Geochemistry of natural waters – The legacy of V.I. Vernadsky and his students

The geochemist, Vladimir Ivanovich Vernadsky has only recently become recognised internationally, despite being regarded as one of the greatest names in science of the 20th century in his homeland Russia. There are several reasons for his lack of renown in the west, but mainly because his most important work “The Biosphere” was only fully translated into English in 1997. This book and the ideas it contains are now becoming regarded as one of the pioneering works of the last century. It defines the biosphere as a unifying, holistic concept for the earth system at a time when reductionism was the driving motivation in scientific research. Above all, for earth scientists, Vernadsky regarded life as the driving geological force. However another, as yet unpublished work (in three volumes) entitled “The History of Natural Waters” also deserves similar attention. This book explores many concepts in hydrogeology, geochemistry, geofluid circulation and especially biology in which water is described as an integral part of the biosphere.     

Cordierite-garnet-sillimanite-quartz equilibrium: I. New experimental calibration in the system FeO−Al2O3−SiO2−H2O and certain P-T-X H2O relations

The equilibrium in which hydrous Fe-cordierite breaks down to almandine, sillimanite, quartz, and water was previously experimentally determined by Richardson (1968) and Holdaway and Lee (1977) using QMF buffer and by Weisbrod (1973) using QIF buffer. All these studies yielded similar results — a negative dP/dT slope for the equilibrium curve. However, based on theoretical arguments, Martignole and Sisi (1981), and based on Fe-Mg partitioning experiments on coexisting cordierite and garnet in equilibrium with sillimanite and quartz, Aranovich and Podlesskii (1983) suggested that this equilibrium curve has a positive dP/dT slope and its position depends on the water content of the equilibrium cordierite. We have redetermined this equilibrium using a much improved tecnique of detecting reaction direction, and cordierite starting material that contained virtually no hercynite. Hercynite was present as a contaminant in the cordierites of previous experimental studies and possibly reacted with quartz during the experimental runs to expand the apparent stability field of Fe-cordierite. We synthesized Fe-cordierite from reagent grade oxides at 710°C and 2 kbar (using QMF buffer) with two intermediate stages of grinding and mixing. The cordierite has a unit cell volume of 1574.60 ų (molar volume=23.706 J/bar) and no Fe³⁺ as indicated by X-ray diffraction and room temperature Mössbauer studies respectively. Reaction direction was concluded by noting20% change of the ratios of intensities of two key X-ray diffraction peaks of cordierite and almandine. Our results show that the four-phase equilibrium curve passes through the points 2.1 kbar, 650°C and 2.5 kbar, 750°C. This disagrees with all previous experimental studies. H₂O in the Fe-cordierite, equilibrated at 2.2 kbar and 700°C and determined by H-extraction line in the stable isotope laboratory, is 1.13 wt% (n=0.41 moles). H₂O content of pure Mg-cordierite equilibrated under identical conditions and determined by thermogravimentric conditions and determined by thermogravimetric analysis is 1.22 wt% (n=0.40). Similar determinations on Fe-cordierite and Mg-cordierite equilibrated at 2.0 kbar and 650°C show 1.27 wt% (n=0.46) and 1.47 wt% (n=0.48) of H₂O respectively. Thus, H₂O content appears to be independent of Fe/Mg ratio in cordierite, a conclusion which supports previous experimental determinations. The experimentally determined equilibrium curve represents conditions of P_H2O=P_total. From this we calculated the anhydrous curve representing equilibrium under conditions of X _H2O ^V =0.0. A family of calculated equilibrium curves of constant n _H2O ^Cord cut the experimentally determined curve at a very small angle indicating a slight variation in n _H2O ^Cord in cordierite in equilibrium with almandine, sillimanite, and quartz under the conditions of constant X _H2O ^V . Ancther set of calculated equilibrium curves, each representing constant a _H2O ^V demonstrate that the slopes of the curves vary with X _H2O ^V , and are all positive in the full range of 0.0X _H2O ^V 1.0.     

The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

The Dynamical Model of Chemical Oscillaiton in CaF2—HCl—H2O Solid—Liquid Reaction System

Based on the physical chemistry principle ,this paper proposes that the surface adsorption catalytic mechanism of HF is the key to dissolving the oscillation of the CaF2-HCl-H2OL solid-liquid reaction system.Meanwhile the dynamical model of this system has been established in order to study its non-linear dynamical genesis.Although this mathematics model is based on CSTR reaction apparatus,it is applicable to the foliate flow reaction apparatus,too.     

