Articles | Volume 37, issue 1
https://doi.org/10.5194/ejm-37-111-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/ejm-37-111-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
26 Feb 2025
Research article |
| 26 Feb 2025
| 26 Feb 2025
Tungsten solubility and speciation in hydrothermal solutions revealed by in situ X-ray absorption spectroscopy
Manuela Borchert
Institut für Mineralogie, Universität Münster, Corrensstrasse 24, 48149 Münster, Germany
Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, 22607 Hamburg, Germany
Maria A. Kokh
Institut für Mineralogie, Universität Münster, Corrensstrasse 24, 48149 Münster, Germany
Institut für Geowissenschaften, Universität Potsdam, Karl-Liebknecht-Str. 24–25, 14476 Potsdam, Germany
Marion Louvel
Institut für Mineralogie, Universität Münster, Corrensstrasse 24, 48149 Münster, Germany
Institut des Sciences de la Terre d'Orléans, CNRS–BRGM–Univ. Orléans, 1A rue de la Ferollerie, 45100 Orléans, France
Elena F. Bazarkina
Institute of Resource Ecology, Helmholtz-Zentrum Dresden-Rossendorf (HZDR), P.O. Box 510119, 01314 Dresden, Germany
The Rossendorf Beamline, European Synchrotron Radiation Facility (ESRF), CS40220, 38043 Grenoble CEDEX 9, France
Anselm Loges
Institut für Geologische Wissenschaften, Freie Universität Berlin, Malteserstr. 74–100, 12249 Berlin, Germany
Edmund Welter
Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, 22607 Hamburg, Germany
Denis Testemale
Université Grenoble Alpes, CNRS, Institut Néel, 38000 Grenoble, France
Rami Al Abed
Institut für Geowissenschaften, Universität Potsdam, Karl-Liebknecht-Str. 24–25, 14476 Potsdam, Germany
Stephan Klemme
Institut für Mineralogie, Universität Münster, Corrensstrasse 24, 48149 Münster, Germany
Institut für Geowissenschaften, Universität Potsdam, Karl-Liebknecht-Str. 24–25, 14476 Potsdam, Germany
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Rock lenses from the diamond stability field (>120 km depth) within ordinary gneiss are enigmatic. Even more when these lenses form an alternating exposure pattern with ordinary lenses. We studied 10 lenses from W Norway and found that many of them have a hidden history. Tiny needles of quartz enclosed in old pyroxene cores are evidence for a rock origin at great depth. These needles survived the rocks' passage to the surface that variably obscured the mineral chemistry – the rocks' memory.
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Eur. J. Mineral., 34, 507–521, https://doi.org/10.5194/ejm-34-507-2022, https://doi.org/10.5194/ejm-34-507-2022, 2022
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We investigated the effect that fluoride and protons have on each other as structural neighbors in the mineral topaz. This was done using spectroscopic methods, which measure the interaction of electromagnetic radiation with matter. The forces between atoms distort the spectroscopic signals, and this distortion can thus be used to understand the corresponding forces and their effect on the physical properties of the mineral.
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Eur. J. Mineral., 34, 411–424, https://doi.org/10.5194/ejm-34-411-2022, https://doi.org/10.5194/ejm-34-411-2022, 2022
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Carbonates reduce the melting point of the mantle, and carbonate melts produced in low-degree melting of a carbonated mantle are considered the precursor of CO2-rich magmas. We established experimentally the melting relations of carbonates up to 9 GPa, showing that Mg-carbonates melt incongruently to periclase and carbonate melt. The trace element signature of carbonate melts parental to kimberlites is approached by melting of Mg-rich carbonates.
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Metamorphic rocks contain information about their original rocks and thus provide insight into the earlier stages of a region of interest. Here, we used the whole-rock chemical composition and stable boron isotopes of a suite of rocks from the Alps (Italy–Austria), which were deposited in a restricted intramontane basin before the Alpine orogeny. It is possible to reconstruct the depositional conditions for these sediments, which are now common metamorphic rocks such as schists and gneisses.
Cited articles
Akinfiev, N. N. and Diamond, L. W.: Thermodynamic description of aqueous nonelectrolytes at infinite dilution over a wide range of state parameters, Geochim. Cosmochim. Acta, 67, 613–629, 2003.
Barin, I. (Ed.): Thermochemical Data of Pure substances. VCH Verlagsgesellschaft mbH, Weinheim, Germany, ISBN 3-527-28745-0, 1995.
