Skip to main content

Advertisement

SpringerLink
Log in

Control and monitoring of oxygen fugacity in piston cylinder experiments

  • Original Paper
  • Published:
Contributions to Mineralogy and Petrology Aims and scope Submit manuscript

Abstract

We present a newly developed capsule design that resolves some common problems associated with the monitoring and control of oxygen fugacity (fO2) in high-pressure piston cylinder experiments. The new fO2 control assembly consists of an AuPd outer capsule enclosing two inner capsules: one of AuPd capsule containing the experimental charge (including some water), and the other of Pt containing a solid oxygen buffer plus water. The inner capsules are separated by crushable alumina. The outer capsule is surrounded by a Pyrex sleeve to simultaneously minimise hydrogen loss from the cell and carbon infiltration from the graphite furnace. Controlled fO2 experiments using this cell design were carried out at 1.0 GPa and 1,000 °C. We used NiPd, CoPd and (Ni, Mg)O fO2 sensors, whose pressure sensitivity is well calibrated, to monitor the redox states achieved in experiments buffered by Re–ReO2, Ni–NiO and Co–CoO, respectively. Results for the fO2 sensors are in good agreement with the intended fO2 established by the buffer, demonstrating excellent control for durations of 24–48 h, with uncertainties less than ± 0.3 log bar units of fO2.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Apted MJ (1982) Control of loss of iron to platinum capsules and effects on samarium partitioning between garnet and melt. Am Mineral 67:1069–1073

    Google Scholar 

  • Balta JB, Beckett JR, Asimow PD (2011) Thermodynamic properties of alloys of gold-74/palladium-26 with variable amount of iron and the use of Au–Pd–Fe alloys as containers for experimental petrology. Am Mineral 96:1467–1474. doi:10.2138/am.2011.3637

    Article  Google Scholar 

  • Barr AJ, Grove TL (2010) AuPdFe ternary solution model and applications to understanding the fO2 of hydrous, high-pressure experiments. Contrib Mineral Petrol 160(5):631–643. doi:10.1007/s00410-010-0497

    Article  Google Scholar 

  • Brey GP, Green DH (1976) Solubility of CO2 in olivine melilitite at high pressures and role of CO2 in the Earth’s upper mantle. Contrib Mineral Petrol 55:217–230

    Article  Google Scholar 

  • Brooker R, Holloway JR, Hervig R (1998) Reduction in piston-cylinder experiments: the detection of carbon infiltration into platinum capsules. Am Mineral 83:985–994

    Google Scholar 

  • Brooker RA, Kohn SC, Holloway JR, McMillan PF, Carroll MR (1999) Solubility, speciation and dissolution mechanisms for CO2 in melts on the NaAlO2–SiO2 join. GCA 63:3549–3565

    Google Scholar 

  • Bultitude RJ, Green DH (1971) Experimental study of crystal-liquid relationships at high pressures in olivine nephelinite and basanite compositions. J Petrol 12:121–147

    Article  Google Scholar 

  • Burgisser A, Scaillet B (2007) Redox evolution of a degassing magma rising to the surface. Nature 445:194–197. doi:10.1038/nature05509

    Article  Google Scholar 

  • Carmichael ISE (1991) The redox states of basic and silicic magmas: a reflection of their source regions? Contrib Mineral Petrol 106:129–141. doi:10.1007/BF00306429

    Article  Google Scholar 

  • Carmichael ISE, Ghiorso MS (1986) Oxidation-reduction relations in basic magma: a case for homogeneous equilibria. EPSL 78:200–210

    Article  Google Scholar 

  • Chou IM (1986) Permeability of precious metals to hydrogen at 2 kb total pressure and elevated temperatures. Am J Sci 286:638–658

    Article  Google Scholar 

  • Cottrell E, Kelley K, Lanzirotti A, Fischer R (2009) High-precision determination of iron oxidation state in silicate glasses using XANES. Chem Geol 268(3–4):167–179