The inhibiting action of intrinsic impurities in natural calcium carbonate minerals to their dissolution kinetics in aqueous H2O–CO2 solutions

We have measured the surface controlled dissolution rates of natural calcium carbonate minerals (limestone and marble) in H₂O–CO₂ solutions by using free drift batch experiments under closed system conditions with respect to CO₂, at 10°C with an initial partial pressure of carbon dioxide of 5 · 10⁻² atm. All experiments revealed reaction rates F, which can be described by the empirical relation: F_n1 = k_n1 · (1 − c/c_eq)^n₁ for c < c_s, which switches to a higher order n₂ for calcium concentrations c ≥ c_s described by F_n2 = k_n2 · (1 − c/c_eq)^n₂. k_n1 and k_n2 are rate constants in mmole/(cm² · s), c_eq is the equilibrium concentration with respect to calcite. The values of the constants n₁, n₂, k_n1, k_n2 and c_s depend on the V/A ratio employed, where V is the volume of the solution and A is the surface area of the reacting mineral. Different calcium carbonate minerals exhibit different values of the kinetic constants. But generally with increasing V/A, there is a steep variation in the values of all kinetic constants, such that the rates are reduced with increasing V/A ratio. Finally with sufficiently large V/A these values become constant. These results are explained by assuming intrinsic inhibitors in the bulk of the mineral. During dissolution these are released from the calcite matrix and are adsorbed irreversibly at the reacting surface, where they act as inhibitors. The thickness d of the mineral layer removed by dissolution is proportional to the V/A ratio. The amount of inhibitors released per surface area is given by d · c_int, where c_int is their concentration in the bulk of the mineral. At low thicknesses up to ≈3 · 10⁻⁴ cm in the investigated materials, the surface concentration of inhibitors increases until saturation is attained for thicknesses above this value.To analyze the surface concentration and the type of the inhibitors we have used Auger spectroscopy, which revealed the presence of aluminosilicate complexes at the surface of limestone, when a thickness of d ≈ 10⁻³ cm had been removed by dissolution. In unreacted samples similar signals, weaker by one order of magnitude, were observed. Depth profiles of the reacted sample obtained by Ar-ion sputtering showed the concentration of these complexes to decrease to the concentration observed in the unreacted sample within a depth of about 10 nm. No change of the concentration with depth was observed in unreacted samples. These data suggest that complexes of aluminosilicates act as inhibitors, although other impurities cannot be excluded.     

The solubility of gold and silver in the system AuAgSO2H2O at 25°C and 1 atm.

During supergene alteration of auriferous carbonate ore, the weathering fluids formed are likely to be alkaline and therefore unsuitable as a medium for gold transport as a chloride complex. Secondary gold remobilization in such deposits can often be attributed instead to gold complexing by sulphur-bearing ligands. Gold and silver solubility in the systems AuSO₂H₂O and AgSO₂H₂O respectively, from the thermodynamic data available, is due to complex formation with thiosulphate and bisulphide ligands. The most stable gold complexes, Au(S₂O₃)₂³⁻ (at φO₂ > 10⁻⁶⁰) and Au(HS)⁻₂ (atφO₂ < 10⁻⁶⁰), exist in neutral or alkaline solutions. Like gold, silver forms a stable thiosulphate complex, Ag(S₂O₃)³⁻₂ in moderately oxidizing, and bisulphide complexes, AgHS⁰ and Ag(HS)⁻₂ in reducing, alkaline media. Silver solubility in highly oxidized, neutral or acid solutions is increased by formation of AgS₂O₃⁻, Ag⁺ and AgSO₄⁻ complexes.Colloidal, crystalline and alloyed gold and silver reacted with 0.1 M Na₂S₂O₃ do not, however, demonstrate independent solubility. The rate of gold solubility in 0.1 M Na₂S₂O₃, for example, is increased both by the presence of silver-thiosulphate complexes and alloyed silver. It is possible that such behaviour is due to the formation a mixed metal complex of the type (Au, Ag)(S₂O₃)₂³⁻.The nature and mineral association of secondary gold in the oxidized zone of carbonate ore at Wau. in Papua New Guinea, is consistent with prior remobilization as a thiosulphate complex. Here the secondary gold is coarsely crystalline, alloyed with 50–75 at% Ag and enriched at the watertable and with manganese dioxide in the oxidized zone.     