Barin, I. and Knacke, O. (Eds.): Thermochemical properties of inorganic substances: Berlin, Springer-Verlag, 921 pp., 1973.
Bianconi, A., DelliìAriccia, M., Gargano, A., and Natoli, C. R.: Bond length determination using XANES, in: EXAFS and Near Edge Structure, edited by: Bianconi, A., Incoccia, L., and Stilpcich, S., Springer Series in Chemistry and Physics, Berlin, 27, 57–61, 1983.
Borchert, M., Kokh, M. A., Louvel, M., Bazarkina, E. F., Loges, A., Testemale, D., Al Abed, R., Klemme, S., and Wilke, M.: Tungsten concentrations and tungsten EXAFS and XANES data in hydrothermal solutions, GFZ Data Services [data set], https://doi.org/10.5880/fidgeo.d.2024.002, 2024.
Borg, S., Liu, W., Etschmann, B., Tian, Y., and Brugger, J.: An XAS study of molybdenum speciation in hydrothermal chloride solutions from 25–385 °C and 600 bar, Geochim. Cosmochim. Acta, 92, 292–307, 2012.
Brugger, J., Liu, W., Etschmann, B., Mei, Y., Sherman, D. M., and Testemale, D.: A review of the coordination chemistry of hydrothermal systems, or do coordination changes make ore deposits?, Chem. Geol., 447, 219–253, 2016.
Bryzgalin, O. V. and Rafal'sky, R. P.: Estimation of instability constants for ore-element complexes at elevated temperatures, Geochem. Intern., 19, 839–849, 1982.
Bychkov, A. Y. and Zuykov, V. V.: Solubility of tungstic acid and forms of tungsten transport in sodium chloride solutions at 25 °C, Dokladi akademii nauk, 400, 69–71, 2005.
Carocci, E., Truche, L., Cathelineau, M., Caumon, M. C., and Bazarkina, E. F.: Tungsten (VI) speciation in hydrothermal solutions up to 400 °C as revealed by in situ Raman spectroscopy, Geochim. Cosmochim. Acta, 317, 306–324, 2022.
Crerar, D. A., Wood, S., Brantley, S., and Bocarsly, A.: Chemical controls on solubility of ore-forming minerals in hydrothermal systems, Can. Mineral., 23, 333–352, 1985.
Dewan, J. C. and Kepert, D. L.: Rapid Acidification of Solutions containing Tungstate Anions, J. Chem. Soc., Dalton Transactions, 224–225, 1973.
Diehl, R., Brandt, G., and Salje, E.: The crystal structure of triclinic WO3, Acta Cryst., B34, 1105–1111, 1978.
Driesner, T.: The System H2O-NaCl. II. Correlations for molar volume, enthalpy, and isobaric heat capacity from 0 to 1000 degrees C, 1 to 5000 bar, and 0 to 1 XNaCl, Geochim. Cosmochim. Acta, 71, 4902–4919, 2007.
Driesner, T. and Heinrich, C. A.: The System H2O-NaCl. I. Correlation Formulae for Phase Relations in Temperature-Pressure-Composition Space from 0 to 1000 °C, 0 to 5000 bar, and 0 to 1 XNaCl, Geochim. Cosmochim. Acta, 71, 4880–4901, 2007.
Elam, W. T., Ravel, B. D., and Sieber, J. R.: A new atomic database for X-ray spectroscopic calculations, Rad. Phys. Chem., 63, 121–128, 2002.
Farrugia, L. J.: Sodium tungstate dihydrate: a redetermination, Acta Cryst., E63, i142, https://doi.org/10.1107/S1600536807023355, 2007.
Franck, E. U., Rosenzweig, S., and Christoforakos, M.: Calculation of the dielectric constant of water to 1000 °C and very high pressures, Bunsen-Ges. Phys. Chem., 94, 199–203, 1990.
Fuggle, J. C. and Mårtensson, N.: Core-level binding energies in metals, J. Electron. Spectrosc. Relat. Phenom., 21, 275–281, https://doi.org/10.1016/0368-2048(80)85056-0, 1980.
Gibert, F., Moine, B., Schott, J., and Dandurand, J. L.: Modeling of the transport and deposition of tungsten in the scheelite-bearing calc-silicate gneisses of the Montagne Noire, France, Contrib. Mineral. Petrol., 112, 371–384, 1992.
