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Title: Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C

Abstract

The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 degrees C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at similar to 300 degrees C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental datamore » are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 degrees C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D-Zr similar to 10(-25) m(2)/s at 650 degrees C and similar to 10(-30) m(2)/s at 250 degrees C) with diffusion length-scales of <0.2 mu m in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change during the experiment, and the measured concentration of Zr in the fluid was used to calculate the concentration of Ti (i.e., the solubility of rutile) in the fluid. The salts NaF, NaCl, and KCl were systematically added to the aqueous fluid, and the relative effects of fluid composition, pressure, and temperature on rutile solubility were quantified. The results indicate that fluid composition exerts the greatest control on rutile solubility in aqueous fluid, consistent with previous studies, and that increasing temperature has a positive, albeit less pronounced, effect. The solubility of Zr-rutile in aqueous fluid increases with the addition of halides in the following order: 2 wt% NaF < 30 wt% KCl < 30 wt% NaCl < 3 wt% NaF < (10 wt% NaCl + 2 wt% NaF) < 4 wt% NaF. The solubility of rutile in the fluid increases with the 2nd to 3rd power of the Cl- concentration, and the 3rd to 4th power of the F- concentration. These new data are consistent with observations from field studies of exhumed terranes that indicate that rutile is soluble in complex aqueous fluids, and that fluid composition is the primary control on rutile solubility and HFSE mobility« less

Authors:
 [1];  [1];  [1];  [2];  [2];  [3];  [4];  [2]
  1. Univ. of Michigan, Ann Arbor, MI (United States). Earth & Environmental Sciences
  2. Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab., High Pressure Collaborative Access Team (HPCAT)
  3. Memorial Univ. of Newfoundland (Canada)
  4. Univ. of Nevada, Las Vegas, NV (United States). HiPSEC; Univ. of Nevada, Las Vegas, NV (United States). Dept. of Geoscience
Publication Date:
Research Org.:
Univ. of Nevada, Las Vegas, NV (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Canadian Natural Sciences and Research Council (NSERC)
OSTI Identifier:
1332399
Alternate Identifier(s):
OSTI ID: 1328137
Grant/Contract Number:  
NA0001982; NA0001974; FG02-99ER45775; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 177; Journal Issue: C; Journal ID: ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; SUBDUCTION-ZONE FLUIDS; DIAMOND-ANVIL CELL; TI-NB-TA; HIGH-PRESSURE; ZIRCON SOLUBILITY; HIGH-TEMPERATURES; TRACE-ELEMENTS; SILICATE MELTS; MOBILITY; ECLOGITES

