively. Traces of Raman microprobe analyses perpendicular to the rhythmic zoning of agates revealed that the moganite-to-quartz ratio is often not uniform but shows a cyclic pattern that correlates with the observed cathodoluminescence pattern (colour and intensity). Data obtained from an agate sample from a fluorite deposit near Okorusu, Namibia and from a volcanic agate from Los Indios, Cuba were selected for detailed presentation. Variations of cathodoluminescence and Raman data between single bands in agates suggest alternating formation of fine-grained, highly defective chalcedony intergrown with moganite, and coarse-grained low-defect quartz. Multiple zones indicate dynamic internal growth during a self-organizational crystallization process from silica-rich fluids. Received: 4 December 1997 / Accepted 19 June 1998     

Are spherulitic lacustrine carbonates an expression of large-scale mineral carbonation? A case study from the East Kirkton Limestone,Scotland

Lacustrine carbonate deposits with spherulitic facies are poorly understood, but are key to understanding the economically important “Pre-Salt” Mesozoic strata of the South Atlantic. A major barrier to research into these unique and spectacular facies is the lack of good lacustrine spherulite-dominated deposits which are known in outcrop. Stratigraphy and petrography suggest one of the best analogue systems is found in the Carboniferous of Scotland: the East Kirkton Limestone. Here we propose a hydrogeochemical model that explains why the CaCO₃, SiO₂, Mg-Si-Al mineral suite associated with spherular radial calcite facies forms in alkaline lakes above basaltic bedrock. Demonstrating links between igneous bedrock chemistry, lake and spring water chemistry and mineral precipitation, this model has implications for studies of lacustrine sediments in rift basins of all ages. Using empirical and theoretical approaches, we analyze the relationship between metal mobilization from sub-surface volcaniclastic rocks and the potential for precipitation of carbonate minerals, various Mg-bearing minerals and chalcedony in a lacustrine spherulitic carbonate setting. This suite of minerals is most likely formed by in-gassing of CO₂ to a carbon-limited alkaline spring water, consistent with the reaction of alkali igneous rocks in the subsurface with meteoric groundwater. We suggest that an analogous system to that at East Kirkton caused development of the ‘Pre-Salt’ spherulitic carbonate deposits.     

Magmatic infiltration and melting in the lower crust and upper mantle beneath the Cima volcanic field,California

 Xenoliths of lower crustal and upper mantle rocks from the Cima volcanic field (CVF) commonly contain glass pockets, veins, and planar trains of glass and/or fluid inclusions in primary minerals. Glass pockets occupy spaces formerly occupied by primary minerals of the host rocks, but there is a general lack of correspondence between the composition of the glass and that of the replaced primary minerals. The melting is considered to have been induced by infiltration of basaltic magma and differentiates of basaltic magma from complex conduits formed by hydraulic fracturing of the mantle and crustal rocks, and to have occurred during the episode of CVF magmatism between ∼7.5 Ma and present. Variable compositions of quenched melts resulted from mixing of introduced melts and products of melting of primary minerals, reaction with primary minerals, partial crystallization, and fractionation resulting from melt and volatile expulsion upon entrainment of the xenoliths. High silica melts ( >∼60% SiO₂) may result by mixing introduced melts with siliceous melts produced by reaction of orthopyroxene. Other quenched melt compositions range from those comparable to the host basalts to those with intermediate Si compositions and elevated Al, alkalis, Ti, P, and S; groundmass compositions of CVF basalts are consistent with infiltration of fractionates of those basalts, but near-solidus melting may also contribute to formation of glass with intermediate silica contents with infiltration only of volatile constituents. Received: 15 June 1995 / Accepted: 13 December 1995     

Shock-wave compression of silica gel as a model material for comets

A shock-wave compression experiment using synthesized silica gel was investigated as a model for a comet impact event on the Earth’s surface. The sample shocked at 20.7 GPa showed considerable structural changes, a release of water molecules, and the dehydration of silanol (Si–OH) that led to the formation of a new Si–O–Si network structure containing larger rings (e.g., six-membered ring of SiO₄ tetrahedra). The high aftershock temperature at 20.7 GPa, which could be close to 800 °C, influenced the sample structure. However, some silanols, which were presumed to be the mutually hydrogen-bonded silanol group, remained at pressures >20.7 GPa. This type of silanol along with a small number of water molecules may remain even after shock compression at 30.9 GPa, although the intermediate structure of the sample recovered was similar to that of silica glass.     