Han, B., Khoroshilov, A., Tyurin, A., Baranchikov, A., Razumov, M., Ivanova, O., Gavrichev, K., and Ivanov, V.: WO3 thermodynamic properties at 80–1256 K revisited, Chem. J. Therm. Anal. Calo., 142, 1533–1543, 2020.
Han, Z., Golev, A., and Edraki, M.: A Review of Tungsten Resources and Potential Extraction from Mine Waste, Minerals, 11, 701, https://doi.org/10.3390/min11070701, 2021.
Heinrich, C. A.: The chemistry of hydrothermal tin (-tungsten) ore deposits, Econ. Geol., 85, 457–481, 1990.
Helgeson, H. C. and Kirkham, D. H.: Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures; I, Summary of the thermodynamic/electrostatic properties of the solvent, Am. J. Sci., 274, 1089–1198, 1974.
Helgeson, H. C., Kirkham, D. H., and Flowers, G. C.: Theoretical prediction of thermodynamic behavior of aqueous electrolytes at high temperatures and pressures. IV. Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 5 kb and 600 °C, Am. J. Sci., 281, 1249–1516, 1981.
Hoffmann, M. M., Darab, J. G., Heald, S. M., Yonker C. R., and Fulton J. L.: New experimental developments for in situ XAFS studies of chemical reactions under hydrothermal conditions, Chem. Geol., 167, 89–103, 2000.
Hulsbosch, N., Boiron, M.-Ch., Dewaele, S., and Muchez, P.: Fluid fractionation of tungsten during granite-pegmatite differentiation and the metal source of peribatholitic W quartz veins: Evidence from the Karagwe-Ankole Belt (Rwanda), Geochim. Cosmochim. Acta, 175, 299–318, 2016.
Ivanova, G. F. and Khodakovskiy, I. L.: Chemical forms of tungsten transport in hydrothermal solutions, Geokhimiya, 8, 426, 1968 (in Russian).
Ivanova, G. F. and Khodakovskiy, I. L.: About chemical state of tungsten in hydrothermal solutions, Geokhimiya, 11, 1426–1433, 1972 (in Russian).
Johnson, J. W., Oelkers, E. H., and Helgeson, H. C.: SUPCRT92: a software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000 °C, Comput. Geosci., 18, 899–947, 1992.
Kestin, J., Sengers, J. V., Kamgar-Parsi, B., and Sengers J. M. H. L.: Thermophysical properties of fluid H2O, J. Phys. Chem. Ref. Data, 13, 175–183, 1984.
Klemme, S., Feldhaus, M., Potapkin, V., Wilke, M., Borchert, M., Louvel, M., Loges, A., Rohrbach, A., Weitkamp, P., Welter, E., Kokh, M., Schmidt, C., and Testemale, D.: A hydrothermal apparatus for x-ray absorption spectroscopy of hydrothermal fluids at DESY, Rev. Sci. Instrum., 92, 063903, https://doi.org/10.1063/5.0044767, 2021.
Klimek, P., Obersteiner, M., and Thurner, S.: Systemic trade risk of critical resources, Sci. Adv., 1, e1500522, https://doi.org/10.1126/sciadv.1500522, 2015.
Korges, M., Weis, P., Lüders, V., and Laurent, O.: Depressurization and boiling of a single magmatic fluid as a mechanism for tin-tungsten deposit formation, Geology, 46, 75–78, 2018.
Kozlik, M. and Raith, J.: Variscan metagranitoids in the central Tauern Window (Eastern Alps, Austria) and their role in the formation of the Felbertal scheelite deposit, Lithos, 278–281, 303–320, 2017.
Kwak, T. A. P.: W-Sn skarn deposits and related metamorphic skarns and granitoids, in: Developments in Economic Geology, 24, Amsterdam, Elsevier Science, 468 pp., 1987.
Lecumberri-Sanchez, P., Vieira, R., Heinrich, C. A., Pinto, F., and Wälle, M.: Fluid-rock interaction is decisive for the formation of tungsten deposits, Geology, 45, 579–582, 2017.
Lemmon, E. W., McLinden, M. O., and Friend, D. G.: Thermophysical Properties of Fluid Systems, in: NIST Chemistry WebBook, edited by: Linstrom, P. J. and Mallard, W. G., NIST Standard Reference Database. National Institute of Standards and Technology, Gaithersburg MD, https://doi.org/10.18434/T4D303, 2019.