A new,rapid and reliable method for the determination of reduced sulphur (S2−) species in natural water discharges

The determination of reduced S species in natural waters is particularly difficult due to their high instability and chemical and physical interferences in the current analytical methods. In this paper a new, rapid and reliable analytical procedure is presented, named the Cd–IC method, for their determination as ΣS²⁻ via oxidation to ${\text{SO}}_4^{2-}$ after chemical trapping with an ammonia–cadmium solution that allows precipitation of all the reduced S species as CdS. The S²⁻–SO₄ is analysed by ion-chromatography. The main advantages of this method are: low cost, high stability of CdS precipitate, absence of interferences, low detection limit (0.01 mg/L as SO₄ for 10 mL of water) and low analytical error (about 5%). The proposed method has been applied to more than 100 water samples from different natural systems (water discharges and cold wells from volcanic and geothermal areas, crater lakes) in central-southern Italy.     

The hydro geochemical characterization of ground waters in Tunisian Chott’s region.

Tunisian Chott’s region is one of the most productive artesian basins in Tunisia. It is located in the southwestern part of the country, and its groundwater resources are developed for water supply and irrigation. The chemical composition of the water is strongly influenced by the interaction with the basinal sediments and by hydrologic characteristics such as the flow pattern and time of residence. The system is composed of an upper unconfined “Plio-Quaternary” aquifer with a varying thickness of 20–200 m, an intermediate confined/unconfined “Complex Terminal” aquifer about 100 m in thickness and a deeper “Continental Intercalaire” aquifer about 150 m in thickness separated by thick clay and marl layers. The dissolution of evaporites and carbonates explains part of the contained Na⁺, Ca²⁺, Mg²⁺, K⁺, SO₄²⁻ and Cl^-, but other processes, such carbonate precipitation, also contributes to the water composition. The stable isotope composition of waters establishes that the deep groundwater (depleted as compared to present corresponding local rainfall) is ancient water recharged probably during the late Pleistocene and the early Holocene periods. The relatively recent water in the Plio-Quaternary aquifer is composed of mixed waters resulting presumably from upward leakage from the deeper groundwater.     

Reactivity of aquatic iron(III) oxyhydroxides—implications for redox cycling of iron in natural waters

The reactivity of iron(III) oxyhydroxides as reflected by their tendency to dissolve is of great importance in the redox cycling of iron and the bioavailability of iron to phytoplankton in natural waters. In this study, various iron(III) oxyhydroxides were produced by oxygenation of iron(II) in the presence of solutes, such as phosphate, sulfate, bicarbonate, valeric acid, TRIS, humic and fulvic acids, and in the presence of minerals, such as bentonite and δ-Al₂O₃ under conditions encountered in aquatic systems. The reactivity of the different iron(III) oxyhydroxides was subsequently assessed by means of a reductive dissolution using ascorbate and non-reductive dissolution using HQS (8-hydroxyquinoline-5-sulfonic acid) or oxalate. The experimental results show that the iron(III) oxyhydroxides with a low degree of polymerization exhibit higher reactivity than those with a high degree of polymerization or with high crystallinity. The quantity of active surface sites and the coordination arrangement of the functional groups at the surface of the iron(III) oxyhydroxides, especially the extent of the endstanding -OH groups per iron(III) ion determine the reactivity of iron(III) oxyhydroxides toward dissolution.Surfaces, such as clay and aluminum oxides, not only accelerate the oxygenation reaction of iron(II), but also induce the formation of iron(III) oxyhydroxides which are more active toward the dissolution reactions. Polymerization of iron(III) oxyhydroxides on the surfaces occurs predominantly in two dimensions rather than in three dimensions.In a laboratory experiment, the iron(III) oxyhydroxide formed in the presence of TRIS can be reduced by fulvic acid in a closed system under the following conditions: Fe(OH)₃(s) 0.01 g/l, fulvic acid 5 mg/l, pH 7.5, 20°C. The kinetics of the reaction depend on the reactivity of iron(III) oxyhydroxide and reducing power of fulvic acid. Although reductants other than fulvic acid may be of importance in antural waters, this result provides the laboratory evidence that the >Fe^III-OH/Fe(II) is able to act as an electron transfer mediator for the oxidation of natural organic substances, such as fulvic acid, by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O±Al2O3

The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H₂O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al₂O₃ in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.     

Effect of particles on the photodegradation of PAHs in natural waters—A case study for the Yellow River

Photodegradation of chrysene, benzo (a) pyrene and benzo (g, h, i) perylene in natural water of the Yellow River was studied using simulation sunlight. The effects of particulates on the photodegradation were explored. Several results arose from this stud…     

Hydrogen incorporation in enstatite in the system MgO–SiO2–H2O–NaCl

The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na⁺ on the defect chemistry or an exchange between OH^- and Cl⁻in enstatite, appear much less important. A partition coefficient D _Na ^En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.     

