Geochemistry of mineral water and gases of the Razdolnoe Spa (Primorye,Far East of Russia)

New isotopic and chemical data on the sodium bicarbonate water and associated gases from the Razdolnoe Spa located in the coastal zone of Primorsky Kray of the Russian Far East, together with previous stable isotope data (δ¹⁸O, δD, δ¹³C), allow elucidation of the origin and evolution of the groundwater and gases from the spa. The water is characterized by low temperature (12 °C), TDS – 2.5–6.0 g/L, high contents of B (∼5 mg/L) and F (4.5 mg/L) and low contents of Cl and SO₄. Water isotopic composition indicates its essentially meteoric origin which may comply with an older groundwater that was recharged under different (colder) climatic conditions. Major components of bubbling gases are CH₄ (68 vol%), N₂ (28%) and CO₂ (4%). The obtained values δ¹³C and δD for CO₂ and CH₄ definitely indicate the marine microbial origin of methane. Thus the high methane content in the waters relates to the biochemical processes and presence of a dispersed organic matter in the host rocks. Based on the regional hydrogeology and the geological structure of the Razdolnoe Spa, Mesozoic fractured rocks containing Na–HCO₃ mineral water and gases are reservoir rocks, a chemical composition of water and gases originates in different environmental conditions.     

Geochemistry of Thermal Waters of Continental Margin of Far East of Russia

Studied waters belong to warm(T=30-50℃),alkaline(pH=8.9-9.3),low mineralized(TDS235 mg/1)Na-HCO_3 or Na-SO_4-HCO_3 thermal waters with high content of SiO_2(up to 81 mg/l)and F(up to 3.9 mg/1),occur on modern volcano-tectonic rejuvenated areas of Eastern Sikhote-Alin orogenic belt.Low~3He concentration as well as N_2/O_2 and N_2/Ar ratios exclude influence of deep mantle fluid.New rare earth element data constrain our understandmg of water-rock interaction occurring in the water source region.Meteoric origin of waters is proved by stable isotope values varying from-71‰to-136.1‰and from-10.8‰to-18.8‰forδ~2U andδ~(18)O respectively.REE patterns reflect high pH,resultfing from water-rock interaction and oxidative conditions.Calculations of deep aquifer temperature using Na-K and quartz geothermometers show 116.8-131.1°C and 82.2-125.8℃respectively.Presence of deep faults both with abnormal thermal gradient(~45-50 K/km)define unique geochemical shape of thermal waters of Sikhote-Alin,area,where no present volcanic activity is registered.     

Geochemical characteristics of shallow groundwater in Datong basin, northwestern China

Located in semi-arid regions of northwestern China, Datong basin is a Quaternary sedimentary basin, where groundwater is the most important source for water supply. It is very important to study groundwater characteristics and hydrogeochemical processes for better management of the groundwater resource. We have identified five geochemical zones of shallow groundwater (between 5 and 80 m) at Datong: A. Leaching Zone (Zone I); B. Converging Zone (Zone II); C. Enriching Zone (Zone III); D. Reducing Zone (Zone IV); E. Oxidizing Zone (Zone V). In Zones I, II, and V and some parts of Zones III and IV, hydrolysis of albite/K-feldspar/chalcedony system and/or albite/K-feldspar/quartz system enhanced concentrations of Na⁺, K⁺, HCO₃⁻ and silicate. In Zone I, dissolution of carbonate and hydrolysis of feldspar generally controlled the groundwater chemistry. Infiltration of meteoric water promoted the formation of HCO₃⁻ in the water. In Zone II, the main geochemical processes influencing the groundwater chemistry were dissolutions of calcite and dolomite, ion exchange and evaporation. In Zones III and IV, in addition to ion exchange, evaporation and precipitation of calcite and dolomite, leaching of NaHCO₃ in saline–alkaline soils dominated the water quality. Zone IV was under anoxic condition, and reduction reactions led to the decrease of SO₄²⁻, NO₃⁻ and occurrence of H₂S, with the highest arsenic content (mean value of 366 μg/L), far exceeding Maximum Contaminant Level (MCL). Abnormal arsenic in the groundwater resulted in endemic disease of waterborne arsenic poisoning among local people. Zone V overlapped Zone I was intensively affected by coal mining activities. Sulfide minerals, such as pyrite, would have been oxidized when exposed to air due to coal mining, which directly added sulfate to groundwater and thus increased SO₄²⁻ concentration. Oxidization of sulfide minerals also decreased pH and promoted dissolutions of calcite and dolomite.     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