Li, G., Bridges, F., and Brown, G. S.: Multielectron X-ray photoexcitation observations in X-ray-absorption fine-structure background, Phys. Rev. Lett., 68, 1609–1612, 1992.
Marshall, W. L. and Franck, E. U.: Ion product of water substance, 0–1000 °C, 1–10,000 bars new international formulation and its background, J. Phys. Chem. Ref. Data, 10, 295–304, 1981.
Mei, Y., Liu, W., Guan, O., Brugger, J., Etschmann, B., Siégel, C., Wykes, J., and Ram, R.: Tungsten speciation in hydrothermal fluids, Geochim. Cosmochim. Acta, https://doi.org/10.1016/j.gca.2024.06.030, in press, 2024.
Minubaeva, Z.: UV Spectroscopic Studies of the Hydrothermal Geochemistry of Molybdenum and Tungsten, PhD Thesis, ETH Zurich, 142 pp., https://doi.org/10.3929/ethz-a-005557770, 2007.
Naumov, V. B., Dorofeev, V. A., and Mironova, O. F.: Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits, Geochem. Int., 49, 1002–1021, 2011.
Oelkers, E. H. and Helgeson, H. C.: Triple-ion anions and polynuclear complexing in supercritical electrolyte solutions, Geochim. Cosmochim. Acta, 54, 727–738, 1990.
Oelkers, E. H. and Helgeson, H. C.: Calculation of activity coefficients and degrees of formation of neutral ion pairs in supercritical electrolyte solutions, Geochim. Cosmochim. Acta, 55, 1235–1251, 1991.
Ordosch, A., Raith, J. G., Schmidt, S., and Aupers, K.: Polyphase scheelite and stanniferous silicates in a W-(Sn) skarn close to Felbertal tungsten mine, Eastern Alps, Mineral. Petrol., 113, 703–725, 2019.
Pearson, R. G.: Hard and soft acids and bases, Am. Chem. Soc. J., 85, 3533–3539, 1963.
Perrin, D. D.: Dissociation constants of inorganic acids and bases in aqueous solution, Butterworth & Co., London, 112 pp., ISBN 978-0408700153, 1969.
Pokrovski, G. S., Schott, J., and Sergeyev, A. S.: Experimental determination of the stability constants of NaSO
Pokrovski, G. S., Roux, J., Hazemann, J.-L., and Testemale, D.: An X-ray absorption spectroscopy study of argutite solubility and aqueous Ge(IV) speciation in hydrothermal fluids to 500 °C and 400 bar, Chem. Geol., 217, 127–145, 2005.
Proux, O., Biquard, X., Lahera, E., Menthonnex, J.-J., Prat, A., Ulrich, O., Soldo, Y., Trevisson, P., Kapoujyan, G., Perroux, G., Taunier, P., Grand, D., Jeantet, P., Deleglise, M., Roux, J.-P., and Hazemann, J.-L.: FAME: a new beamline for X-ray absorption investigations of very diluted systems of environmental, material and biological interests, Phys. Scr., T115, 970–973, 2005.
Proux, O., Nassif, V., Prat, A., Ulrich, O., Lahera, E., Biquard, X., Menthonnex, J.-J., and Hazemann, J.-L.: Feedback system of a liquid-nitrogen-cooled double-crystal monochromator: design and performances, J. Synchrotron Rad., 13, 59–68, 2006.
Qiao, S., Loges, A., and John, T.: Formation of topaz-greisen by a boiling fluid: a case study from the Sn-W-Li deposit, Zinnwald/Cínovec, Econ. Geol., 119, 805–828, 2024.
Rafal'sky, R. P., Bryzgalin, O. V., and Fedorov, P. L.: Transport of tungsten and scheelite deposition under hydrothermal conditions, Geochem. Intern., 5, 611–624, 1984.
Rehr, J. J., Kas, J. J., Vila, F. D., Prange, M. P., and Jorissen, K.: Parameter-free calculations of x-ray spectra with FEFF9, Phys. Chem. Chem. Phys., 12, 5503–5513, 2010.
Robie, R. A. and Hemingway, B. S.: Thermodynamic properties of minerals and related substances at 298.15 K and 1 Bar (105 Pascals) pressure and at higher temperatures, U.S., Geological Survey Bulletin, 2131, 1995.
