Hydrothermal processes along mid-ocean ridges: An experimental investigation

An experimental investigation of high-temperature seawater/basalt interactions has been conducted in order to better evaluate the geochemical and economic implications of hydrothermal circulation of seawater in the oceanic crust along active mid-ocean ridges. The results indicate that, as seawater reacts with basalt between 200 ° C and 500 ° C at 500–800 bars, the fluid tends to change from an oxygenated, slightly alkaline, Na⁺, Mg⁺⁺, SO₄ ⁼, Cl^? solution to a reducing, acidic, Na⁺, Ca⁺⁺, Cl^?, solution with Fe, Mn and Cu concentrations up to 1500, 190 and 0.3 ppm respectively. Silica concentrations in the fluid reach concentrations of 200–600 ppm; however, Al abundances remain very low (～0.5 ppm). Gray and green smectites, anhydrite, albite, tremolite-actinolite, chalcopyrite, pyrrhotite and hematite were the dominant alteration products formed. These data imply that large-scale circulation of seawater in the oceanic crust could account for the Al-deficient metalliferous sediments associated with mid-ocean ridges and could be important in the genesis of certain Fe-Cu sulfide ore deposists. The process could also affect the geochemical budgets of certain elements and exert substantial control of the steady-state composition of seawater by removing excess Na and Mg and adding Ca, Si, and H to the oceans.     

Estimation of the dielectric constant of H2O from experimental solubilities of quartz,and calculation of the thermodynamic properties of aqueous species to 900°C at 2 kb

Experimental quartz solubilities in H₂O (Anderson and Burnham, 1965, 1967) were used together with equations of state for quartz and aqueous species (Helgesonet al., 1978; Walther and Helgeson, 1977) to calculate the dielectric constant of H₂O () at pressures and temperatures greater than those for which experimental measurements (Heger, 1969; Lukashovet al., 1975) are available ($\text{0.001 ? P ? 5}\text{kb}$ and $\text{0 ? T ? 600°C}$). Estimates of computed in this way for 2 kb (which are the most reliable) range from 9.6 at 600°C to 5.6 at 800°C. These values are 0.5 and 0.8 units greater, respectively, than corresponding values estimated by Quist and Marshall (1965), but they differ by <0.3 units from extrapolated values computed from Pitzer's (1983) adaptation of the Kirkwood (1939) equation. The estimates of generated from quartz solubilities at 2 kb were fit with a power function of temperature, which was then used together with equations and data given by Helgeson and Kirkham (1974a,b, 1976) Helgesonet al. (1981), and Helgeson (1982b, 1984) to calculate Born functions, Debye Hückel parameters, and the thermodynamic properties of Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, and other aqueous species of geologic interest at temperatures to 900°C.     

Chemical composition of the primary aqueous phase of the earth and origin of life

Prokaryotes and cytoplasm of eukaryotes are dominated by K⁺, whereas the extracellular fluid of most species of multicellular organisms is dominated by Na⁺. It was substantiated that the K⁺/Na⁺ ratio in the salt constituent of the cells of modern organisms qualitatively reflects the proportions between these elements in the aqueous phase, in which the first forms of life and the protocell originated. The same conclusion is done by Armen Y. Mulkidjanian et al. (PNAS 13, 2012, E821-830). The chemical composition of primary aqueous phase of the Earth was reconstructed using thermodynamic numerical simulation of the equilibrium composition of the ??carbonaceous chondrite material-water??, ??primitive mantle material-water??, ??ultramafic rock-water??, ??mafic rocks-water?? systems that are open with respect to CO₂ and CH₄. It was shown that at 25°C, total pressure of 1 bar, and partial pressures of CO₂ and CH₄ 10^?5?C10^?8 and 10^?2?C10^?8 bar, respectively, the aqueous phase of the systems with carbonaceous chondrite and primitive mantle has K⁺/Na⁺ > 1, which corresponds to the proportions of these elements in the intracellular solution. The aqueous phase is characterized by pH = 8?C9, Eh = ?450 ± 50 mV, the presence of ammonium nitrogen, and concentrations of K, Na, and Mg close to those in the inferred intracellular fluid. The interaction of water with ultramafic and mafic rocks provides K⁺/Na⁺ < 1 in aqueous solution, which corresponds to the chemical composition of the modern natural waters of the Earth??s crust. Simulation results show that the protocell could arise in the primary aqueous phase of the Earth during differentiation of chondritic material into the Earth??s core and mantle, after the formation of the nitrogen atmosphere containing CH₄, CO₂, NH₃, H₂, H₂S, CO and other gases, but prior to the formation of the modern rocks of the Earth??s crust (first billion years of the planet??s lifetime).     

