Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which is attributed to reduction of the highly soluble perrhenate ion (Re(VII)O4-) to insoluble Re(IV) species. Anoxic sediments typically contain Fe(II) and sulfide species, which could potentially reduce Re(VII) to Re(IV). In this study, we examined the interactions of KReO4 with magnetite (Fe3O4), siderite (FeCO3), vivianite (Fe3(PO4)2•8H2O), green rust (mixed Fe(II)/Fe(III) layered double hydroxide), mackinawite (FeS), and chemically reduced nontronite (NAu-1) using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to determine the valence state and speciation of Re. Uptake of Re by green rust was rapid, with ~50% associated with the solids within 2 days. In contrast, there was <10% uptake by the other Fe(II) phases over 48 days. Reduction of Re(VII) to Re(IV) was only observed in the presence of green rust, producing clusters of bidentate-coordinated Re(IV)O6 octahedra.. These results suggest that except for green rust, the potential for other Fe(II)-bearing minerals to act as reductants for ReO4- in sedimentary environments requires further investigation.
Kilber, Anthony W. N., et al. "Interactions of Perrhenate (Re(VII)O<sub>4</sub><sup>-</sup>) with Fe(II)-Bearing Minerals." Minerals, vol. 14, no. 2, Feb. 2024. https://doi.org/10.3390/min14020181
Kilber, Anthony W. N., Boyanov, Maxim I., Kemner, Kenneth M., & O’Loughlin, Edward J. (2024). Interactions of Perrhenate (Re(VII)O<sub>4</sub><sup>-</sup>) with Fe(II)-Bearing Minerals. Minerals, 14(2). https://doi.org/10.3390/min14020181
Kilber, Anthony W. N., Boyanov, Maxim I., Kemner, Kenneth M., et al., "Interactions of Perrhenate (Re(VII)O<sub>4</sub><sup>-</sup>) with Fe(II)-Bearing Minerals," Minerals 14, no. 2 (2024), https://doi.org/10.3390/min14020181
@article{osti_2468633,
author = {Kilber, Anthony W. N. and Boyanov, Maxim I. and Kemner, Kenneth M. and O’Loughlin, Edward J.},
title = {Interactions of Perrhenate (Re(VII)O<sub>4</sub><sup>-</sup>) with Fe(II)-Bearing Minerals},
annote = {Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which is attributed to reduction of the highly soluble perrhenate ion (Re(VII)O4-) to insoluble Re(IV) species. Anoxic sediments typically contain Fe(II) and sulfide species, which could potentially reduce Re(VII) to Re(IV). In this study, we examined the interactions of KReO4 with magnetite (Fe3O4), siderite (FeCO3), vivianite (Fe3(PO4)2•8H2O), green rust (mixed Fe(II)/Fe(III) layered double hydroxide), mackinawite (FeS), and chemically reduced nontronite (NAu-1) using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to determine the valence state and speciation of Re. Uptake of Re by green rust was rapid, with ~50% associated with the solids within 2 days. In contrast, there was 6 octahedra.. These results suggest that except for green rust, the potential for other Fe(II)-bearing minerals to act as reductants for ReO4- in sedimentary environments requires further investigation.},
doi = {10.3390/min14020181},
url = {https://www.osti.gov/biblio/2468633},
journal = {Minerals},
issn = {ISSN 2075-163X},
number = {2},
volume = {14},
place = {United States},
publisher = {MDPI},
year = {2024},
month = {02}}
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER). Earth & Environmental Systems Science (EESS); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)