Citation Formats

Tanis, Elizabeth A., Simon, Adam, Zhang, Youxue, Chow, Paul, Xiao, Yuming, Hanchar, John M., Tschauner, Oliver, and Shen, Guoyin. Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C. United States: N. p., 2016. Web. doi:10.1016/j.gca.2016.01.003.
Tanis, Elizabeth A., Simon, Adam, Zhang, Youxue, Chow, Paul, Xiao, Yuming, Hanchar, John M., Tschauner, Oliver, & Shen, Guoyin. Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C. United States. https://doi.org/10.1016/j.gca.2016.01.003
Tanis, Elizabeth A., Simon, Adam, Zhang, Youxue, Chow, Paul, Xiao, Yuming, Hanchar, John M., Tschauner, Oliver, and Shen, Guoyin. Thu . "Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C". United States. https://doi.org/10.1016/j.gca.2016.01.003. https://www.osti.gov/servlets/purl/1332399.
@article{osti_1332399,
title = {Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C},
author = {Tanis, Elizabeth A. and Simon, Adam and Zhang, Youxue and Chow, Paul and Xiao, Yuming and Hanchar, John M. and Tschauner, Oliver and Shen, Guoyin},
abstractNote = {The complex nature of trace element mobility in subduction zone environments is thought to be primarily controlled by fluid-rock interactions, episodic behavior of fluids released, mineral assemblages, and element partitioning during phase transformations and mineral breakdown throughout the transition from hydrated basalt to blueschist to eclogite. Quantitative data that constrain the partitioning of trace elements between fluid(s) and mineral(s) are required in order to model trace element mobility during prograde and retrograde metamorphic fluid evolution in subduction environments. The stability of rutile has been proposed to control the mobility of HFSE during subduction, accounting for the observed depletion of Nb and Ta in arc magmas. Recent experimental studies demonstrate that the solubility of rutile in aqueous fluids at temperatures >700 degrees C and pressures <2 GPa increases by several orders of magnitude relative to pure H2O as the concentrations of ligands (e.g., F and Cl) in the fluid increase. Considering that prograde devolatilization in arcs begins at similar to 300 degrees C, there is a need for quantitative constraints on rutile solubility and the partitioning of HFSE between rutile and aqueous fluid over a wider range of temperature and pressure than is currently available. In this study, new experimental data are presented that quantify the solubility of rutile in aqueous fluids from 0.5 to 2.79 GPa and 250 to 650 degrees C. Rutile solubility was determined by using synchrotron X-ray fluorescence to measure the concentration of Zr in an aqueous fluid saturated with a Zr-bearing rutile crystal within a hydrothermal diamond anvil cell. At the PT conditions of the experiments, published diffusion data indicate that Zr is effectively immobile (log D-Zr similar to 10(-25) m(2)/s at 650 degrees C and similar to 10(-30) m(2)/s at 250 degrees C) with diffusion length-scales of <0.2 mu m in rutile for our run durations (<10 h). Hence, the Zr/Ti ratio of the starting rutile, which was quantified, does not change during the experiment, and the measured concentration of Zr in the fluid was used to calculate the concentration of Ti (i.e., the solubility of rutile) in the fluid. The salts NaF, NaCl, and KCl were systematically added to the aqueous fluid, and the relative effects of fluid composition, pressure, and temperature on rutile solubility were quantified. The results indicate that fluid composition exerts the greatest control on rutile solubility in aqueous fluid, consistent with previous studies, and that increasing temperature has a positive, albeit less pronounced, effect. The solubility of Zr-rutile in aqueous fluid increases with the addition of halides in the following order: 2 wt% NaF < 30 wt% KCl < 30 wt% NaCl < 3 wt% NaF < (10 wt% NaCl + 2 wt% NaF) < 4 wt% NaF. The solubility of rutile in the fluid increases with the 2nd to 3rd power of the Cl- concentration, and the 3rd to 4th power of the F- concentration. These new data are consistent with observations from field studies of exhumed terranes that indicate that rutile is soluble in complex aqueous fluids, and that fluid composition is the primary control on rutile solubility and HFSE mobility},
doi = {10.1016/j.gca.2016.01.003},
journal = {Geochimica et Cosmochimica Acta},
number = C,
volume = 177,
place = {United States},
year = {2016},
month = {1}
}

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Works referenced in this record:

A new diamond anvil cell for hydrothermal studies to 2.5 GPa and from −190 to 1200 °C
journal, August 1993

  • Bassett, W. A.; Shen, A. H.; Bucknum, M.
  • Review of Scientific Instruments, Vol. 64, Issue 8
  • DOI: 10.1063/1.1143931

Solubility of rutile in subduction zone fluids, as determined by experiments in the hydrothermal diamond anvil cell
journal, April 2005


Rutile solubility and mobility in supercritical aqueous fluids
journal, January 1993

  • Ayers, John C.; Watson, E. Bruce
  • Contributions to Mineralogy and Petrology, Vol. 114, Issue 3
  • DOI: 10.1007/BF01046535

Zircon solubility in aqueous fluids at high temperatures and pressures
journal, October 2013


On the Origin of High-Alumina Arc Basalt and the Mechanics of Melt Extraction
journal, August 1986


Zr-in-rutile thermometry in eclogite at Jinheqiao in the Dabie orogen and its geochemical implications
journal, March 2008


Zr and Hf diffusion in rutile
journal, September 2007

  • Cherniak, D. J.; Manchester, J.; Watson, E. B.
  • Earth and Planetary Science Letters, Vol. 261, Issue 1-2
  • DOI: 10.1016/j.epsl.2007.06.027