Hydrochemical and isotope characteristics of spring water and travertine in the Baishuitai area (SW China) and their meaning for paleoenvironmental reconstruction

A method of combining hydrochemical data logging and in situ titrating with measurement of stable carbon and oxygen isotopes was used to reveal the hydrochemical and isotopic characteristics in the Baishuitai travertine scenic area of SW China. It was found that the travertine-forming springs have a very high concentration of calcium and bicarbonate, and accordingly very high CO₂ partial pressures, which are not likely to be produced by biological activity in soil alone. Further analysis of the stable carbon isotopes of the springs shows that the high pressure of CO₂ is mainly related to an endogenic CO₂ source. That means the Baishuitai travertine is endogenic in origin. This is contrast to the commonly accepted saying that the travertine deposition in this study simply is a product of warm and humid conditions in a karst ecological environment. Rapid CO₂ degassing from the water is triggered by the much higher partial pressures in water than that of the surrounding air. Consequently, as the waters flow downstream of the spring the pH increases, the waters become supersaturated with respect to calcite, and travertine is deposited. The preferential release of ¹²CO₂ to the atmosphere results in a progressive increase of travertine ¹³C downstream. This is concluded with a preliminary discussion of variation in travertine-forming water temperatures, according to differences in stable oxygen isotopic compositions of the travertine formed in different epochs at Baishuitai. It was found that the change in water temperature is as high as 13 °C, i.e., from 23 °C at about 2500 years b.p., to 10 °C at present. This may mainly reflect that the effect of geothermal source on water temperature is decreasing. The problems involved in paleoenvironmental reconstruction with endogene travertine are also discussed. They are the impacts of "dead carbon" in radiocarbon dating and the enrichment in ¹³C of travertine by endogenic CO₂ and degassing of CO₂ from water, which has to be considered in paleovegetation reconstruction when using ¹³C data of the endogene carbonate deposits.     

The impact of vegetation on fractionation of rare earth elements (REE) during water–rock interaction

Previous studies on waters of a streamlet in the Vosges mountains (eastern France) have shown that Sr and rare earth elements (REE) principally originate from apatite dissolution during weathering. However, stream water REE patterns normalized to apatite are still depleted in light REE (LREE, La–Sm) pointing to the presence of an additional LREE depleting process. Speciation calculations indicate that complexation cannot explain this additional LREE depletion. In contrast, vegetation samples are strongly enriched in LREE compared to water and their Sr and Nd isotopic compositions are comparable with those of apatite and waters. Thus, the preferential LREE uptake by the plants at the root–water–soil (apatite) interface might lead to an additional LREE depletion of the waters in the forested catchment. Mass balance calculations indicate that the yearly LREE uptake by vegetation is comparable with the LREE export by the streamlet and, therefore, might be an important factor controlling the LREE depletion in river waters.     

Crustal Evolution of Island-Arc Ultramafic Magma: Galmoenan Pyroxenite-Dunite Plutonic Complex, Koryak Highland (Far East Russia)