    Article  Google Scholar 

  • Crabtree SM, Lange RA (2012) An evaluation of the effect of degassing on the oxidation state of hydrous andesite and dacite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations. Contrib Mineral Petrol 163:209–224

    Article  Google Scholar 

  • Creighton S, Stachel T, Matveev S, Höfer H, McCammon C, Luth RW (2009) Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism. Contrib Mineral Petrol 157:491–504

    Article  Google Scholar 

  • Eggler DH, Mysen BO, Hoering TC (1974) Gas species in sealed capsules in solid media, high pressure apparatus. Carnegie Inst Wash Year B 73:228–232

    Google Scholar 

  • Eugster HP (1957) Heterogeneous reactions involving oxidation and reduction at high pressures and temperature. J Chem Phys 26:1760–1761. doi:10.1063/1.1743626

    Article  Google Scholar 

  • Evans KA, Elburg MA, Kamenetsky VS (2012) Oxidation state of subarc mantle. Geology 40:783–786. doi:10.1130/G33037.1

    Article  Google Scholar 

  • Feig ST, Koepke J, Snow JE (2010) Effect of oxygen fugacity and water on phase equilibria of a hydrous tholeiitic basalt. Contrib Mineral Petrol 160:551–568. doi:10.1007/s00410-010-0493-3

    Article  Google Scholar 

  • Foley SF (2011) A reappraisal of redox melting in the Earth’s mantle as a function of tectonic setting and time. J Petrol 52:1363–1391. doi:10.1093/petrology/egq061

    Article  Google Scholar 

  • Freda C, Baker DR, Ottolini L (2001) Reduction of water loss from gold-palladium capsules during piston-cylinder experiments by use of pyrophyllite powder. Am Mineral 86:234–237

    Google Scholar 

  • Frost DJ, McCammon CA (2008) The redox state of Earth’s mantle. Annu Rev Earth Planet Sci 36:389–420

    Article  Google Scholar 

  • Giggenbach WF (1992) Magma degassing and mineral deposition in hydrothermal systems along convergent plate boundaries. Econ Geol 97:1927–1944

    Google Scholar 

  • Hall LJ, Brodie J, Wood BJ, Carroll MR (2004) Iron and water losses from hydrous basalts contained in Au80Pd20 capsules at high pressure and temperature. Mineral Mag 68:75–81

    Article  Google Scholar 

  • Humphreys MCS, Brooker RA, Fraser DG, Burgisser A, Mangan MT, McCammon C (in press) The interaction between volatile activity and Fe oxidation state during arc magma ascent. J Petrol

  • Ito K, Kennedy GC (1968) Melting and phase relations in the plane tholeiite-lherzolite-nepheline basanite system to 40 kbars with geological implications. Contrib Mineral Petrol 19:177–211

    Article  Google Scholar 

  • Jakobsson S (2012) Oxygen fugacity control in piston-cylinder experiments. Contrib Mineral Petrol 164:397–406. doi:10.1007/s00410-012-0743-7

    Article  Google Scholar 

  • Jakobsson S, Holloway JR (1986) Crystal–liquid experiments in the presence of a C–O–H fluid buffered by graphite + iron + wustite: experimental method and near-liquidus relations in basanite. J Volcanol Geotherm Res 29:265–291

    Article  Google Scholar 

  • Jakobsson S, Blundy J, Moore G (2014) Oxygen fugacity control in piston-cylinder experiments: a re-evaluation. Contrib Mineral Petrol 167:1007. doi:10.1007/s00410-014-1007-5

    Article  Google Scholar 

  • Jenner FE, O’Neill HSC, Arculus RJ, Mavrogenes JA (2010) The magnetite crisis in the evolution of arc-related magmas and the initial concentration of Au, Ag and Cu. J Petrol 51:2445–2464. doi:10.1093/petrologyegq063

    Article  Google Scholar 

  • Joyce DB, Holloway JR (1993) An experimental determination of the thermodynamic properties of H2O–CO2–NaCl fluids at high pressures and temperatures. GCA 57:733–746