On the stability of magmatic cordierite and new thermobarometric equations for cordierite-saturated liquids

In this work, we have reviewed a large compositional dataset (571 analyses) for natural and experimental glasses to understand the physico-chemical and compositional conditions of magmatic cordierite crystallization. Cordierite crystallizes in peraluminous liquids (A/CNK ≥1) at temperatures ≥750 °C, pressures ≤700 MPa, variable H₂O activity (0.1–1.0) and relatively low fO₂ conditions (≤NNO ? 0.5). In addition to A/CNK ratio ≥1, a required condition for cordierite crystallization is a Si + Al cation value of the rhyolite liquid of 4 p8O (i.e. calculated on the 8 oxygen anhydrous basis), which is consistent with low Fe³⁺ contents and the absence or low content of non-bridging oxygens (NBO). This geochemical condition is strongly supported by the rare, if not unique, structure of cordierite where the tetrahedral framework is composed almost exclusively of Si and Al cations the sum of which is equal to 4 p8O [i.e. (Mg,Fe)_8/9Al_16/9Si_20/9O₈], indicating that aluminium (and cordierite) saturation is limited by rhyolite liquids with Al = 4 ? Si. Indeed, synthetic or natural systems with Al > 4 ? Si always show metastable glass-in-glass separation or crystallization of refractory minerals such as corundum (Al_16/3O₈) and aluminosilicates (Al_16/5Si_8/5O₈). Multivariate regression analyses of literature data for experimental glasses coexisting with magmatic cordierite produced two empirical equations to independently calculate the T (±13 °C; ME, maximum error = 29 °C) and P (±16 %; ME% = 27 %) conditions of cordierite saturation. The greatest influence on the two equations is exerted by H₂O_melt and Al concentrations, respectively. Testing of these equations with other thermobarometric constraints (e.g. feldspar-liquid, GASP, Grt–Bt and Grt–Crd equilibria) and thermodynamic models (NCKFMASHTO and NCKFMASH systems) was successfully performed for Crd-bearing rhyolites and residual enclaves from San Vincenzo (Tuscany, Italy), Morococala Field (Bolivia) and El Hoyazo (Spain). The reliability of each calculated P–T pair was graphically evaluated using the minimum and maximum P–T–H₂O relationships for peraluminous rhyolite liquids modified after the metaluminous relationships in this work. Both P–T calculations and checking can be easily performed with the attached user-friendly spreadsheet (i.e. Crd-sat_TB).     

Characterization of a Pleistocene thermal spring in Mozambique

A hydrogeological study was conducted with the objective to investigate the only currently known hot spring of Sofala Province in Mozambique with respect to the origin of the water, the discharge, and its chemical composition. Field investigations comprised a general land use survey, mapping of sediment and water temperatures, discharge measurements and on-site water chemistry as well as sampling for further chemical analyses and groundwater dating. Thermal water discharge occurs along a 100 m long NE–SW zone with water temperatures ranging from 42 to 64.5°C. The thermal water is a low-mineralized sodium-chloride-sulfate water enriched in phosphate, fluorine and nickel. The silica geothermometer, the silica concentration of 43 mg/kg and the ratios of Br/Cl and I/Cl of 2.5?×?10^–3, suggest that the thermal water stems from approximately 5,000 m depth and had a long residence time with silicate rocks. This points towards Gorongosa Mountain as the water source area. ¹⁴C dating suggests a groundwater age of 11,000 years.     

Features of mineral and chemical composition of the Khamambettu Carbonatites, Tamil Nadu

The paper presents mineralogical features and EPMA results of the Khamambettu carbonatites. The mineralogical data suggest that these rocks have been generated in magmatic and hydrothermal stages. Mineral geothermometer for carbonatite give temperatures of 790°–980°C. Fluid inclusion measurements in monazite (hydrothermal stage) give temperatures of 220°–290°C. One of the features of the carbonatites is high content of magnesia that is defined by the presence of dolomite, olivine, spinel, phlogopite, Mg-rich ilmenite. Chloritization, serpentinization, amphibolization, silicification processes and occurrence of barite, monazite-(Ce), strontianite, celestine are related to hydrothermal stage. Hydrothermal minerals at the Khamambettu were formed by recrystallization of primary carbonatite minerals in the presence of Ba, (SO₄)^2?, REE and Si carried in solution by the hydrothermal fluid.