The effect of Cl on Pt solubility in haplobasaltic melt: Implications for micronugget formation and evidence for fluid transport of PGEs

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Original languageEnglish
Pages (from-to)7792-7805
Number of pages14
JournalGeochimica et Cosmochimica Acta
Volume75
Issue number24
Early online date17 Oct 2011
Publication statusPublished - 15 Dec 2011

Abstract

Platinum solubility was determined in a haplobasaltic, diopside-anorthite melt at 1523K and 0.2GPa as a function of oxygen fugacity and chlorine content. Synthetic glass powder of an An42Di58 composition was sealed in a platinum or platinum-iridium alloy capsule and equilibrated with a solid CaCl2 and MgCl2 chlorine source, water and the noble-metal capsule. All experiments were run in an internally-heated pressure-vessel equipped with a rapid-quench device with oxygen fugacity controlled by the water content and intrinsic hydrogen fugacity of the autoclave (MnO-Mn3O4). Resultant glasses were analyzed by isotope dilution ICP-MS and LA-ICP-MS to determine the solubility and distribution of Pt and assess potential Cl-complexation of Pt in the melt.Experiments with run durations longer than 96. h show Pt solubilities consistent with solubilities determined for the equivalent Cl-free diopside-anorthite system, under the same P-T conditions. These results indicate that chlorine has no discernable effect on Pt solubility and there is no evidence of Pt-Cl complexing in the silicate melt from 0.6 to 2.75. wt% Cl (saturation).However, products from short run duration experiments (<96. h) contain Pt concentrations which are orders of magnitude higher than those of the Pt-free starting glass and of the experimental products of the longer run duration experiments. These anomalously high levels are most pronounced in the shortest experiments and Pt concentration decreases with increasing run duration. It is suggested that this excess platinum is dissolved within the Cl-bearing fluid during the heating stages of the experiment and is left behind as the fluid dissolves into the melt leaving small amounts of Pt as " micronuggets" , increasing the bulk Pt concentration. With increasing run duration the platinum appears to migrate out of the melt, back to the capsule walls, decreasing the amount of Pt contained within the glass. This behavior offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt under magmatic conditions.Mass balance calculations on the excess amount of Pt in the glass (above inherent solubility) in short duration experiments lead to an estimation of Pt concentration in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. The correspondingly high estimated apparent partition coefficients of 103-104 suggest that Cl-bearing fluids can be highly efficient at enriching and transporting platinum in mafic magmatic-hydrothermal ore-forming systems. These values strongly contrast with recent experimental results in felsic systems, highlighting the potential importance of melt composition on partitioning, the need for composition specific partitioning experiments, as well as a detailed understanding of Pt distribution in experimental products.

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The effect of Cl on Pt solubility in haplobasaltic melt: Implications for micronugget formation and evidence for fluid transport of PGEs. / Blaine, F. A.; Linnen, R. L.; Holtz, Francois et al.
In: Geochimica et Cosmochimica Acta, Vol. 75, No. 24, 15.12.2011, p. 7792-7805.