Alaskan-type platinum-bearing plutons and potassium-enrichedmafic to ultramafic volcanic rocks are temporally and spatiallyassociated within the Late Cretaceous–Paleocene Achaivayam–Valaginskiiintra-oceanic palaeo-arc system, allochthonously present inthe Koryak Highland and Kamchatka Peninsula (Far East Russia).The compositions of the parental magmas to the Alaskan-typecomplexes are estimated using the Galmoenan plutonic complexas an example. This complex, composed of dunites, pyroxenitesand minor gabbros, is the largest (20 km³) in the system andthe best studied owing to associated platinum placer deposits.The compositions of the principal mineral phases in the Galmoenanintrusive rocks [olivine (Fo_79–92), clinopyroxene (1–3·5wt % Al₂O₃, 0·1–0·5 wt % TiO₂), and Cr-spinel(5–15 wt % Al₂O₃ and 0·3–0·7 wt %TiO₂)] are typical of liquidus assemblages in primitive island-arcmagmas in intra-oceanic settings, and closely resemble the mineralcompositions in the Achaivayam–Valaginskii ultramaficvolcanic rocks. The temporal and spatial association of intrusiveand extrusive units, and the similarity of their mineral compositions,suggest that both suites were formed from similar parental magmas.The composition of the parental magma for the Galmoenan plutonicrocks is estimated using previously reported data for the Achaivayam–Valaginskiiultramafic volcanic rocks and phenocryst-hosted melt inclusions.Quantitative simulation of crystallization of the parental magmain the Galmoenan magma chamber shows that the compositions ofthe cumulate units are best modelled by fractional crystallizationwith periodic magma replenishment. The model calculations reproducewell the observed mineral assemblages and the trace elementabundances in clinopyroxene. Based upon the estimated compositionof the parental magmas and their mantle source, we considerthat fluxing of a highly refractory mantle wedge (similar tothe source of boninites) by chlorine-rich aqueous fluids isprimarily responsible for both high degrees of partial meltingand the geochemical characteristics of the magmas, includingtheir enrichment in platinum-group elements. KEY WORDS: subduction; platinum-group elements; clinopyroxene; trace elements; fractional crystallization; Alaskan-type plutons     

The origin of fluoride-rich groundwater in Mizunami area, Japan — Mineralogy and geochemistry implications

The aim of this paper was to explore new factors that might be reasons for the occurrence of fluoride-rich groundwater in the area around a construction site. During the construction of two deep shafts of the Mizunami Underground Research Laboratory (MIU) in Mizunami city, central Japan, a large quantity of groundwater with high fluoride concentration was charged into the shafts. Chemical investigation carried out during the excavation revealed that fluoride concentrations in the area around the MIU site greatly exceeded those prescribed by Japanese standards. Therefore, the origin of fluoride ion was experimentally investigated. Samples were collected from the core of a deep borehole drilled in the study area. The weathering - and alteration levels of the collected granites varied greatly. Granitic powders were used to measure fluoride content in the granitic rock mass. The fluoride content ranged between 200 and 1300 mg/kg. The powders were reacted with purified water for 80 days. The results of water–rock interaction showed granitic rock to be one of the main sources of fluoride-rich groundwater in Mizunami area. Fluoride concentrations in these solutions that were shaken for 80 days varied between 2 and 7 mg/l. This change may have occurred as a result of the spatial distribution of fluoride ions in the granite mass as evidenced by mineralogical analysis of fluoride content in several specimens. X-ray powder diffraction analysis of the rock before- and after the water–rock interaction tests manifested that the presence of fluorite mineral was relatively small compared to other minerals. The degree of weathering and alteration might be an additional factor causing dissolution of fluoride-rich minerals. However, it was difficult to interpret the change in fluorite composition by X-ray diffraction analysis.     

Hydrogeochemical modeling of the water seepages through Tannur Dam,southern Jordan

This paper reveals the geochemical processes of dissolution, precipitation and cation exchange that took place during water–rock interaction between water seepages through the Tannur Dam. The Schoeller diagram indicates that there are three major water types originating during water–rock interaction. The first water type is characterized by low salinity that ranges from 1,300 to 2,800 µs/cm, which represents the reservoir water and the water in the right side of the central gallery. The second water type is in the left side of the central gallery, which exhibits medium salinity that reaches about 4,400 µs/cm. The third water type is characterized by very high salinity that reaches a value of around 8,500 µs/cm and represents the water in the right existing adit. The increase of salinity can be explained due to the dissolution of carbonate and sulfate minerals that form the matrix of the foundation and the abutment rocks, and the dissolution of the grout curtain, which is composed of cement and bentonite. Hydrogeochemical modeling, using a computer code PHREEQC, was used to obtain the saturation indices of specific mineral phases, which might be related to interaction with water seepages, and to identify the chemical species of the dissolved ions. The thermodynamic calculations indicate that most of the water samples were undersaturated with respect to gypsum, anhydrite and halite, and were saturated and/or supersaturated with respect to calcite and dolomite. Ca(HCO₃)₂ is the primary water type, as a result of dissolution of carbonate minerals such as calcite and dolomite prevailing at the dam site. However, cation-exchange processes are responsible for the formation of the Na₂SO₄ water type from the CaSO₄ type that formed due to the dissolution of gypsum.     

