Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg2SiO4) When Water Is Limited

Mergelsberg, Sebastian T.; Rajan, Bavan P.; Legg, Benjamin A.; Kovarik, Libor; Burton, Sarah D.; Bowers, Geoffrey M.; Bowden, Mark E.; Qafoku, Odeta; Thompson, Christopher J.; Kerisit, Sebastien N.; Ilton, Eugene S.; Loring, John S.

doi:10.1021/acs.estlett.2c00866

Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg₂SiO₄) When Water Is Limited

Journal Article · Tue Dec 27 23:00:00 EST 2022 · Environmental Science & Technology Letters (Online)

DOI:https://doi.org/10.1021/acs.estlett.2c00866· OSTI ID:1909803

^[1]; Rajan, Bavan P. ^[2]; Legg, Benjamin A. ^[1]; Kovarik, Libor ^[1]; ^[1]; ^[3]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; Loring, John S. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Rice Univ., Houston, TX (United States)
St. Mary’s College of Maryland, St. Mary’s City, MD (United States)

Passivation of silicate surfaces by accumulated reaction products is an obstacle to efficient CO₂ mineralization. In this study, we investigate a unique passivation effect during the carbonation of the basalt mineral forsterite (Mg₂SiO₄) in humid supercritical CO₂ (50 °C, 90 bar). Using in situ high-pressure infrared spectroscopy, we demonstrate that dissolution of forsterite into a thin water film slows significantly after reaction for ˜24 h, even under far-from-equilibrium conditions. Further, ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy detects a highly polymerized amorphous silica at this stage. On the basis of transmission electron microscopy and energy dispersive X-ray spectroscopy, we show that the silica is present as a Mg-depleted layer that is just 2–3 nm thick on the reacted forsterite particles. The decrease in the level of forsterite dissolution in the presence of an extraordinarily thin Mg-depleted layer can be strongly linked to properties of the thin fluid film at the surface, highlighting the importance of water during mineral carbonation. This study furthers our understanding of silicate mineral carbonation under select low-water, humidified fluid conditions relevant to basaltic geologic reservoirs, recovery of critical elements by carbonation of mafic ores, and sequestration of atmospheric CO₂ by enhanced rock weathering.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1909803

Report Number(s):: PNNL-SA-178504

Journal Information:: Environmental Science & Technology Letters (Online), Journal Name: Environmental Science & Technology Letters (Online) Journal Issue: 1 Vol. 10; ISSN 2328-8930

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg2SiO4) When Water Is Limited

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Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg₂SiO₄) When Water Is Limited