Analytical and numerical solutions for carbonated waterflooding

We develop a Riemann solver for transport problems including geochemistry related to oil recovery. The example considered here concerns one-dimensional incompressible flow in porous media and the transport for several chemical components, namely H₂O, H⁺, OH^?, CO₂, \(\text {CO}_{3}^{2-}\), \(\text {HCO}_{3}^{-}\), and decane; they are in chemical equilibrium in the aqueous and oleic phases, leading to mass transfer of CO₂ between the oleic and aqueous phases. In our ionic model, we employ equations with zero diffusion coefficients. We do so because it is well known that for upscaled equations, the convection terms dominate the diffusion terms. The Riemann solution for this model can therefore be applied for upscaled transport processes in enhanced oil recovery involving geochemical aspects. In our example, we formulate the conservation equations of hydrogen, oxygen, hydrogen, and decane, in which we substitute regression expressions that are obtained by geochemical software. This can be readily done because Gibbs phase rule together with charge balance shows that all compositions can be rewritten in terms of a single composition, which we choose to be the hydrogen ion concentration (p H). In our example, we use the initial and boundary conditions for the carbonated aqueous phase injection in an oil reservoir containing connate water with some carbon dioxide. We compare the Riemann solution with a numerical solution, which includes capillary and diffusion effects. The significant new contribution is the effective Riemann solver we developed to obtain solutions for oil recovery problems including geochemistry and a variable total Darcy velocity, a situation in which fractional flow theory does not readily apply. We thus obtain an accurate solution for a carbonated waterflood, which elucidates some mechanisms of low salinity carbonated waterflooding.     

Chemical reactions and porosity changes during sedimentary diagenesis

It is of interest to simulate the porosity changes associated with fluid flow and water–rock reactions in sedimentary systems. The chemical species taken into account are: {H₂O, H⁺, Ca⁺⁺, HCO₃⁻, Mg⁺⁺, Al(OH)₄⁻, H₄SiO₄, K⁺, Na⁺, Cl⁻}. The solution is assumed to be locally at equilibrium with different mineral assemblages including at least calcite, dolomite and one Mg–Al-silicate. These assemblages buffer the partial pressure of CO₂ (Pco₂ ) which increases with temperature (T) as is commonly observed in natural systems. The nature of the Mg–Al-silicate and the presence or absence of other at-equilibrium minerals (i.e. the feldspars) do not modify the Pco₂–T relationship. Considering complete transfer between the solution and the solid phases, computed relative porosity increases with increasing temperature for all the systems that were investigated. However, the direction and the amount of the clay transfer depend on the presence of feldspars. Furthermore, it is shown that computing mass transfer using a prescribed Pco₂, as is commonly done, leads to very different values of mineral transfers. Hence, it must be concluded that prescribing a Pco₂ value, even if the proper Pco₂–T relationship is used, leads to erroneous results.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.     