Equations of state of MgO, Au, Pt, NaCl-B1, and NaCl-B2: Internally consistent high-temperature pressure scales
journal, December 2007


Rutile/melt partition coefficients for trace elements and an assessment of the influence of rutile on the trace element characteristics of subduction zone magmas
journal, March 2000


Growth of early continental crust controlled by melting of amphibolite in subduction zones
journal, June 2002

  • Foley, Stephen; Tiepolo, Massimo; Vannucci, Riccardo
  • Nature, Vol. 417, Issue 6891
  • DOI: 10.1038/nature00799

Mobilization of Ti–Nb–Ta during subduction: Evidence from rutile-bearing dehydration segregations and veins hosted in eclogite, Tianshan, NW China
journal, October 2007


Experimental evidence for the role of accessory phases in magma genesis
journal, July 1981


Raman studies on species in aqueous solutions. Part II. Oxy-species of metals of Groups VIA, VA, and IVA
journal, January 1967

  • Griffith, W. P.; Wickins, T. D.
  • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
  • DOI: 10.1039/j19670000675

Rare earth elements in synthetic zircon: Part 1. Synthesis, and rare earth element and phosphorus doping
journal, May 2001

  • Hanchar, John M.; Finch, Robert J.; Hoskin, Paul W. O.
  • American Mineralogist, Vol. 86, Issue 5-6
  • DOI: 10.2138/am-2001-5-607

Rutile solubility in supercritical NaAlSi3O8–H2O fluids
journal, May 2011


Dehydration of subducting serpentinite: Implications for halogen mobility in subduction zones and the deep halogen cycle
journal, August 2011

  • John, Timm; Scambelluri, Marco; Frische, Matthias
  • Earth and Planetary Science Letters, Vol. 308, Issue 1-2
  • DOI: 10.1016/j.epsl.2011.05.038

Volcanic arcs fed by rapid pulsed fluid flow through subducting slabs
journal, May 2012

  • John, Timm; Gussone, Nikolaus; Podladchikov, Yuri Y.
  • Nature Geoscience, Vol. 5, Issue 7
  • DOI: 10.1038/ngeo1482

HFSE residence and Nb/Ta ratios in metasomatised, rutile-bearing mantle peridotites
journal, May 2002


Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones
journal, May 2005

  • Klemme, Stephan; Prowatke, Stefan; Hametner, Kathrin
  • Geochimica et Cosmochimica Acta, Vol. 69, Issue 9
  • DOI: 10.1016/j.gca.2004.11.015

Ti(IV) hydrolysis constants derived from rutile solubility measurements made from 100 to 300°C
journal, July 2001


Zr complexation in high pressure fluids and silicate melts and implications for the mobilization of HFSE in subduction zones
journal, March 2013

  • Louvel, Marion; Sanchez-Valle, Carmen; Malfait, Wim J.
  • Geochimica et Cosmochimica Acta, Vol. 104
  • DOI: 10.1016/j.gca.2012.11.001

The chemistry of subduction-zone fluids
journal, June 2004


Rutile solubility in albite-H2O and Na2Si3O7-H2O at high temperatures and pressures by in-situ synchrotron radiation micro-XRF
journal, August 2008

  • Manning, Craig E.; Wilke, Max; Schmidt, Christian
  • Earth and Planetary Science Letters, Vol. 272, Issue 3-4
  • DOI: 10.1016/j.epsl.2008.06.004

Thermodynamic properties of aqueous NaCl solutions to 1073 K and 4.5 GPa, and implications for dehydration reactions in subducting slabs
journal, November 2013

  • Mantegazzi, Davide; Sanchez-Valle, Carmen; Driesner, Thomas
  • Geochimica et Cosmochimica Acta, Vol. 121
  • DOI: 10.1016/j.gca.2013.07.015

Rutile and its applications in earth sciences
journal, September 2010


Dielectric properties of water under extreme conditions and transport of carbonates in the deep Earth
journal, March 2013

  • Pan, D.; Spanu, L.; Harrison, B.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 17
  • DOI: 10.1073/pnas.1221581110

