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Title: A first principles method to determine speciation of carbonates in supercritical water

Journal Article · · Nature Communications
ORCiD logo [1];  [2]
  1. Hong Kong Univ. of Science and Technolgoy (China); HKUST Fok Ying Tung Research Inst., Guangzhou (China)
  2. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
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The determination of the speciation of ions and molecules in supercritical aqueous fluids under pressure is critical to understanding their mass transport in the Earth's interior. Unfortunately, there is no experimental technique yet available to directly characterize species dissolved in water at extreme conditions. Here we present a strategy, based on first-principles simulations, to determine ratios of Raman scattering cross-sections of aqueous species under extreme conditions, thus providing a key quantity that can be used, in conjunction with Raman measurements, to predict chemical speciation in aqueous fluids. Due to the importance of the Earth's carbon cycle, we focus on carbonate and bicarbonate ions. Our calculations up to 11 GPa and 1000 K indicate a higher concentration of bicarbonates in water than previously considered at conditions relevant to the Earth's upper mantle, with important implications for the transport of carbon in aqueous fluids in the Earth's interior.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Advanced Materials for Energy-Water Systems (AMEWS)
Sponsoring Organization:
Alfred P. Sloan Foundation; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1630419
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 11; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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