Ryzhenko, B. N., Bryzgalin, O. V., Artamkina, I. Y., Spasennykh, M. Y., and Shapkin, A. I.: An electrostatic model for the electrolytic dissociation of inorganic substances dissolved in water, Geochem. Int., 22, 128–144, 1985.
Seward, T. M.: Metal complex formation in aqueous solutions at elevated temperatures and pressures, Phys. Chem. Earth, 13–14, 113–132, 1981.
Seward, T. M. and Barnes, H. L.: Metal transport by hydrothermal ore fluids, in: Geochemistry of Hydrothermal Ore Deposits, edited by: Barnes, H. L., John Wiley & Sons, New York, 435–486, https://doi.org/10.5860/choice.35-2126, 1997.
Shock, E. L., Sassani, D. C., Willis, M., and Sverjensky, D. A.: Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes, Geochim. Cosmochim. Acta, 61, 907–950, 1997.
Shvarov, Y. V.: HCh: new potentialities for the thermodynamic simulation of geochemical systems offered by Windows, Geochem. Intern., 46, 834–839, 2008.
Shvarov, Y. V.: A suite of programs, OptimA, OptimB, OptimC, and OptimS compatible with the Unitherm database, for deriving the thermodynamic properties of aqueous species from solubility, potentiometry and spectroscopy measurements, Appl. Geochem., 55, 17–27, 2015.
Shvarov, Y. V. and Bastrakov, E.: HCh: a software package for geochemical equilibrium modelling, User’s Guide, Australian Geological Survey Organization, record 25, 1999.
Sirbescu, M.-L., Krukowski, E. G., Schmidt, C., Thomas, R., Samson, I. M., and Bodnar, R. J.: Analysis of boron in fluid inclusions by microthermometry, laser ablation ICP-MS, and Raman spectroscopy: Application to the Cryo-Genie Pegmatite, San Diego County, California, USA, Chem. Geol., 342, 138–150, 2013.
Sverjensky, D. A., Shock, E. L., and Helgeson H. C.: Prediction of the thermodynamic properties of aqueous metal complexes to 1000 °C and 5 kb, Geochim. Cosmochim. Acta, 61, 1359–1412, 1997.
Sverjensky, D. A., Harrison, B., and Azzolini, D.: Water in the deep Earth: the dielectric constant and the solubilities of quartz and corundum to 60 kb and 1200 C, Geochim. Cosmochim. Acta, 129, 125–145, 2014.
Tagirov, B. R., Zotov, A. V., and Akinfiev, N. N.: Experimental study of dissociation of HCl from 350 to 500 °C and from 500 to 2500 bars: Thermodynamic properties of HCl0 (aq), Geochim. Cosmochim. Acta, 61, 4267–4280, 1997.
Tanger, J. C. and Helgeson, H. C.: Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures; revised equations of state for the standard partial molal properties of ions and electrolytes, Am. J. Sci., 288, 19–98, 1988.
Testemale, D., Argoud, R., Geaymond, O., and Hazemann, J.-L.: High pressure/high temperature cell for x-ray absorption and scattering techniques, Rev. Sci. Instrum., 76, 043905, https://doi.org/10.1063/1.1884188, 2005.
Testemale, D., Brugger, J., Liu, W., Etschmann, B., and Hazemann. J.-L.: In-situ X-ray absorption study of Iron (II) speciation in brines up to supercritical conditions, Chem. Geol., 264, 295–310, 2009.
Testemale, D., Prat, A., Lahera, E., and Hazemann, J.-L.: Novel high-pressure windows made of glass-like carbon for x-ray analysis, Rev. Sci. Instrum., 87, 075115, https://doi.org/10.1063/1.4959110, 2016.
Testemale, D., Pokrovski, G.S., Lahera, E., Prat, A., Kieffer, I., Delnet, W., Proux, O., Louvel, M., Sanchez-Valle, C., and Hazemann, J. L.: In situ X-ray absorption spectroscopy using the FAME autoclave: a window into fluid-mineral-melt interactions in the Earth's crust, High Pressure Res., 44, 277–293, 2024.
Wang, X., Qui, Y., Chou, I.-M., Zhang, R., Li, G., and Zhong, R.: Effects of pH and salinity on the hydrothermal transport of tungsten: insights from in situ Raman spectroscopic characterization of K2WO4-NaCl-HCl-CO2 solutions at temperatures up to 400 °C, Geofluids, 2020, 2978984, https://doi.org/10.1155/2020/2978984, 2020a.