    Google Scholar 

  • Kelley KA, Cottrell E (2009) Water and the oxidation state of subduction zone magmas. Science 325:605–607

    Article  Google Scholar 

  • Kelley KA, Cottrell E (2012) The influence of magmatic differentiation on the oxidation state of Fe in a basaltic arc magma. EPSL 329–330:109–121

    Article  Google Scholar 

  • Kessel R, Beckett JR, Stolper EM (2001) Thermodynamic properties of the Pt-Fe system. Am Mineral 86:1003–1014

    Google Scholar 

  • Kress VC (1997) Magma mixing as a source for Pinatubo sulphur. Nature 389:591–593

    Article  Google Scholar 

  • Kress VC, Carmichael ISE (1991) The compressibility of silicate liquids containing Fe2O3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states. Contrib Mineral Petrol 108:82–92. doi:10.1007/BF00307328

    Article  Google Scholar 

  • Lee C-TA, Leeman WP, Canil D, Li Z-XA (2005) Similar V/Sc systematics in MORB and arc basalts: implications for the oxygen fugacities of their mantle source regions. J Petrol 46:2313–2336

    Article  Google Scholar 

  • Lee C-TA, Luffi P, Le Roux V, Dasgupta R, Albarède F, Leeman WP (2010) The redox state of arc mantle using Zn/Fe systematics. Nature 468:681–685. doi:10.1038/nature09617

    Article  Google Scholar 

  • Li Y, Audètat A (2012) Partitioning of V, Mn Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions. EPSL 355–356:327–340. doi:10.1016/j.epsl.2012.08.008

    Article  Google Scholar 

  • Liu Y, Samaha NT, Baker DR (2007) Sulfur concentration at sulfide saturation (SCSS) in magmatic silicate melts. GCA 71:1783–1799. doi:10.1016/j.gca.2007.01.004

    Google Scholar 

  • Luth RW (1989) Natural versus experimental control of oxidation state: effects on the composition and speciation of C–O–H fluids. Am Minearal 74:50–57

    Google Scholar 

  • Mallmann G, O’Neill HSC (2009) The crystal/melt partitioning of V during mantle melting as a function of oxygen fugacity compared with some other elements (Al, P, Ca, Sc, Ti, Cr, Fe, Ga, Y, Zr and Nb). J Petrol 50(9):1765–1794. doi:10.1093/petrology/egp053

    Article  Google Scholar 

  • Matjuschkin V, Brey GP, Höfer HE, Woodland AB (2014) The influence of Fe3+ on garnet-orthopyroxene and garnet-olivine geothermometers. Contrib Mineral Petrol 167:972

    Article  Google Scholar 

  • Matzen AK, Baker MB, Beckett JR, Stolper EM (2011) Fe–Mg partitioning between olivine and high-magnesian melts and the nature of Hawaiian parental liquids. J Petrol 52:1243–1263. doi:10.1093/petrology/egq089

    Article  Google Scholar 

  • McDade P, Wood BJ, Van Westrenen W, Brooker R, Gudmundsson G, Soulard H, Najorka J, Blundy J (2002) Pressure corrections for a selection of piston-cylinder cell assemblies. Mineral Mag 66:1021–1028

    Article  Google Scholar 

  • Medard E, McCammon CA, Barr JA, Grove TL (2008) Oxygen fugacity, temperature reproducibility, and H2O contents of nominally anhydrous piston-cylinder experiments using graphite capsules. Am Mineral 93:1838–1844

    Article  Google Scholar 

  • O’Neill HSC, Mavrogenes JA (2002) The sulfide capacity and the sulfur content at sulfide saturation of silicate melts at 1,400 °C and 1 bar. J Petrol 43:1049–1087