Geochemical characteristics of natural gases in the Sichuan basin

The Sichuan basin is one of the largest gas-oil-bearing basins in China. Ool and. gas pools occur in Mesozoic, Paleozoic and Proterozoic strata in this basin, with natural gases being dominant. A good wealth of data from 2000 drill wells on the distribution of natural gases (hydrocarbons: CH₄ C₂H ₆ ⁺ ; non-hydrocarbons: H₂S, CO₂, N₂; noble gases: He, Ar) show that natural gases in the basin are predominated by oil-thermocracked and coal-series gases. Geological-factor analysis of the geochemical characteristics of natural gases provide evidence suggesting that the occurrence of natural gases, especially dry gases, is attributed to the high maturity of organic matter, and the multi-productive formation has a great bearing on the multi-source rocks; the anomalies of some components (e. g. H₂S) are related not only to the type of primary organic matter, but also to the lithological characters of reservoir beds. Also discussed in this paper are some geochemical characteristics of coalseries and noncoal-series gases at the same degree of maturat ion, demonstrating that the former is characterized by high proportions of CH₄ and gaseous Hg, high C₁/C₂ ratio, high δ¹³C, low C ₂ ⁺ , and high iC₄/nC₄.     

Features of the Ore Forming Process on the Dvoinoye Epithermal Au–Ag Deposit (Western Chukotka)

The results of thermobaric geochemical study of ores of the Dvoinoye epithermal Au–Ag deposit are considered. Study of the fluid inclusions has shown that the ores were formed from low-salinity hydrothermal solutions with Na, Ka, and Mg chlorides and CO₂, HS^–, CH₄ trace fluxes at the time when the temperature dropped from 370 to 130°C. The results are compared with data obtained from the closely located Kupol and Sentyabr’skoye deposits.     

Characterization of hydrogeochemical process and evaluation of water quality of seven geothermal springs,Bakreswar, India

A study was conducted in seven geothermal springs located in Bakreswar, District Birbhum, West Bengal, India, in order to assess numerous geochemical processes which were responsible for chemical composition of thermal and mineralized water. The study area lies over the Sone, Narmada, and Tapti lineament of Precambrian Chotanagpur Gneissic Complex. Water chemistry has been carried out based on reaction stoichiometry and geo-statistical tools to identify geochemical process. Piper and Gibbs diagram suggest that the spring water belongs to Ca²⁺-Mg²⁺-HCO₃^??+?CO₃^2? water type and are controlled by rock dominance. Dissolution and precipitation of calcite, dolomite, gypsum, and fluorite minerals were identified as principle source of major ions in seven geothermal spring water. Principle component analyses revealed that major ions of spring water are derived from geogenic processes such as weathering, dissolution, and precipitation of various minerals. Overall results suggest that major ions of the spring’s water are derived from natural origin because no evidence of anthropogenic sources was observed during the study period. This study has also revealed that water quality of spring’s water is not suitable for drinking purposes and quite suitable for irrigation because of high abundance of Na⁺, K⁺, Cl^?, and HCO₃^? ions.     

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

The solubility of gold in aqueous sulphide solutions has been determined from pH_20°C ≈ 4 to pH_20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with m_NaHS = 0.15 m, pH_20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au₂(HS)₂S^2? predominated in alkaline solution, the Au(HS)₂^? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu₂(HS)₂S^2? and Au (HS)₂^? emphasize their high stability. In the temperature range from 175 to 250°C, values of pβ for Au₂(HS)₂S^2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)₂^?. Equilibrium constante for the dissolution reactions, $\text{Au° + H}{}_2\text{S + HS}{}^{\mathrm{?}}\text{? Au(HS)}{}_2{}^{\mathrm{?}}\text{+}\text{1}\text{2}\text{H}{}_2$ and 2Au° + H₂S + 2H8^? ? Au(HS)₂^? + H₂ vary from pK_m = +2.4 to +2.55 (±0.10) for Au₂(HS)₂S^2? and from pK_n = + 1.29 to + 1.19 (±0.10) for Au(HS)₂^? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔH_m° = ?5.2 ±2.0 kcal/mol and ΔH_n° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.     

