Sulphur Isotopes, Trace Elements and Mineral Stability Diagrams of Waters from the Abandoned Fe–Cu Mines of Libiola and Vigonzano (Northern Apennines, Italy)

2008 ◽  
Vol 192 (1-4) ◽  
pp. 85-103 ◽  
Author(s):  
Gianni Cortecci ◽  
Tiziano Boschetti ◽  
Enrico Dinelli ◽  
Roberto Cabella
1996 ◽  
Vol 465 ◽  
Author(s):  
Robert J. Finch

ABSTRACTGibbs free energies of formation (ΔG°ƒ) for several structurally related U(VI) minerals are estimated by summing the Gibbs energy contributions from component oxides. The estimated ΔG°f values are used to construct activity-activity (stability) diagrams, and the predicted stability fields are compared with observed mineral occurrences and reaction pathways. With some exceptions, natural occurrences agree well with the mineral stability fields estimated for the systems Sio2-Cao-Uo3-UOH2O and Co2-caO-UO3-H2O providing confidence in the estimated thermodynamic values. Activity-activity diagrams are sensitive to small differences in ΔG°f values, and mineral compositions must be known accurately, including structurally bound H2O. The estimated ΔG°f values are not considered reliable for a few minerals for two major reasons: (1) the structures of the minerals in question are not closely similar to those used to estimate the ΔG°f* values of the component oxides, and/or (2) the minerals in question are exceptionally fine grained, leading to large surface energies that increase the effective mineral solubilities.


1997 ◽  
Vol 9 (1) ◽  
pp. 92-99 ◽  
Author(s):  
G.M. Marion

Don Juan Pond, located in the Wright Valley, Victoria Land, is unique for several reasons. It is the most saline of the Antarctic lakes, being a near-saturated CaCl2 solution. As a consequence of this high salinity, Don Juan Pond generally remains unfrozen in winter, even at temperatures below -50°C. Don Juan Pond is the site where antarcticite (CaCl2·6H2O) was first identified forming naturally. The objective of this paper is to demonstrate the utility of a chemical thermodynamic model (FREZCHEM) by developing theoretical stability diagrams for ice, halite (NaCl), hydrohalite (NaCl·2H2O), and antarcticite in Don Juan Pond, using experimental data collected on 34 days between 1961 and 1983. The composition of Don Juan Pond at the calculated eutectic temperature (-51.8°C) was CaCl2 = 3.72 mol kg−1 and NaCl = 0.50 mol kg−1, which is similar but not identical to a pure NaCl–CaCl2–H2O system. The low eutectic temperature and high CaCl2 concentrations of Don Juan Pond account for lack of freezing during winter. The model is compatible with the experimental data, and predicts the formation of ice during rare high water periods, halite, and antarcticite. These solid phases have all been reported from Don Juan Pond. The model also predicts the formation of hydrohalite at subzero temperatures; hydrohalite has never been observed at Don Juan Pond, but this may simply reflect that most sampling was done during the summer when halite is thermodynamically more stable than hydrohalite. The FREZCHEM model may prove useful in elucidating the physicochemical behaviour, the origin of salinity, and the evolution of Antarctic lakes.


1985 ◽  
Vol 50 ◽  
Author(s):  
David Savage ◽  
Mark R. Cave ◽  
Antoni E Milodowski

AbstractHydrothermal rock-water experiments at 80°, 150° and 250° C have been carried out to investigate the origin of saline groundwaters in the Carnmenellis Granite, Cornwall, UK which have previously been attributed to be derived via dissolution of biotite and plagioclase feldspar by dilute meteoric groundwaters. The nature of product fluid and solid phases in the experiments was dominated by the dissolution of plagioclase and potassium feldspars, coupled with the precipitation of laumontite, calcite and smectite. However, the release of chloride from the rock was minimal, suggesting minor dissolution of the major chloride bearing mineral, biotite. The relative inertness and stability of biotite during the experiments was borne out by direct physical observation of reacted biotites and by consideration of the fluid phase composition in terms of thermodynamic mineral stability diagrams. It is concluded that the experimental and natural systems are buffered under different chemical conditions, which may be due to acidity generated via oxidation of localised sulphide zones within the granite and absent in the experiments. Dissolution of biotite may be an important mechanism for enhancing the salinity of groundwaters in granitic rocks if groundwaters are buffered to be outside the stability of biotite and convective circulation is significant.