Phase relations in the MgO–P2O5–H2O system and the stability of phosphoellenbergerite: petrological implications

The polymorphic relations for Mg₃(PO₄)₂ and Mg₂PO₄OH have been determined by reversed experiments in the temperature-pressure (T-P) range 500–1100 °C, 2–30 kbar. The phase transition between the low-pressure phase farringtonite and Mg₃(PO₄)₂-II, the Mg analogue of sarcopside, is very pressure dependent and was tightly bracketed between 625 °C, 7 kbar and 850 °C, 9 kbar. The high-temperature, high-pressure polymorph, Mg₃(PO₄)₂-III, is stable above 1050 °C at 10 kbar and above 900 °C at 30 kbar. The low-pressure stability of farringtonite is in keeping with its occurrence in meteorites. The presence of iron stabilizes the sarcopside-type phase towards lower P. From the five Mg₂PO₄OH polymorphs only althausite, holtedahlite, β-Mg₂PO₄OH (the hydroxyl analogue of wagnerite) and ɛ-Mg₂PO₄OH were encountered. Relatively speaking, holtedahlite is the low-temperature phase (<600 °C), ɛ-Mg₂PO₄OH the high-temperature, low-pressure phase and β-Mg₂PO₄OH the high-temperature, high-pressure phase, with an intervening stability field for althausite which extends from about 3 kbar at 500 °C to about 12 kbar at 800 °C. Althausite and holtedahlite are to be expected in F-free natural systems under most geological conditions; however, wagnerite is the most common Mg-phosphate mineral, implying that fluorine has a major effect in stabilizing the wagnerite structure. Coexisting althausite and holtedahlite from Modum, S. Norway, show that minor fluorine is strongly partitioned into althausite (K_D ^F/OH≈ 4) and that holtedahlite may incorporate up to 4 wt% SiO₂. Synthetic phosphoellenbergerite has a composition close to (Mg_0.9□_0.1)₂Mg₁₂P₈O₃₈H_8.4. It is a high-pressure phase, which breaks down to Mg₂PO₄OH + Mg₃(PO₄)₂ + H₂O below 8.5 kbar at 650 °C, 22.5 kbar at 900 °C and 30 kbar at 975 °C. The stability field of the phosphate end-member of the ellenbergerite series extends therefore to much lower P and higher T than that of the silicate end-members (stable above 27 kbar and below ca. 725 °C). Thus the Si/P ratio of intermediate members of the series has a great barometric potential, especially in the Si-buffering assemblage with clinochlore + talc + kyanite + rutile + H₂O. Application to zoned ellenbergerite crystals included in the Dora-Maira pyrope megablasts, western Alps, reveals that growth zoning is preserved at T as high as 700–725 °C. However, the record of attainment of the highest T and/or of decreasing P through P-rich rims (1 to 2 Si pfu) is only possible in the presence of an additional phosphate phase (OH-bearing or even OH-dominant wagnerite in these rocks), otherwise the trace amounts of P in the system remain sequestered in the core of Si-rich crystals (5 to 8 Si pfu) and can no longer react. Received: 7 April 1995 / Accepted: 12 November 1997     

Experimental modeling of native carbon formation in a C–O–H fluid system

Integrated data are presented on structure–morphology features, as well as on the material and phase composition, of a fluid-produced carbonaceous substance (CS) formed under known thermodynamic conditions of the experiment (C–O–H system, 500–800°C, and 500–1000 atm). Solid products of the synthesis were examined by means of X-ray phase and thermal analyses, scanning electron microscopy combined with microprobe analysis, transmission electron microscopy, high-resolution Raman spectroscopy, IR spectroscopy, and CHN-analysis. The characteristics of the experimental CS may be applicable in genetic modeling of natural ore-bearing fluidal carbonaceous systems.     

Experimental Study of Dissolution Rates of Fluorite in HCl–H2O Solutions

The experiments of the dissolution kinetics of fluorite were performed in aqueous HCl solutions over the temperature range of 25–100 °C using a flow-through experimental apparatus. With a constant input of aqueous HCl solution through the reactor, output concentrations of the dissolved species Ca, F, Cl vary with flow rate, as well as with the surface compositions. Measured output concentrations of dissolved species and the pH can be used to determine a rate law for fluorite dissolution. Fluorite dissolution rates are found to be pH dependent. Usually, dissolution rates of fluorite decreases with increasing dissolved Ca in the output solution at 25 and 100 °C. Dissolution rate can be expressed as