Ore Genesis of the Kalatongke Cu–Ni Sulfide Deposits, Western China: Constraints from Volatile Chemical and Carbon Isotopic Compositions

The Kalatongke Cu–Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt (CAOB). The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200–400°C, 400–900°C and 900–1200°C. The released volatiles from silicate mineral separates at 400–900°C and 900–1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O (av. ~92 mol%) with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values (from ?20.86‰ to ?12.85‰) of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantle-derived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200–400°C are dominated by H2O with minor CO2, N2+CO and SO2, with δ13CCO2 values (?25.66‰ to ?22.98‰) within the crustal ranges, and are considered to be related to secondary tectonic– hydrothermal activities.     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Geochemical evolution of Sb migration species in carbonate and thermal waters in relation to Sb hydrogenic mineralization

Based on the synthesis of hydrogeochemical materials on Sb occurrence in carbonate and thermal waters and thermodynamic simulations, genetic analysis was conducted of the transformations of probable Sb migration species (particularly oxygen-bearing and sulfide ones), and their transformations were calculated depending on the main parameters of hydrogeochemical systems (\(P_{CO_2 } \), T, R/W, Eh, and pH). The oxygen 2HSbO ₂ ⁰ + 3H₂S = Sb₂S₃ + 4H₂O (2SbO ₂ ^? + 3HS^? + 5H⁺ = Sb₂S₃ + 4H₂O) and sulfide HSb₂S ₄ ^? + H⁺ = Sb₂S₃ cr + H₂S (Sb₂S ₄ ^2? + 2H⁺ = Sb₂S₃cr + H₂S) models for the genesis of hydrogenic Sb₂S₃(cr) were simulated. Information on occurrences of carbonate and thermal waters in various regions worldwide was generalized, and the reasons were identified for the geochemical separation of As and Sb in carbonate and thermal waters. The causes and conditions of an increase in Sb concentrations in thermal waters were revealed, and Sb migration species in carbonate and thermal waters were identified for various parameters of hydrogeochemical systems. Variations in Sb speciation were demonstrated for hydrogeochemical systems depending on their boundary conditions (\(P_{CO_2 } \), T, and R/W). Models were outlined responsible for the precipitation of Sb₂S₃(cr) from carbonate and thermal waters.     

Solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions

An experimental study of the solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions was conducted at temperatures from 200° to 350 °C and at saturated vapor pressure. A 500-mL Bridgemantype pressure vessel constructed of titanium, and equipped with a motor-driven magnetic stirrer was employed. The pH and the oxidation state were buffered by the coexistence of H₂S/HS^–/SO _inf4 ^sup2– . The pH at temperature was calculated to be in the range 5.91–9.43, and S was 0.3–2.2 m. Under the experimental conditions, the measured solubility of gold is about two to three orders of magnitude greater than that of either platinum and palladium, and the measured solubility of platinum is, in general, approximately equal to that of palladium, in molal units. The solubilities are found to be in the range: platinum 4–800 ppb, palladium 1–400 ppb, and gold 2–300 ppm. The solubility data can be modeled adequately using the following reactions: Au+H₂S+HH^–=Au(HS) ₂ ^– +1/2H₂ (K₁₄); PtS+HS^–+H⁺=Pt (HS) ₂ ⁰ (K₁₅); PdS+HS^–+H⁺=Pd (HS) ₂ ⁰ (K₁₆); PtS₂+H₂=Pt (HS) ₂ ⁰ (K₂₁).With equilibrium constants determined as follows (errors represent two standard deviations): Preliminary measurements of the solubilities of metallic Pt, Pd and Au as hydroxide complexes were also conducted using a second titanium pressure vessel, at temperatures of 200° to 350 °C and vapor saturation pressure, with pH and the oxidation state controlled or buffered by adding known amounts of NaOH and H₂ gas. The concentration of NaOH was in the range 0.01–1.3 m, and the partial pressure of H₂ at 200 °C was 62–275 bars, initially. Under the temperature and pressure conditions of these experiments, the solubility of platinum in 1 m NaOH solution is less than 100 ppb, that of palladium is less than 10 ppb and that of gold is less than 0.2 ppm; and in 0.01 m NaOH solutions, both Pt and Pd solubilities are less than 1 ppb. These data indicate that the contributions of hydroxide complexes to the total solubilities in the bisulfide runs, where the pH was in the range of 5.9–9.4, are negligible. The concentrations of both Pt and Pd as bisulfide complexes in the Salton Sea geothermal system predicted using the stability constants determined in this work agree very well with those values measured by McKibben et al. (1990). This calculation strongly suggests that the PGE are transported in moderately reducing, near neutral hydrothermal fluids as bisulfide complexes, as is gold. However, the much lower maximum solubility of the PGE relative to gold severely constrains models of re genesis, and may explain the relative rarity of hydrothermal PGE deposits compared to the relative abundance of hydrothermal Au deposits.     

Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin: I. Calculation of the solubility of cassiterite at high pressures and temperatures

Estimation of equation of state parameters for Sn⁺⁺ and calculation of the thermodynamic properties of other aqueous species and dissociation constants for various stannous and stannic complexes as a function of temperature permit prediction of the high temperature solution chemistry of tin and calculation of the solubility of cassiterite in hydrothermal solutions. The results of these calculations indicate that in the absence of appreciable chloride and fluoride concentrations, Sn(OH)₂⁰ and Sn(OH)₄⁰ are the predominant tin species in H₂O up to 350°C at ~2 $\text{\$}\text{?}$pH $\text{\$}\text{?}$7.5. The calculations also indicate that chloride complexes of Sn⁺⁺ predominate by several orders of magnitude over their fluoride and hydroxide counterparts in 1–3 molal (m) NaCl solutions, except in the presence of geologically unrealistic concentrations of fluoride or a pH greater than ~3.5 at 250°C or ~5.0 at 350°C. At higher pH values, most of the tin in solution is present as hydroxide complexes, even at concentrations of NaCl as high as 3 m. Calculated values of the solubility of cassiterite at high temperatures compare favorably with experimental data reported in the literature. Depending on the fugacity of oxygen and solution composition, the solubility of cassiterite in hydrothermal solutions may exceed 100 ppm under geologically realistic conditions.     

Verteilung anorganischer Fremdionen bei der Kristallisation von Alkalichloriden

Investigations were made on the distribution of the foreign cations Na⁺, K⁺, Rb⁺, Cs⁺, NH ₄ ⁺ , Ca⁺⁺, Sr⁺⁺, Ba⁺⁺ and Pb⁺⁺ between NaCl-, KCl- and RbCl-single crystals and their aqueous solutions or melts. The growth conditions were kept as constant as possible: large single crystals grew slowly, that is from melts at constant undercooling and from solutions at low and constant supersaturation. The distribution coefficient D=C _s /C _l was calculated for the different systems (C _s =concentration of the foreign substance in the crystal, C _l =concentration of the foreign substance in the liquid phase, both in Mol-%). The different values for D can be explained qualitatively with the help of the ionic radii or by comparing the gain of energy with the expenditure of energy, which play an important part during the process of crystallization.

---

---

Meinem hochverehrten Lehrer, Prof. Dr. W. v. Engelhardt, gilt mein besonderer Dank für die Überlassung des interessanten Themas und für seine wertvolle Unterstützung und Beratung während dieser Arbeit. Herrn Prof. Dr. S. Haussühl bin ich für viele Ratschläge und Hinweise zu Dank verpflichtet. Ferner danke ich allen wissenschaftlichen und technischen Mitarbeitern des Tübinger Mineralogischen Instituts, die mir mit Rat und Tat bei der Durchführung dieser Arbeit behilflich waren.     

Statistical analysis of the hydrogeochemical evolution of groundwater in hard rock coastal aquifers of Thoothukudi district in Tamil Nadu, India