    Article  Google Scholar 

  • O’Neill HSC, Pownceby MI (1993) Thermodynamic data from redox reactions at high temperatures. I. An experimental and theoretical assessment of the electrochemical method using stabilized zirconia electrolytes, with revised values for the Fe–“FeO”, Co–CoO, Ni–NiO and Cu–C2O oxygen buffers, and new data for W–WO2 buffer. Contrib Mineral Petrol 114:296–314

    Article  Google Scholar 

  • Ockwig NW, Nenoff TM (2007) Membranes for hydrogen separation. Chem Rev 107:4078–4110

    Article  Google Scholar 

  • Okamoto H, Massalski TB (1985) The Au–Pd (gold–palladium) system. J Phase Equilib 6(3):229–235

    Google Scholar 

  • Parkinson IJ, Arculus RJ (1999) The redox state of subduction zones: insights from arc-peridotites. Chem Geol 160:409–423

    Article  Google Scholar 

  • Patino Douce AE, Beard JS (1994) H2O loss from hydrous melts during fluid-absent piston cylinder experiments. Am Mineral 79:585–588

    Google Scholar 

  • Patino Douce AE, Beard JS (1995) Dehydration-melting of biotite gneiss and quartz amphi- bolite from 3 to 15 kbar. J Petrol 36:707–738

    Article  Google Scholar 

  • Pichavant M (1981) An experimental study of the effect of boron on a water-saturated haplogranite at 1 kbar pressure: geological applications. Contrib Mineral Petrol 76:430–439

    Article  Google Scholar 

  • Pownceby MI, O’Neill HSC (1994a) Thermodynamic data from redox reactions at high temperatures. IV. Calibrations of the Re–ReO2 oxygen buffer from EMF and NiO + Ni–Pd redox sensors measurements. Contrib Mineral Petrol 118:130–137

    Article  Google Scholar 

  • Pownceby MI, O’Neill HSC (1994b) Thermodynamic data from redox reactions at high temperatures. III. Activity-composition relations in Ni–Pd alloys from EMF measurements at 850–1,250 K, and calibration of the NiO + Ni–Pd assemblage as a redox sensor. Contrib Mineral Petrol 116:327–339. doi:10.1007/BF00306501

    Article  Google Scholar 

  • Pownceby MI, O’Neill HSC (2000) Thermodynamic data from redox reactions at high temperatures. VI. Thermodynamic properties of CoO–MnO solid solutions from emf measurements. Contrib Mineral Petrol 140:28–39. doi:10.1007/s004100000162

    Article  Google Scholar 

  • Ratajeski K, Sisson TW (1999) Loss of iron to gold in rock-melting experiments. Am Mineral 84:1521–1527

    Google Scholar 

  • Robie RA, Hemingway BS, Fisher JR (1978) 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; For sale by the Supt. of Docs., U.S. G.P.O., Bulletin 1452, iii, p 456. http://pubs.usgs.gov/bul/1452/report.pdf

  • Rohrbach A, Ballhaus C, Golla-Schindler U, Ulmer P, Kamenetsky VS, Kuzmin DV (2007) Metal saturation in the upper mantle. Nature 449:456–458. doi:10.1038/nature06183

    Article  Google Scholar 

  • Rosenbaum JM, Slagel MM (1995) C-O-H speciation in piston-cylinder experiments. Am Mineral 80:109–114

    Google Scholar 

  • Rushmer T (1991) Partial melting of two amphibolites: contrasting experimental results under fluid-absent conditions. Contrib Mineral Petrol 107:41–59. doi:10.1007/BF00311184

    Article  Google Scholar 

  • Scaillet B, Pichavant M, Roux J, Humbert G, Lefevre A (1992) Improvements of the Shaw membrane technique for measurement and control of fH2 at high temperatures and pressures. Am Mineral 77:647–655

    Google Scholar 

  • Schwerdtfeger K, Muan A (1965) Activity measurements in Pt-Ni, Pd-Ni, and Pd-Co alloys at 1,000 and 1,200 °C. Acta Metall 13:509–515

