Wolframite solubility and precipitation in hydrothermal ... XC-202… · 3. Species and reactions in fluid-buffered thermodynamic models Two limiting cases of fluid-rock interactions
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Wolframite solubility and precipitation in hydrothermal fluids: insight fromthermodynamic modeling
Received Date: 6 August 2019Revised Date: 26 November 2019Accepted Date: 14 December 2019
Please cite this article as: X. Liu, C. Xiao, Wolframite solubility and precipitation in hydrothermal fluids: insightfrom thermodynamic modeling, Ore Geology Reviews (2019), doi: https://doi.org/10.1016/j.oregeorev.2019.103289
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a coverpage and metadata, and formatting for readability, but it is not yet the definitive version of record. This version willundergo additional copyediting, typesetting and review before it is published in its final form, but we are providingthis version to give early visibility of the article. Please note that, during the production process, errors may bediscovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
used in this study. Tian Yuan’ and Mei Yuan’s explanations also helped X.C. Liu understand
different Mn(II) chloride complexes in thei paper. The author appreciates Weihua Liu,
another anonymous reviewer, and the editor for their comments and advices on the original
manuscript.
Appendix 1
Nonlinear equations driven by reaction and balance constraints shown in Table 3 and
Table 4 were solved by the the R package rootSolve. Good initial values of the variables are
a prerequisite for deriving the optimal roots (Crerar, 1975). The procedure of solving the
nonlinear equations in the models is as follows:
(1) The initial ionic strength is set to be half of the morlality of NaCl in solutions, and the 𝐼0
initial activities of both Na+ and Cl- equal . 𝐼0
(2) Calculate the activity coefficients of all ionic speices using the equation (9) with the initial
ionic strength . Note that the only species-specific parameter required in equation (9) is 𝐼0
the electrical charge, meaning that the activity coefficient of Na+ equals that of H+ and the
activity coefficient of Fe2+ equals that of WO42-.
(3) Calculate the concentration of H+ using its activity coefficient and a given pH. According
the non-linear equations like equation (8), calculate all other species’ initial activities one
by one using using the initial activities of H+, Na+, and Cl-. These initial activities of ionic
speices will be used as initial values for solving the nonlinear equations.
(4) Solve the nonlinear equations simultaneously using the R package rootSolve. Then,
update the ionic strength and the activity coefficients of ionic speices and take the roots as
the initial values for the next solving.
(5) Repeat step (4) until the absolute error of the ionic strength is less than a threshond. A
threshold of 0.01 was used in the models, and 3-5 iterations were often needed before
22
terminating iterations.
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Fig. 17 The Mn/Fe molality ratios at a fixed 50 ppm (a) and 200 ppm (b) W concentration
For the case of W=50 ppm, the molalities of Mn and Fe were calculated from the models of
W-Mn-Cl-Na-O-H and W-Fe-Cl-Na-O-H, respectively. The dashed box represents the typical pH of
W-mineralizing fluids. More Mn than Fe is needed to form mineralizing fluids with the same W
concentration.
1. Fluid-buffered thermodynamic models were built for vein-type tungsten deposits.2. Tungsten solubility in acidic fluids is sensitive to temperature, pH, and salinity.3. MnWO4 and FeWO4 can be significantly dissolved in alkaline hydrothermal fluids.4. Tungsten solubility in alkaline fluids is insensitive to temperature and salinity.5. The Mn/Fe ratio of mineralizing fluids controls Mn/Fe ratios in wolframite.