Speciation and Transport of Metals and Metalloids in Geological Vapors
journal, January 2013

  • Pokrovski, G. S.; Borisova, A. Y.; Bychkov, A. Y.
  • Reviews in Mineralogy and Geochemistry, Vol. 76, Issue 1
  • DOI: 10.2138/rmg.2013.76.6

Extremely high solubility of rutile in chloride and fluoride-bearing metamorphic fluids: An experimental investigation
journal, April 2010

  • Rapp, J. F.; Klemme, S.; Butler, I. B.
  • Geology, Vol. 38, Issue 4
  • DOI: 10.1130/G30753.1

Rutile saturation in magmas: implications for TiNbTa depletion in island-arc basalts
journal, December 1987


Dissolution of strontianite at high P-T conditions: An in-situ synchrotron X-ray fluorescence study
journal, July 2003

  • Sanchez-Valle, Carmen; Martinez, Isabelle; Daniel, Isabelle
  • American Mineralogist, Vol. 88, Issue 7
  • DOI: 10.2138/am-2003-0705

Tracer impurity diffusion in single-crystal rutile (TiO2−x)
journal, January 1985


Transverse geochemical variations across the Antarctic Peninsula: Implications for the genesis of calc-alkaline magmas
journal, February 1980

  • Saunders, Andrew D.; Tarney, John; Weaver, Stephen D.
  • Earth and Planetary Science Letters, Vol. 46, Issue 3
  • DOI: 10.1016/0012-821X(80)90050-3

In situ synchrotron-radiation XRF study of REE phosphate dissolution in aqueous fluids to 800 °C
journal, April 2007


Diamond formation due to a pH drop during fluid–rock interactions
journal, November 2015

  • Sverjensky, Dimitri A.; Huang, Fang
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9702

Solubility of xenotime in a 2 M HCl aqueous fluid from 1.2 to 2.6 GPa and 300 to 500  C
journal, September 2012

  • Tanis, E. A.; Simon, A.; Tschauner, O.
  • American Mineralogist, Vol. 97, Issue 10
  • DOI: 10.2138/am.2012.4009

The mobility of Nb in rutile-saturated NaCl- and NaF-bearing aqueous fluids from 1–6.5 GPa and 300–800 °C
journal, July 2015

  • Tanis, Elizabeth A.; Simon, Adam; Tschauner, Oliver
  • American Mineralogist, Vol. 100, Issue 7
  • DOI: 10.2138/am-2015-5031

Zircon solubility and zirconium complexation in H2O+Na2O+SiO2±Al2O3 fluids at high pressure and temperature
journal, October 2012

  • Wilke, Max; Schmidt, Christian; Dubrail, Julien
  • Earth and Planetary Science Letters, Vol. 349-350
  • DOI: 10.1016/j.epsl.2012.06.054

Fluorine partitioning between hydrous minerals and aqueous fluid at 1GPa and 770–947°C: A new constraint on slab flux
journal, October 2013


Trace element abundances in rutiles from eclogites and associated garnet mica schists
journal, March 2002


Works referencing / citing this record:

Silicate, Oxide and Sulphide Trends in Neo-Archean Rocks from the Nilgiri Block, Southern India: the Role of Fluids During High-grade Metamorphism
journal, May 2019

  • Samuel, Vinod O.; Harlov, Daniel E.; Kwon, Sanghoon
  • Journal of Petrology, Vol. 60, Issue 5
  • DOI: 10.1093/petrology/egz023

TiO 2 Solubility and Nb and Ta Partitioning in Rutile-Silica-Rich Supercritical Fluid Systems: Implications for Subduction Zone Processes
journal, June 2018

  • Chen, Wei; Xiong, Xiaolin; Wang, Jintuan
  • Journal of Geophysical Research: Solid Earth, Vol. 123, Issue 6
  • DOI: 10.1029/2018jb015808

High-pressure studies with x-rays using diamond anvil cells
journal, November 2016


Fluids, Metals, and Mineral/Ore Deposits
journal, January 2018


A genetic link between magnetite mineralization and diorite intrusion at the El Romeral iron oxide-apatite deposit, northern Chile
journal, January 2018