Experimental identification of CO2–water–rock interactions caused by sequestration of CO2 in Westphalian and Buntsandstein sandstones of the Campine Basin (NE-Belgium)

Geological sequestration of CO₂ is one of the options studied to reduce greenhouse gas emissions. Although the feasibility of this concept is proven, apart from literature data on modelling still little is known about the CO₂–water–rock interactions induced by CO₂-injection.To evaluate the effect of CO₂–water–rock interactions on three sandstone aquifers in NE-Belgium an experimental setup was built. Eighteen experiments were performed in which sandstones were exposed to supercritical CO₂. CO₂–water–rock interactions were deduced from the evolution of aqueous concentrations of 25 species and a thorough characterisation of the sandstones before and after treatment. The results show that dissolution of ankerite/dolomite and Al-silicates could enhance porosity/permeability. The observed precipitation of end-member carbonates could increase storage capacity if it exceeds carbonate dissolution. Precipitation of the latter and of K-rich clays as observed, however, can hamper the injection.     

Direct and Indirect pCO2 Measurements in a Wide Range of pCO2 and Salinity Values (The Scheldt Estuary)

Recent improvements in both Infra-red spectroscopy and equilibrator techniqueshave allowed to determine, for the first time, pCO₂using simultaneously and continuously both the direct and indirect methods in an estuary where pCO₂ values range from 500 to 8500 atm and salinity from 0 to 30. Our results show that both methods are in excellent agreement in the wholeestuary (r² = 0.999, n = 1075, p < 0.0001). Thus, the NBS (US National Bureau of Standards) scale, although inadequate for seawater samples, is appropriate for estuarine waters and can be applied with confidence to calculate pCO₂.     

Rare earth element transport and fractionation in small streams of a mixed basaltic–granitic catchment basin (Massif Central, France)

We present dissolved load (< 0.45 μm) rare earth element (REE) patterns of small streams from a catchment basin in the Massif Central in order to characterize the individual fractionation stages for the dissolved REE from the source to the catchment outlet. The upper part of the catchment is located on a basalt plateau, followed downstream by deep and narrow valleys with granitic and orthogneissic bedrock. Stream water has basalt-like REE patterns on the basaltic plateau close to the source, followed by a continuous depletion in light REE (La-Sm, LREE) downstream. Strontium and neodymium isotope ratios of stream water demonstrate that the dissolved REE are essentially of basaltic origin, even in the lower, granitic and gneissic part of the catchment. Mixing with gneiss or granite derived REE thus cannot explain the observed evolution of the REE patterns. There seems also to be no link with the calculated speciation of the dissolved REE. In contrast, a correlation between saturation indexes for hematite and La/Yb ratios suggests that REE fractionation is mainly controlled by precipitation of Fe-oxide particles that preferentially remove LREE from solution.     

Hydrogeochemical evolution of groundwater in a Mediterranean coastal aquifer, Mersin-Erdemli basin (Turkey)

In this study, hydrogeologic and hydrochemical information from the Mersin-Erdemli groundwater system were integrated and used to determine the main factors and mechanisms controlling the chemistry of groundwaters in the area and anthropogenic factors presently affecting them. The PHREEQC geochemical modeling demonstrated that relatively few phases are required to derive water chemistry in the area. In a broad sense, the reactions responsible for the hydrochemical evolution in the area fall into four categories: (1) silicate weathering reactions; (2) dissolution of salts; (3) precipitation of calcite, amorphous silica and kaolinite; (4) ion exchange. As determined by multivariate statistical analysis, anthropogenic factors show seasonality in the area where most contaminated waters related to fertilizer and fungicide applications that occur during early summer season.     