    Article  Google Scholar 

  • Serra E, Calza Bini A, Cosoli G, Pilloni L (2005) Hydrogen permeation measurements on alumina. J Am Ceram Soc 88(1):15–18. doi:10.1111/j.1551-2916.2004.00003.x

    Article  Google Scholar 

  • Sisson TW, Ratajeski K, Hankins WB, Glazner AF (2005) Voluminous granitic magmas from common basaltic sources. CMP 148:635–661

    Google Scholar 

  • Stamper CC, Melekhova E, Blundy JD, Arculus RJ, Humphreys MCS, Brooker RA (2014) Oxidised phase relations of a primitive basalt from Grenada, Lesser Antilles. CMP 167:954. doi:10.1007/s00410-013-0954-6

    Google Scholar 

  • Taylor WR, Green DH (1988) Measurement of reduced peridotite-C–O–H solidus and implications for redox melting of the mantle. Nature 332:349–352. doi:10.1038/332349a0

    Article  Google Scholar 

  • Taylor JR, Wall VJ, Pownceby MI (1992) The calibration and application of accurate redox sensors. Am Mineral 77:284–295

    Google Scholar 

  • Truckenbrodt J, Ziegenbein D, Johannes W (1997) Redox conditions in pisto-cylinder apparatus: the different behavior of boron nitride and unfired pyrophyllite assemblies. Am Mineral 82:337–344

    Google Scholar 

  • Uemiya S (1999) State-of-the-art of supported metal membranes for gas separation. Sep Purif Method 28(1):51–85. doi:10.1080/03602549909351644

    Article  Google Scholar 

  • Wendlandt RF, Huebner JS (1982) The redox potential of boron nitride and implications for its use as a crucible material in experimental petrology. Am Mineral 67:170–174

    Google Scholar 

  • Wood BJ, Bryndzia T, Johnson KE (1990) Mantle oxidation state and its relationship to tectonic environment and fluid speciation. Science 248:337–345

    Article  Google Scholar 

  • Yaxley GM, Berry AJ, Kamenetsky VS, Woodland AB, Golovin AV (2012) An oxygen fugacity profile through the Sibirean Craton: Fe K-edge XANES determination of Fe3+/ΣFe in garnets in peridotite xenoliths from the Udachnaya east kimberlite. Lithos 140–141:142–151. doi:10.1016/j.lithos.2012.01.016

    Article  Google Scholar 

Download references

Acknowledgments

CCS, RAB and JDB were funded by an ERC Advanced Grant (CRITMAG). VM, BT and JDB were funded by a research Grant from BHP Billiton. We would like to acknowledge members of Bristol Experimental Earth Study Group (BEEST) for helpful advice, in particular Dr. Susanne Skora for sharing their personal experience and helping in the lab. H. O’Neill is thanked for his help in conducting ‘JG’ piston cylinder experiments. The assistance of M.C.S. Humphreys in carrying of µXANES analyses is gratefully acknowledged, and we thank C-J. de Hoog for assistance with the SIMS analyses. Comments by JB Balta, RW Luth and an anonymous reviewer are much appreciated.

Author information

Authors and Affiliations

  1. School of Earth Sciences, University of Bristol, Wills Memorial Building, Queen’s Road, Bristol, BS8 1RJ, UK

    Vladimir Matjuschkin, Richard A. Brooker, Brian Tattitch, Jon D. Blundy & Charlotte C. Stamper

Authors
  1. Vladimir Matjuschkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Richard A. Brooker
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Brian Tattitch
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jon D. Blundy
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Charlotte C. Stamper
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vladimir Matjuschkin.

Additional information

Communicated by Jochen Hoefs.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 6667 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Matjuschkin, V., Brooker, R.A., Tattitch, B. et al. Control and monitoring of oxygen fugacity in piston cylinder experiments. Contrib Mineral Petrol 169, 9 (2015). https://doi.org/10.1007/s00410-015-1105-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00410-015-1105-z

Keywords

Search

Navigation