The solubility of nantokite (CuCl(s)) and Cu speciation in low-density fluids near the critical isochore: An in-situ XAS study

Liu, Weihua; Brugger, Joël; Etschmann, Barbara; Testemale, Denis; Hazemann, Jean‐Louis

doi:10.1016/j.gca.2008.05.056

Cited by 43 publications

(24 citation statements)

References 65 publications

(118 reference statements)

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“…0.02-0.09 g/cm 3 ( Table 1). The bond distance and angles are consistent with results of the in situ X-ray absorption spectroscopy (XAS) studies of Cu(I)-Cl and Cu(I)-HS complexes [6,12,32]. The CuCl distance determined in these simulations is also similar to that determined by Mei et al [14] for the linear CuCl 2 − complex for high-density (0.67-1.03 g/cm 3 ) solutions and higher ionic strength (4 m Cl − ) at 300 ∘ C. Table 2.…”

Section: Hydration Number and H-bondssupporting

confidence: 83%

“…In contrast, in low-density vapors, there is increasing experimental evidence showing that, aside from the fugacity of HCl 0 , the solubility of Cu minerals is controlled primarily by fluid density, which correlates with the fugacity of water. Specifically, mineral solubility increases exponentially with increasing fluid density in HCl-bearing water vapor [3,11,12].…”

Section: Introductionmentioning

confidence: 99%

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CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

et al. 2018

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We investigated the hydration of the CuCl 0 complex in HCl-bearing water vapor at 350 ∘ C and a vapor-like fluid density between 0.02 and 0.09 g/cm 3 using ab initio molecular dynamics (MD) simulations. The simulations reveal that one water molecule is strongly bonded to Cu(I) (first coordination shell), forming a linear [H 2 O-Cu-Cl] 0 moiety. The second hydration shell is highly dynamic in nature, and individual configurations have short life-spans in such low-density vapors, resulting in large fluctuations in instantaneous hydration numbers over a timescale of picoseconds. The average hydration number in the second shell (m) increased from ∼0.5 to ∼3.5 and the calculated number of hydrogen bonds per water molecule increased from 0.09 to 0.25 when fluid density (which is correlated to water activity) increased from 0.02 to 0.09 g/cm 3 ( H 2 O 1.72 to 2.05). These changes of hydration number are qualitatively consistent with previous solubility studies under similar conditions, although the absolute hydration numbers from MD were much lower than the values inferred by correlating experimental Cu fugacity with water fugacity. This could be due to the uncertainties in the MD simulations and uncertainty in the estimation of the fugacity coefficients for these highly nonideal "vapors" in the experiments. Our study provides the first theoretical confirmation that beyond-first-shell hydrated metal complexes play an important role in metal transport in low-density hydrothermal fluids, even if it is highly disordered and dynamic in nature.

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Section: Hydration Number and H-bondssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

et al. 2018

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“…The metal concentrations in these MD simulations are high compared to the concentrations in natural fluids (Liu W et al, 2008;Seward and Barnes, 1997;Sherman, 2007;Etschmann et al, 2010 (Driesner et al, 1998;Harris et al, 2001;Sherman, 2001;2010;Sherman and Collings, 2002); however, in ab initio MD, it is very costly in terms of CPU time (Hutter and Curioni, 2005). In this study, for a typical MD simulation with 173 atoms and a box length of 13.066 Å, it took ~16 hours to obtain one picosecond by parallel calculations using 24 cores.…”

Section: Simulations Vs Experimentsmentioning

confidence: 79%

Ab initio molecular dynamics simulation and free energy exploration of copper(I) complexation by chloride and bisulfide in hydrothermal fluids

Mei

Sherman

Liu

et al. 2013

Geochimica et Cosmochimica Acta

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Ab initio molecular dynamics simulation and free energy exploration of copper(I) complexation by chloride and bisulfide in hydrothermal fluids Geochimica et Cosmochimica Acta, 2013; 102:45-64 © 2012 Elsevier Ltd. All rights reserved. NOTICE: this is the author's version of a work that was accepted for publication in Geochimica et Cosmochimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Geochimica et Cosmochimica Acta, 2013; 102:45-64 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.Ab initio MD simulation of Cu(I) complexation

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“…The importance of bisulfide complexes for the transport of base metals (Cu, Pb and Zn) has been proposed in magmatic vapors and low density supercritical fluids, because reduced sulfur will partition preferentially into the low density phase during immiscibility (Heinrich et al, 1992;Mavrogenes et al, 2002;Williams-Jones and Heinrich, 2005;Liu et al, 2008;Seo et al, 2009). In contrast, the current consensus assumes that Cu, Pb, and Zn are transported as chloride complexes in high density magmatic fluids (e.g., Yardley, 2005;Lukanin et al, 2013).…”

Section: Implications For Hydrothermal Mineralizationmentioning

confidence: 99%

Contrasting regimes of Cu, Zn and Pb transport in ore-forming hydrothermal fluids

et al. 2015

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The solubility of nantokite (CuCl(s)) and Cu speciation in low-density fluids near the critical isochore: An in-situ XAS study

Cited by 43 publications

References 65 publications

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics simulation and free energy exploration of copper(I) complexation by chloride and bisulfide in hydrothermal fluids

Contrasting regimes of Cu, Zn and Pb transport in ore-forming hydrothermal fluids

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