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Root size and soil physicochemical properties drive microscale spatial patterns of Fe and As retention in the rice rhizosphere

Background and Aims: Radial oxygen loss from rice roots in flooded soils oxidizes and precipitates dissolved Fe(II), Mn(II), and As(III) into mixed Fe(III), Mn(III/IV), and As(V) as root plaque and in the rhizosphere soil. It is unknown how different soils and root sizes impact the spatial extent of Fe and As retention outside the root. Methods: We imaged cross-sections of 90 roots from 6 different soils using synchrotron μXRF imaging followed by k-means clustering and elliptical averaging to distinguish bulk soil, rhizosphere, plaque, and roots based on As and Fe patterns. Results: We found preferential As retention in the plaque and rhizospheres of most roots except small (< 0.45 mm) roots in silty soils with low P or high As. In contrast, clayey soils had similar As-Fe correlations across plaque, rhizosphere, and bulk soil. Large (> 0.45 mm) roots often had no oxidized rhizosphere region. We obtained an extensive dataset of 256 As and 155 Mn synchrotron μXANES measurements, which revealed that rhizosphere and plaque As was mainly inorganic As(V) and As(III), and Mn oxidation state varied between soils but not between belowground locations. Conclusion: Small roots in coarse-textured soils were less likely to have As retention in the plaque or rhizosphere compared to large roots and fine-textured soils. Furthermore, the unique and extensive data in this study provides new insight into soil and root size impacts on As retention in the rhizosphere. It is essential to investigate a representative number of samples to draw conclusions from XRF imaging.

36 MATERIALS SCIENCE↗

Materials Data on Fe12As5 by Materials Project

Fe12As5 crystallizes in the trigonal R32 space group. The structure is three-dimensional. there are four inequivalent Fe sites. In the first Fe site, Fe is bonded in a 2-coordinate geometry to ten Fe and four As atoms. There are a spread of Fe–Fe bond distances ranging from 2.47–2.87 Å. There are two shorter (2.66 Å) and two longer (2.77 Å) Fe–As bond lengths. In the second Fe site, Fe is bonded in a 4-coordinate geometry to three equivalent Fe and four As atoms. There are a spread of Fe–As bond distances ranging from 2.38–2.63 Å. In the third Fe site, Fe is bonded in a distorted trigonal non-coplanar geometry to three equivalent Fe and three equivalent As atoms. All Fe–As bond lengths are 2.35 Å. In the fourth Fe site, Fe is bonded in a trigonal bipyramidal geometry to five As atoms. There are two shorter (2.33 Å) and three longer (2.34 Å) Fe–As bond lengths. There are two inequivalent As sites. In the first As site, As is bonded in a 9-coordinate geometry to nine Fe atoms. In the second As site, As is bonded in a 10-coordinate geometry to ten Fe atoms.

36 MATERIALS SCIENCE↗

Materials Data on FeAs2 by Materials Project

FeAs2 is zeta iron carbide structured and crystallizes in the orthorhombic Pnnm space group. The structure is three-dimensional. Fe3+ is bonded to six equivalent As+1.50- atoms to form a mixture of corner and edge-sharing FeAs6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are two shorter (2.36 Å) and four longer (2.39 Å) Fe–As bond lengths. As+1.50- is bonded in a 4-coordinate geometry to three equivalent Fe3+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Fe2As by Materials Project

Fe2As crystallizes in the tetragonal P4/nmm space group. The structure is three-dimensional. there are two inequivalent Fe sites. In the first Fe site, Fe is bonded in a 5-coordinate geometry to five equivalent As atoms. There are one shorter (2.42 Å) and four longer (2.61 Å) Fe–As bond lengths. In the second Fe site, Fe is bonded to four equivalent As atoms to form a mixture of distorted edge and corner-sharing FeAs4 tetrahedra. All Fe–As bond lengths are 2.39 Å. As is bonded in a 9-coordinate geometry to nine Fe atoms.

36 MATERIALS SCIENCE↗

Materials Data on FeAs by Materials Project

FeAs is Modderite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Fe3+ is bonded to six equivalent As3- atoms to form a mixture of distorted corner, edge, and face-sharing FeAs6 octahedra. The corner-sharing octahedra tilt angles range from 44–56°. There are a spread of Fe–As bond distances ranging from 2.32–2.50 Å. As3- is bonded in a 6-coordinate geometry to six equivalent Fe3+ atoms.

36 MATERIALS SCIENCE↗