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Title: Field Validation of Supercritical CO 2 Reactivity with Basalts

Abstract

Continued global use of fossil fuels places a premium on developing technology solutions to minimize increases in atmospheric CO 2 levels. CO 2 storage in reactive basalts might be one of these solutions by permanently converting injected gaseous CO 2 into solid carbonates. Herein we report results from a field demonstration where ~1000 MT of CO 2 was injected into a natural basalt formation in Eastern Washington State. Following two years of post-injection monitoring, cores were obtained from within the injection zone and subjected to detailed physical and chemical analysis. Nodules found in vesicles throughout the cores were identified as the carbonate mineral, ankerite Ca[Fe, Mg, Mn](CO 3) 2. Carbon isotope analysis showed the nodules are chemically distinct as compared with natural carbonates present in the basalt and clear correlation with the isotopic signature of the injected CO 2. These findings provide field validation of rapid mineralization rates observed from years of laboratory testing with basalts.

Authors:
; ORCiD logo; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1344633
Report Number(s):
PNNL-SA-119127
Journal ID: ISSN 2328-8930; 48820; AA7050000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Environmental Science & Technology Letters; Journal Volume: 4; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; Environmental Molecular Sciences Laboratory

Citation Formats

McGrail, B. Peter, Schaef, Herbert T., Spane, Frank A., Cliff, John B., Qafoku, Odeta, Horner, Jake A., Thompson, Christopher J., Owen, Antoinette T., and Sullivan, Charlotte E.. Field Validation of Supercritical CO 2 Reactivity with Basalts. United States: N. p., 2017. Web. doi:10.1021/acs.estlett.6b00387.
McGrail, B. Peter, Schaef, Herbert T., Spane, Frank A., Cliff, John B., Qafoku, Odeta, Horner, Jake A., Thompson, Christopher J., Owen, Antoinette T., & Sullivan, Charlotte E.. Field Validation of Supercritical CO 2 Reactivity with Basalts. United States. doi:10.1021/acs.estlett.6b00387.
McGrail, B. Peter, Schaef, Herbert T., Spane, Frank A., Cliff, John B., Qafoku, Odeta, Horner, Jake A., Thompson, Christopher J., Owen, Antoinette T., and Sullivan, Charlotte E.. Tue . "Field Validation of Supercritical CO 2 Reactivity with Basalts". United States. doi:10.1021/acs.estlett.6b00387.
@article{osti_1344633,
title = {Field Validation of Supercritical CO 2 Reactivity with Basalts},
author = {McGrail, B. Peter and Schaef, Herbert T. and Spane, Frank A. and Cliff, John B. and Qafoku, Odeta and Horner, Jake A. and Thompson, Christopher J. and Owen, Antoinette T. and Sullivan, Charlotte E.},
abstractNote = {Continued global use of fossil fuels places a premium on developing technology solutions to minimize increases in atmospheric CO2 levels. CO2 storage in reactive basalts might be one of these solutions by permanently converting injected gaseous CO2 into solid carbonates. Herein we report results from a field demonstration where ~1000 MT of CO2 was injected into a natural basalt formation in Eastern Washington State. Following two years of post-injection monitoring, cores were obtained from within the injection zone and subjected to detailed physical and chemical analysis. Nodules found in vesicles throughout the cores were identified as the carbonate mineral, ankerite Ca[Fe, Mg, Mn](CO3)2. Carbon isotope analysis showed the nodules are chemically distinct as compared with natural carbonates present in the basalt and clear correlation with the isotopic signature of the injected CO2. These findings provide field validation of rapid mineralization rates observed from years of laboratory testing with basalts.},
doi = {10.1021/acs.estlett.6b00387},
journal = {Environmental Science & Technology Letters},
number = 1,
volume = 4,
place = {United States},
year = {Tue Jan 10 00:00:00 EST 2017},
month = {Tue Jan 10 00:00:00 EST 2017}
}
  • The anionic cluster (HRu{sub 3}(CO){sub 8}({mu}-PPh{sub 2}){sub 2}){sup {minus}} (1) is obtained from the reaction of (HRu{sub 3}(CO){sub 11}){sup {minus}} with PPh{sub 2}H in THF solution. The solid-state structure of 1 has been determined by a single-crystal X-ray analysis of the bis(triphenylphosphine)iminium salt. Crystals are triclinic, space group P{anti 1}, with Z = 2 in a unit cell of dimensions a = 14.690 (6), b = 18.652 (4), c = 12.150 (2) {angstrom}, {alpha} = 106.60 (2), {beta} = 92.17 (2), {gamma} = 95.89 (2){degree}. The reaction of 1 with Wilkinson's catalyst, (PPh{sub 3}){sub 3}RhCl, leads to the formation ofmore » (H{sub 2}Ru{sub 3}Rh({mu}-CO)(CO){sub 6}(PPh{sub 3}){sub 2}({mu}-PPh{sub 2})(PPhC{sub 6}H{sub 4})) (2), and with Vaska's complex, (PPh{sub 3}){sub 2}Ir(CO)Cl, the cluster (H{sub 2}Ru{sub 3}Ir({mu}-CO)(CO){sub 7}(PPh{sub 3})({mu}-Pph{sub 2})(PPhC{sub 6}H{sub 4})) (3) is obtained.« less
  • Basalt samples representing five different formations were immersed in water equilibrated with supercritical carbon dioxide containing 1% hydrogen sulfide (H2S) at reservoir conditions (100 bar, 90°C) for up to 3.5 years. Surface coatings in the form of pyrite and metal cation substituted carbonates were identified as reaction products associated with all five basalts. In some cases, high pressure tests contained excess H2S, which produced the most corroded basalts and largest amount of secondary products. In comparison, tests containing limited amounts of H2S appeared least reacted with significantly less concentrations of reaction products. In all cases, pyrite appeared to precede carbonation,more » and in some instances, was observed in the absence of carbonation such as in cracks, fractures, and within the porous glassy mesostasis. Armoring reactions from pyrite surface coatings observed in earlier shorter duration tests were found to be temporary with carbonate mineralization observed with all the basalts tested in these long duration experiments. Geochemical simulations conducted with the geochemical code EQ3/6 accurately predicted early pyrite precipitation followed by formation of carbonates. Reactivity with H2S was correlated with measured Fe(II)/Fe(III) ratios in the basalts with more facile pyrite formation occurring with basalts containing more Fe(III) phases. These experimental and modeling results confirm potential for long term sequestration of acid gas mixtures in continental flood basalt formations.« less
  • Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less
  • Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less
  • The chemical reactivity of the linear tetranuclear ruthenium cluster toward CO was determined. The conversion of the ligands under exclusion of light took from 3 days to 2 weeks and was reversible. The X-ray crystal structure has also been determined. 44 refs., 1 fig., 5 tabs.