An experimentally-validated numerical model of diffusion and speciation of water in rhyolitic silicate melt

Jason, P Coumans, Ed Llewellin*, Madeleine C. S. Humphreys, Marcus Nowak, Richard A Brooker, Simon A Mathias, Iona M McIntosh

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

22 Downloads (Pure)


The diffusion of water through silicate melts is a key process in volcanic systems. Diffusion controls the growth of the bubbles that drive volcanic eruptions and determines the evolution of the spatial distribution of dissolved water during and after magma mingling, crystal growth, fracturing and fragmentation, and welding of pyroclasts. Accurate models for water diffusion are therefore essential for forward modelling of eruptive behaviour, and for inverse modelling to reconstruct eruptive and post-eruptive history from the spatial distribution of water in eruptive products. Existing models do not include the kinetics of the homogeneous species reaction that interconverts molecular (H2Om) and hydroxyl (OH) water; reaction kinetics are important because final species distribution depends on cooling history. Here we develop a flexible 1D numerical model for diffusion and speciation of water in silicate melts. We validate the model against FTIR transects of the spatial distribution of molecular, hydroxyl, and total water across diffusion-couple experiments of haplogranite composition, run at 800–1200°C and 5 kbar. We adopt a stepwise approach to analysing and modelling the data. First, we use the analytical Sauer-Freise method to determine the effective diffusivity of total water 퐷H2Ot as a function of dissolved water concentration 퐶H2Ot and temperature T for each experiment and find that the dependence of 퐷H2Ot on 퐶H2Ot is linear for 퐶H2Ot ≲ 1.8 wt.% and exponential for 퐶H2Ot ≳ 1.8 wt.%. Second, we develop a 1D numerical forward model, using the method of lines, to determine a piece-wise function for 퐷H2Ot (퐶H2Ot , 푇) that is globally-minimized against the entire experimental dataset. Third, we extend this numerical model to account for speciation of water and determine globally-minimized functions for diffusivity of molecular water 퐷H2Om (퐶H2Ot , 푇) and the equilibrium constant 퐾 for the speciation reaction. Our approach includes three key novelties: 1) functions for diffusivities of H2Ot and H2Om, and the speciation reaction, are minimized simultaneously against a large experimental dataset, covering a wide range of water concentration (0.25 ≤ 퐶H2Ot ≤ 7 wt.%) and temperature (800°퐶 ≤ 푇 ≤ 1200°퐶), such that the resulting functions are both mutually-consistent and broadly applicable; 2) the minimization allows rigorous and robust analysis of uncertainties such that the accuracy of the functions is quantified; 3) the model can be straightforwardly used to determine functions for diffusivity and speciation for other melt compositions pending suitable diffusion-couple experiments. The modelling approach is suitable for both forward and inverse modelling of diffusion processes in silicate melts; the model is available as a Matlab script from the electronic supplementary material.
Original languageEnglish
Pages (from-to)219-238
Number of pages20
JournalGeochimica et Cosmochimica Acta
Early online date2 Mar 2020
Publication statusPublished - 1 May 2020


  • silicate melts
  • magma
  • water diffusion
  • water speciation
  • diffusion modelling
  • Hydroxyl water
  • molecular water

Fingerprint Dive into the research topics of 'An experimentally-validated numerical model of diffusion and speciation of water in rhyolitic silicate melt'. Together they form a unique fingerprint.

Cite this