Wang, X., Qui, Y., Lu, J., Chou, I.-M., Zhang, W., Li, G., Hu, W., Li, Z., and Zhong, R.: In situ Raman spectroscopic investigation of the hydrothermal speciation of tungsten: implication for the ore-forming process, Chem. Geol., 532, 119299, https://doi.org/10.1016/j.chemgeo.2019.119299, 2020b.
Wang, X. S., Timofeev, A., Williams-Jones, A. E., Shang, L. B., and Bi, X. W.: An experimental study of the solubility and speciation of tungsten in NaCl-bearing aqueous solutions at 250, 300, and 350 °C, Geochim. Cosmochim. Acta, 265, 313–329, 2019.
Wang, X. S., Williams-Jones, A. E., Hu, R. Z., Shang, L. B., and Bi, X. W.: The role of fluorine in granite-related hydrothermal tungsten ore genesis: Results of experiments and modeling, Geochim. Cosmochim. Acta, 292, 170–187, 2021.
Welter, E., Chernikov, R., Herrmann, M., and Nemausat, R.: A beamline for bulk sample X-ray absorption spectroscopy at a high brilliance storage ring PETRA III, AIP Conf. Prog., 2054, 040002, https://doi.org/10.1063/1.5084603, 2019.
Wesolowski, D., Drummond, S. E., Mesmer, R. E., and Ohmoto, H.: Hydrolysis equilibria of tungsten (VI) in aqueous sodium-chloride solutions to 300 °C, Inorg. Chem., 23, 1120–1132, 1984.
Wilke, M., Farges, F., Partzsch, G. M., Schmidt, C., and Behrens, H.: Speciation of Fe in silicate glasses and melts by in situ XANES spectroscopy, Am. Mineral., 92, 44–56, 2007.
Winterer, M.: xafsX: a program to process, analyse and reduce X-ray absorption fine structure spectra (XAFS), in: International Tables for Crystallography, Vol I: X-ray Absorption Spectroscopy and Related Techniques, edited by: Chantler, C. T., Bunker, B., and Boscherini, F., https://doi.org/10.1107/s1574870720003481, 2022.
Wood, S. A.: Experimental determination of the solubility of WO3 (s) and the thermodynamic properties of H2WO4 (aq) in the range 300–600 °C at 1 kbar: calculation of scheelite solubility, Geochim. Cosmochim. Acta, 56, 1827–1836, 1992.
Wood, S. A. and Samson, I. M.: The hydrothermal geochemistry of tungsten in granitoid environments: I. Relative solubilities of ferberite and scheelite as a function of T, P, pH, and m NaCl, Econ. Geol., 95, 143–182, 2000.
Wood, S. A. and Vlassopoulos, D.: Experimental determination of the hydrothermal solubility and speciation of tungsten at 500 °C and 1 kbar, Geochim. Cosmochim. Acta, 53, 303–312, 1989.
Xiao, L., Ji, L., Yin, C., Chen, A., Chen, X., Liu, X., Li, J., Sun, F., and Zhao, Z.: Tungsten extraction from scheelite hydrochloric acid decomposition residue by hydrogen peroxide, Miner. Eng., 179, 107461, https://doi.org/10.1016/j.mineng.2022.107461, 2022.
Zalkin, A. and Templeton, D. H.: X-ray diffraction refinement of the calcium tungstate structure, J. Chem. Phys., 40, 501–504, 1964.
Zhang, Y., Gao, J.-F., Ma, D., and Pan, J.: The role of hydrothermal alteration in tungsten mineralization at the Dahutang tungsten deposit, South China, Ore Geol. Rev., 95, 1008–1027, 2018.
Zhidikova, A. P. and Khodakovskiy, I. L.: Thermodynamic properties of ferberite, hubnerite, scheelite and powellite, in: Physicochemical models of petrogenesis and ore formation, edited by: Tauson, L. V., Nauka, Novosibirsk, 145–156, 1984.
Short summary
Tungsten (W) concentrations in fluids in equilibrium with crystalline tungsten oxide are used to improve constraints of thermodynamic parameters for W solubility. W species in the hydrothermal fluids are further characterized by X-ray spectroscopy. Improved thermodynamic properties for a set of W fluid species are provided that cover a wide range of fluid compositions, necessary for understanding and describing the complex processes of W enrichment and mineralization in hydrothermal systems.
Tungsten (W) concentrations in fluids in equilibrium with crystalline tungsten oxide are used to...