The study of groundwater hydrogeochemistry of a hard rock aquifer system in Thoothukudi district has resulted in a large geochemical data set. A total of 100 water samples representing various lithologies like Hornblende Biotite Gneiss, Alluvium Marine, alluvium Fluvial, Quartzite, Charnockite, Granite and Sandstone were collected for two different seasons and analyzed for major ions like Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^?, PO₄ ^?, F^? and H₄SiO₄. Statistical analysis of the data has been attempted to unravel the hidden relationship between ions. Correlation analyses and factor analyses were applied to classify the groundwater samples and to identify the geochemical processes controlling groundwater geochemistry. Factor analysis indicates that sea water intrusion followed by leaching of secondary salts, weathering and anthropogenic impacts are the dominant factors controlling hydrogeochemistry of groundwater in the study area. Factor score overlay indicate major active hydrogeochemical regimes are spread throughout the Eastern, Northwestern and Southeastern parts of the study area. The dominant ions controlling the groundwater chemistry irrespective of season are Cl^?, Na⁺, Mg²⁺, Ca²⁺, SO₄ ^2?, K⁺ and NO₃ ^?. An attempt has also been made to note the seasonal variation of the factor representations in the study area. This study also illustrates the usefulness of statistical analysis to improve the understanding of groundwater systems and estimates of the extent of salinity/salt water intrusion.     

Sorption behavior of the sandy residual unconsolidated materials from the sandstones of the Botucatu Formation,the main aquifer of Brazil

Pollutant transport through porous geological materials depends on the intrinsic characteristics of the materials that define the sorption behavior. This is the main environmental aspect that must be evaluated in terms of natural attenuation and retardation factor of the pollutants. Sorption is directly related to the electrostatic charge of the mineral, the organic matter, and the oxide and hydroxide contents. We assessed the sorption characteristics of the sandy residual unconsolidated material of the Botucatu Formation, which is part of the main aquifer of Brazil, using Batch Equilibrium Tests. The tests used multicomponent solutions of NaCl, KCl, ZnCl₂, and CuCl₂·H₂O with a total concentration that varied from 20 to 1,000 ppm. Different plotting systems were applied so that the isotherms better reflected the sorption behavior of the studied cations onto the unconsolidated materials. The cation Na⁺ was not sorbed. The Langmuir I and Freundlich equations adequately represent the behavior of Cu⁺⁺, the Langmuir II approximation better represented K⁺, and the Langmuir I and Freundlich equations were reasonably fitted Zn⁺⁺.     

Temperature dependence of calcite dissolution kinetics between 1 and 62°C at pH 2.7 to 8.4 in aqueous solutions

The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole^?1 for Carrara marble and 46 ± 4 kJ mole^?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole^?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole^?1 and this high EAAE is consistent with transport dependence on product diffusion in this H⁺-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole^?1, also decreasing with increasing temperature. This is compatible with H⁺-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H⁺-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H⁺-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.     

Study on the Physical and Chemical Conditions of Ore Formation of Hetai Ductile Shear Zone—Hosted Gold Deposit and Discovery of Melt Inclusions

The Hetai ductile shear zone-hosted gold deposit occurs in the deep-seated fault mylonite zone of the Sinian-Silurian metamorphic rock series. In this study there have been discovered melt inclusions, fluid-melt inclusions and organic inclusions in ore-bearing quartz veins of the ore deposit and mylonite for the first time. The homogenization temperatures of the various types of inclusions are 160℃, 180 - 350℃, 530℃ and 870℃ for organic inclusions, liquid inclusions, two-phase immiscible liquid inclusions and melt inclusions, respectively. Ore fluid is categorized as the neutral to basic K+ -Ca2+ -Mg2+ -Na+ - SO2- 4-HCO3-Cl- system. The contents of trace gases follow a descending order of H2O＞CO2＞CH4＞(or ＜ ) H2＞CO＞C2H2＞C2I-I6＞O2＞N2.The concentrations of K , Ca2 + ,SO2-4,HCO3-,Cl- H2O and C2H2 in fluid inclusions are related to the contents of gold and the Au/Ag ratios in ores from different levels of the gold deposit. This is significant for deep ore prospecting in the region. Daughter minerals in melt inclusions were analyzed using SEM. Quartz, orthoclase, wollastonite and other silicate minerals were identified. They were formed in different mineral assemblages.This analysis further proves the existence of melt inclusions in ore veins. Sedimentary metamorphic rocks could form silicate melts during metamorphic anatexis and dynamic metamorphism, which possess melt-solution characteristics. Ore formation is related to the multi-stage forming process of silicate melt and fluid.