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C–O–H–S fluids and granitic magma: how S partitions and modifies CO2 concentrations of fluid-saturated felsic melt at 200 MPa

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Abstract

Hydrothermal volatile-solubility and partitioning experiments were conducted with fluid-saturated haplogranitic melt, H2O, CO2, and S in an internally heated pressure vessel at 900°C and 200 MPa; three additional experiments were conducted with iron-bearing melt. The run-product glasses were analyzed by electron microprobe, FTIR, and SIMS; and they contain ≤0.12 wt% S, ≤0.097 wt% CO2, and ≤6.4 wt% H2O. Apparent values of log f O2 for the experiments at run conditions were computed from the [(S6+)/(S6++S2−)] ratio of the glasses, and they range from NNO −0.4 to NNO + 1.4. The C–O–H–S fluid compositions at run conditions were computed by mass balance, and they contained 22–99 mol% H2O, 0–78 mol% CO2, 0–12 mol% S, and <3 wt% alkalis. Eight S-free experiments were conducted to determine the H2O and CO2 concentrations of melt and fluid compositions and to compare them with prior experimental results for C–O–H fluid-saturated rhyolite melt, and the agreement is excellent. Sulfur partitions very strongly in favor of fluid in all experiments, and the presence of S modifies the fluid compositions, and hence, the CO2 solubilities in coexisting felsic melt. The square of the mole fraction of H2O in melt increases in a linear fashion, from 0.05 to 0.25, with the H2O concentration of the fluid. The mole fraction of CO2 in melt increases linearly, from 0.0003 to 0.0045, with the CO2 concentration of C–O–H–S fluids. Interestingly, the CO2 concentration in melts, involving relatively reduced runs (log f O2 ≤ NNO + 0.3) that contain 2.5–7 mol% S in the fluid, decreases significantly with increasing S in the system. This response to the changing fluid composition causes the H2O and CO2 solubility curve for C–O–H–S fluid-saturated haplogranitic melts at 200 MPa to shift to values near that modeled for C–O–H fluid-saturated, S-free rhyolite melt at 150 MPa. The concentration of S in haplogranitic melt increases in a linear fashion with increasing S in C–O–H–S fluids, but these data show significant dispersion that likely reflects the strong influence of f O2 on S speciation in melt and fluid. Importantly, the partitioning of S between fluid and melt does not vary with the (H2O/H2O + CO2) ratio of the fluid. The fluid-melt partition coefficients for H2O, CO2, and S and the atomic (C/S) ratios of the run-product fluids are virtually identical to thermodynamic constraints on volatile partitioning and the H, S, and C contents of pre-eruptive magmatic fluids and volcanic gases for subduction-related magmatic systems thus confirming our experiments are relevant to natural eruptive systems.

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Acknowledgments

We appreciate thoughtful reviews by Editor Tim Grove and two anonymous referees. We also wish to recognize discussions on analytical methods with Charles Mandeville. Our thanks are offered to Professor David London of the University of Oklahoma who provided the haplogranite starting glass and Professor Harald Behrens of the University of Hannover, Germany, who provided two synthetic glasses with measured H2O contents that were used to test our FTIR analyses. Robert Bodnar and Charles Farley, of Virginia Tech, kindly conducted Raman analyses of 9 of the run-product glasses to determine the dominant volatile species in the vesicles. This research was supported in part by National Science Foundation awards EAR 0308866 and EAR-0836741 to J.D.W.

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Authors and Affiliations

  1. Department of Earth and Planetary Sciences, American Museum of Natural History, Central Park West at 79th Street, New York, NY, 10024-5192, USA

    J. D. Webster & B. Goldoff

  2. Geology and Geophysics Department, Woods Hole Oceanographic Institution, 360 Woods Hole Road, MS 23, Woods Hole, MA, 02543-1541, USA

    N. Shimizu

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  1. J. D. Webster
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  2. B. Goldoff
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Correspondence to J. D. Webster.

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Communicated by T. L. Grove.

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Webster, J.D., Goldoff, B. & Shimizu, N. C–O–H–S fluids and granitic magma: how S partitions and modifies CO2 concentrations of fluid-saturated felsic melt at 200 MPa. Contrib Mineral Petrol 162, 849–865 (2011). https://doi.org/10.1007/s00410-011-0628-1

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