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Blaine FA, Linnen RL, Holtz F, Bruegmann GE. The effect of Cl on Pt solubility in haplobasaltic melt: Implications for micronugget formation and evidence for fluid transport of PGEs. Geochimica et Cosmochimica Acta. 2011 Dec 15;75(24):7792-7805. Epub 2011 Oct 17. doi: 10.1016/j.gca.2011.10.010
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title = "The effect of Cl on Pt solubility in haplobasaltic melt: Implications for micronugget formation and evidence for fluid transport of PGEs",
abstract = "Platinum solubility was determined in a haplobasaltic, diopside-anorthite melt at 1523K and 0.2GPa as a function of oxygen fugacity and chlorine content. Synthetic glass powder of an An42Di58 composition was sealed in a platinum or platinum-iridium alloy capsule and equilibrated with a solid CaCl2 and MgCl2 chlorine source, water and the noble-metal capsule. All experiments were run in an internally-heated pressure-vessel equipped with a rapid-quench device with oxygen fugacity controlled by the water content and intrinsic hydrogen fugacity of the autoclave (MnO-Mn3O4). Resultant glasses were analyzed by isotope dilution ICP-MS and LA-ICP-MS to determine the solubility and distribution of Pt and assess potential Cl-complexation of Pt in the melt.Experiments with run durations longer than 96. h show Pt solubilities consistent with solubilities determined for the equivalent Cl-free diopside-anorthite system, under the same P-T conditions. These results indicate that chlorine has no discernable effect on Pt solubility and there is no evidence of Pt-Cl complexing in the silicate melt from 0.6 to 2.75. wt% Cl (saturation).However, products from short run duration experiments (<96. h) contain Pt concentrations which are orders of magnitude higher than those of the Pt-free starting glass and of the experimental products of the longer run duration experiments. These anomalously high levels are most pronounced in the shortest experiments and Pt concentration decreases with increasing run duration. It is suggested that this excess platinum is dissolved within the Cl-bearing fluid during the heating stages of the experiment and is left behind as the fluid dissolves into the melt leaving small amounts of Pt as {"} micronuggets{"} , increasing the bulk Pt concentration. With increasing run duration the platinum appears to migrate out of the melt, back to the capsule walls, decreasing the amount of Pt contained within the glass. This behavior offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt under magmatic conditions.Mass balance calculations on the excess amount of Pt in the glass (above inherent solubility) in short duration experiments lead to an estimation of Pt concentration in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. The correspondingly high estimated apparent partition coefficients of 103-104 suggest that Cl-bearing fluids can be highly efficient at enriching and transporting platinum in mafic magmatic-hydrothermal ore-forming systems. These values strongly contrast with recent experimental results in felsic systems, highlighting the potential importance of melt composition on partitioning, the need for composition specific partitioning experiments, as well as a detailed understanding of Pt distribution in experimental products.",
author = "Blaine, {F. A.} and Linnen, {R. L.} and Francois Holtz and Bruegmann, {G. E.}",
note = "Funding Information: The authors would like to thank J.D. Webster, J. Brenan and J. Mungall for their helpful and insightful reviews of this manuscript. This project was supported by the Hochschulvergabe Projekt N° 75 of the BGR ( German Geological Survey ), by the DFG ( German Science Foundation , project Ho 1337/9) and by the Natural Science and Engineering Research Council of Canada . We also gratefully acknowledge assistance by J. Berndt, B. Fryer, O. Diedrich, M. Freise, J. Gagnon, Y. Liu, M. Sierralta, and Y. Zhaoping. Copyright: Copyright 2011 Elsevier B.V., All rights reserved.",
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TY - JOUR

T1 - The effect of Cl on Pt solubility in haplobasaltic melt

T2 - Implications for micronugget formation and evidence for fluid transport of PGEs

AU - Blaine, F. A.

AU - Linnen, R. L.

AU - Holtz, Francois

AU - Bruegmann, G. E.

N1 - Funding Information: The authors would like to thank J.D. Webster, J. Brenan and J. Mungall for their helpful and insightful reviews of this manuscript. This project was supported by the Hochschulvergabe Projekt N° 75 of the BGR ( German Geological Survey ), by the DFG ( German Science Foundation , project Ho 1337/9) and by the Natural Science and Engineering Research Council of Canada . We also gratefully acknowledge assistance by J. Berndt, B. Fryer, O. Diedrich, M. Freise, J. Gagnon, Y. Liu, M. Sierralta, and Y. Zhaoping. Copyright: Copyright 2011 Elsevier B.V., All rights reserved.