1995 ◽  
Vol 21 (1) ◽  
pp. 175-185 ◽  
Author(s):  
Dean L. Biddle ◽  
Harry J. Percival ◽  
David J. Chittleborough

2004 ◽  
Vol 38 (13) ◽  
pp. 3641-3648 ◽  
Author(s):  
David G. Kinniburgh ◽  
David M. Cooper

Clay Minerals ◽  
1986 ◽  
Vol 21 (3) ◽  
pp. 389-400
Author(s):  
J. L. Martin de Vidales ◽  
J. Casas ◽  
J. Sanz

AbstractWeathering processes in the Piedrabuena volcano, Ciudad Real province, Central Spain, have produced a smectitic phyllosilicate in four profiles on porphyritic-holocrystalline basalts consisting mainly of titaniferous augites, olivine and pigeonite. Chemical analysis of the purified smectites gave TiO2 contents of 1·89–3·77%. Apart from one profile, the smectites showed high tetrahedral Al-for-Si substitution, with the lattice charge arising from this source exceeding that from octahedral substitution, and thus could be termed beidellites. Octahedral Ti contents ranged from 0·21 to 0·41 per 24 O. A thermodynamic model was used to estimate the ΔG° of formation of these titaniferous smectites. Values ranged between −2503·30 and −2543·26 Kcal/mol. Suitable equilibria were established by calculating their ΔG° of reaction and log Ksp and, from these, the stability diagrams pH - 1/2pMg2+ against log H4SiO4 were derived. Correlations found were: (i) strong and positive between AlVI-X+ (0·91), AlIV-FeVI (0·85), AlVI-FeVI (0·85) and AlVI-MgVI (0·76); (ii) strong and negative between AlIV-octahedral charge; (iii) solubility product (log Ksp) positively correlated with X+ (0·73), AlIV (0·89), FeVI (0·67) and MgVI (0·84). Smectites showing higher tetrahedral charges were the least stable. Conversely, the stabilities of titaniferous smectites were favoured by high values of pH - 1/2pMg2+ and/or activities in soil-matrix solution. When the activities of H4SiO4 decreased, the montmorillonitic smectites became less stable than those showing beidellitic characteristics. Variations in composition and stability of the titaniferous smectites were not correlated with soil depth.


Author(s):  
O.T. Woo ◽  
G.J.C. Carpenter

To study the influence of trace elements on the corrosion and hydrogen ingress in Zr-2.5 Nb pressure tube material, buttons of this alloy containing up to 0.83 at% Fe were made by arc-melting. The buttons were then annealed at 973 K for three days, furnace cooled, followed by ≈80% cold-rolling. The microstructure of cold-worked Zr-2.5 at% Nb-0.83 at% Fe (Fig. 1) contained both β-Zr and intermetallic precipitates in the α-Zr grains. The particles were 0.1 to 0.7 μm in size, with shapes ranging from spherical to ellipsoidal and often contained faults. β-Zr appeared either roughly spherical or as irregular elongated patches, often extending to several micrometres.The composition of the intermetallic particles seen in Fig. 1 was determined using Van Cappellen’s extrapolation technique for energy dispersive X-ray analysis of thin metal foils. The method was employed to avoid corrections for absorption and fluorescence via the Cliff-Lorimer equation: CA/CB = kAB · IA/IB, where CA and CB are the concentrations by weight of the elements A and B, and IA and IB are the X-ray intensities; kAB is a proportionality factor.


Author(s):  
D. A. Carpenter ◽  
Ning Gao ◽  
G. J. Havrilla

A monolithic, polycapillary, x-ray optic was adapted to a laboratory-based x-ray microprobe to evaluate the potential of the optic for x-ray micro fluorescence analysis. The polycapillary was capable of collecting x-rays over a 6 degree angle from a point source and focusing them to a spot approximately 40 µm diameter. The high intensities expected from this capillary should be useful for determining and mapping minor to trace elements in materials. Fig. 1 shows a sketch of the capillary with important dimensions.The microprobe had previously been used with straight and with tapered monocapillaries. Alignment of the monocapillaries with the focal spot was accomplished by electromagnetically scanning the focal spot over the beveled anode. With the polycapillary it was also necessary to manually adjust the distance between the focal spot and the polycapillary.The focal distance and focal spot diameter of the polycapillary were determined from a series of edge scans.


1979 ◽  
Vol 7 (6) ◽  
pp. 1330-1331
Author(s):  
E. D. WILLS

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