Long‐Term Reaction Characteristics of CO2–Water–Rock Interaction: Insight into the Potential Groundwater Contamination Risk from Underground CO2 Storage

CO₂ sequestration into saline aquifers is considered to be one of the most promising options for reducing industrial CO₂ emissions to the atmosphere. However, there are still many uncertainties regarding the storage of CO₂ in the subsurface because of a lack of knowledge about CO₂–water–rock interaction within CO₂ reservoirs and the potential risk of CO₂ leakage. In this study, we construct a semi‐open type experimental system that can reproduce the interactions under conditions close to those of actual CO₂ reservoirs. Using the system, we conduct CO₂–water–rock interaction experiments for 8 months to monitor the long‐term reaction and the mobilization of harmful metal elements. Altered tuffaceous rock is used in the experiment because these tuffaceous rock formations (called “Green Tuff”) are a potential candidate for CO₂ storage in Japan. The results show that the major‐element water composition will converge to the point where host rock dissolution and secondary mineral precipitation are balanced; then, the interaction will proceed under a certain groundwater composition. In addition, we found that groundwater contamination by some metal elements (Ni, Ba, and Mn) may reach unsafe levels for drinking water as a result of CO₂‐water–rock interaction.     

Yellow fluorescence from baghdadite and synthetic Ca3(Zr,Ti)Si2O9

Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca₃(Zr,Ti)Si₂O₉ crystals are synthesized. Synthetic Ca₃(Zr,Ti)Si₂O₉ shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.     

Olivine in the Udachnaya-East Kimberlite (Yakutia, Russia): Types, Compositions and Origins

Olivine is the principal mineral of kimberlite magmas, and isthe main contributor to the ultramafic composition of kimberliterocks. Olivine is partly or completely altered in common kimberlites,and thus unavailable for studies of the origin and evolutionof kimberlite magmas. The masking effects of alteration, commonin kimberlites worldwide, are overcome in this study of theexceptionally fresh diamondiferous kimberlites of the Udachnaya-Eastpipe from the Daldyn–Alakit province, Yakutia, northernSiberia. These serpentine-free kimberlites contain large amountsof olivine (50 vol.%) in a chloride–carbonate groundmass.Olivine is represented by two populations (olivine-I and groundmassolivine-II) differing in morphology, colour and grain size,and trapped mineral and melt inclusions. The large fragmentalolivine-I is compositionally variable in terms of major (Fo_85–94)and trace element concentrations, including H₂O content (10–136ppm). Multiple sources of olivine-I, such as convecting andlithospheric mantle, are suggested. The groundmass olivine-IIis recognized by smaller grain sizes and perfect crystallographicshapes that indicate crystallization during magma ascent andemplacement. However, a simple crystallization history for olivine-IIis complicated by complex zoning in terms of Fo values and traceelement contents. The cores of olivine-II are compositionallysimilar to olivine-I, which suggests a genetic link betweenthese two types of olivine. Olivine-I and olivine-II have oxygenisotope values (+ 5·6 ± 0·1 VSMOW, 1 SD)that are indistinguishable from one another, but higher thanvalues (+ 5·18 ± 0·28) in ‘typical’mantle olivine. These elevated values probably reflect equilibriumwith the Udachnaya carbonate melt at low temperatures and ¹⁸O-enrichedmantle source. The volumetrically significant rims of olivine-IIhave constant Fo values (89·0 ± 0·2 mol%),but variable trace element compositions. The uniform Fo compositionsof the rims imply an absence of fractionation of the melt'sFe²⁺/Mg, which is possible in the carbonatite melt–olivinesystem. The kimberlite melt is argued to have originated inthe mantle as a chloride–carbonate liquid, devoid of ‘ultramafic’or ‘basaltic’ aluminosilicate components, but becameolivine-laden and olivine-saturated by scavenging olivine crystalsfrom the pathway rocks and dissolving them en route to the surface.During emplacement the kimberlite magma changed progressivelytowards an original alkali-rich chloride–carbonate meltby extensively crystallizing groundmass olivine and gravitationalseparation of solids in the pipe. KEY WORDS: kimberlite; olivine; partial melting; carbonatitic melt; oxygen isotopes; H₂O     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