PY - 2011/12/15

Y1 - 2011/12/15

N2 - Platinum solubility was determined in a haplobasaltic, diopside-anorthite melt at 1523K and 0.2GPa as a function of oxygen fugacity and chlorine content. Synthetic glass powder of an An42Di58 composition was sealed in a platinum or platinum-iridium alloy capsule and equilibrated with a solid CaCl2 and MgCl2 chlorine source, water and the noble-metal capsule. All experiments were run in an internally-heated pressure-vessel equipped with a rapid-quench device with oxygen fugacity controlled by the water content and intrinsic hydrogen fugacity of the autoclave (MnO-Mn3O4). Resultant glasses were analyzed by isotope dilution ICP-MS and LA-ICP-MS to determine the solubility and distribution of Pt and assess potential Cl-complexation of Pt in the melt.Experiments with run durations longer than 96. h show Pt solubilities consistent with solubilities determined for the equivalent Cl-free diopside-anorthite system, under the same P-T conditions. These results indicate that chlorine has no discernable effect on Pt solubility and there is no evidence of Pt-Cl complexing in the silicate melt from 0.6 to 2.75. wt% Cl (saturation).However, products from short run duration experiments (<96. h) contain Pt concentrations which are orders of magnitude higher than those of the Pt-free starting glass and of the experimental products of the longer run duration experiments. These anomalously high levels are most pronounced in the shortest experiments and Pt concentration decreases with increasing run duration. It is suggested that this excess platinum is dissolved within the Cl-bearing fluid during the heating stages of the experiment and is left behind as the fluid dissolves into the melt leaving small amounts of Pt as " micronuggets" , increasing the bulk Pt concentration. With increasing run duration the platinum appears to migrate out of the melt, back to the capsule walls, decreasing the amount of Pt contained within the glass. This behavior offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt under magmatic conditions.Mass balance calculations on the excess amount of Pt in the glass (above inherent solubility) in short duration experiments lead to an estimation of Pt concentration in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. The correspondingly high estimated apparent partition coefficients of 103-104 suggest that Cl-bearing fluids can be highly efficient at enriching and transporting platinum in mafic magmatic-hydrothermal ore-forming systems. These values strongly contrast with recent experimental results in felsic systems, highlighting the potential importance of melt composition on partitioning, the need for composition specific partitioning experiments, as well as a detailed understanding of Pt distribution in experimental products.

AB - Platinum solubility was determined in a haplobasaltic, diopside-anorthite melt at 1523K and 0.2GPa as a function of oxygen fugacity and chlorine content. Synthetic glass powder of an An42Di58 composition was sealed in a platinum or platinum-iridium alloy capsule and equilibrated with a solid CaCl2 and MgCl2 chlorine source, water and the noble-metal capsule. All experiments were run in an internally-heated pressure-vessel equipped with a rapid-quench device with oxygen fugacity controlled by the water content and intrinsic hydrogen fugacity of the autoclave (MnO-Mn3O4). Resultant glasses were analyzed by isotope dilution ICP-MS and LA-ICP-MS to determine the solubility and distribution of Pt and assess potential Cl-complexation of Pt in the melt.Experiments with run durations longer than 96. h show Pt solubilities consistent with solubilities determined for the equivalent Cl-free diopside-anorthite system, under the same P-T conditions. These results indicate that chlorine has no discernable effect on Pt solubility and there is no evidence of Pt-Cl complexing in the silicate melt from 0.6 to 2.75. wt% Cl (saturation).However, products from short run duration experiments (<96. h) contain Pt concentrations which are orders of magnitude higher than those of the Pt-free starting glass and of the experimental products of the longer run duration experiments. These anomalously high levels are most pronounced in the shortest experiments and Pt concentration decreases with increasing run duration. It is suggested that this excess platinum is dissolved within the Cl-bearing fluid during the heating stages of the experiment and is left behind as the fluid dissolves into the melt leaving small amounts of Pt as " micronuggets" , increasing the bulk Pt concentration. With increasing run duration the platinum appears to migrate out of the melt, back to the capsule walls, decreasing the amount of Pt contained within the glass. This behavior offers compelling evidence that Cl-bearing fluids have the capacity to transport significant amounts of Pt under magmatic conditions.Mass balance calculations on the excess amount of Pt in the glass (above inherent solubility) in short duration experiments lead to an estimation of Pt concentration in the Cl-bearing fluid ranging from tens to a few hundred ppm, versus ppb levels in the melt. The correspondingly high estimated apparent partition coefficients of 103-104 suggest that Cl-bearing fluids can be highly efficient at enriching and transporting platinum in mafic magmatic-hydrothermal ore-forming systems. These values strongly contrast with recent experimental results in felsic systems, highlighting the potential importance of melt composition on partitioning, the need for composition specific partitioning experiments, as well as a detailed understanding of Pt distribution in experimental products.

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