High-T phase transition of synthetic ANaB(LiMg)CMg5Si8O22(OH)2 amphibole: an X-ray synchrotron powder diffraction and FTIR spectroscopic study

The synthetic amphibole Na_0.95(Li_0.95Mg_1.05)Mg₅Si₈O₂₂(OH)₂ was studied in situ at high-T, using IR OH-stretching spectroscopy and synchrotron X-ray powder diffraction. At room-T the sample has P2₁ /m symmetry, as shown by the FTIR spectrum. It shows in the OH region two well-defined and intense absorptions at 3,748 and 3,712 cm⁻¹, respectively, and two minor bands at 3,667 and 3,687 cm⁻¹. The main bands are assigned to the two independent O–H groups in the primitive structure. The two minor bands evidencing the presence of small amount of vacant A-site (^A□_0.05). With increasing T, these bands shift continuously and merge into a unique absorption at high temperature. A change as a function of increasing T is revealed by the evolution of the refined unit-cell parameters, whose trend shows a transition to C2/m at about 320–330°C. The spontaneous scalar strain, fitted with a tricritical 2–6 Landau potential, gives a T _c of 325(10)°C (β parameter = 0.27). Comparison with the second-order P2₁ /m ⇔ C2/m phase transition at 255°C for synthetic amphibole ^ANa_0.8^B(Na_0.8Mg_1.2)^CMg₅Si₈O₂₂(OH)₂ indicates that the substitution of Na with Li at the B-sites strongly affects the thermodynamic character and the T _c of the phase transition. The comparison of LNMSH amphiboles with cummingtonitic ones shows that the high-T thermodynamic behaviour is affected by A-site occupancy.     

The Speciation of (CH3)2Sn2+ in Electrolyte Solution Containing the Major Components of Natural Waters

Hydrolysis constants of dimethyltin(IV) cation, in different salt solutions (CaCl₂: 0.15 I 0.90; MgCl₂: 0.30 I 0.60; NaCl-–NaClO₄, NaCl-–NaNO₃ mixtures: I = 3; NaCl-–Na₂SO₄ mixtures: I = 1 mol dm^-3) were determined by potentiometric ([H⁺]-glass electrode) measurements. These data, together with previous data (De Stefano et al., 1996b) were interpreted in terms of DHT (Debye–Hückel type) and Pitzer equations. The mixed electrolyte solution results also allowed us to obtain and parameters for the Pitzer equation. Calorimetric measurements were made at different ionic strengths in order to find the temperature dependence of hydrolysis constants and of the relative interaction parameters. The body of results allows us to determine the speciation of natural waters in a wide range of ionic strengths and temperatures.     

Geodynamic setting of gold deposits in Eastern and Central Trans-Baikal (Chita Region, Russia)

It is proposed that there are three types of gold deposits in Eastern and Central Transbaikalia (Trans-Baikal province), namely: (i) high-sulphide intrusion-related deposits with some signs of porphyry deposits, (ii) low-sulphide intrusion-related deposits, and (iii) low-sulphide epithermal Au–Ag deposits. Most of the gold deposits belong to the first two types, and their ages are Middle–Late Jurassic. Deposits of the third type are not numerous, and their age is Early Cretaceous.The majority of the gold mineralization is spatially related to the two branches of the Mongolia–Okhotsk suture, along which Siberia collided, at the Early/Middle Jurassic boundary, with the Mongolia–North China continent and the Onon island-arc terrane located between the two continents. Collision-related thrusting, folding and magmatism lasted until the latest Jurassic, when they gave way to post-collisional rifting that continued until the end of Early Cretaceous.According to their age, relation to magmatism and tectonic framework, the intrusion-related deposits (high- and low-sulphide) were formed in a regional collisional setting. Extensional environments at that time existed only in local areas in the roofs of great magmatic chambers. Low-sulphide epithermal deposits were formed during Early Cretaceous post-collisional rifting.