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Title: Quantitative Antimony Speciation in Shooting-Range Soils by EXAFS Spectroscopy

Abstract

The Sb speciation in soil samples from Swiss shooting ranges was determined using Sb K-edge X-ray absorption spectroscopy (XAS) and advanced statistical data analysis methods (iterative transformation factor analysis, ITFA). The XAS analysis was supported by a spectral data set of 13 Sb minerals and 4 sorption complexes. In spite of a high variability in geology, soil pH (3.1-7.5), Sb concentrations (1000-17,000 mg/kg) and shooting-range history, only two Sb species were identified. In the first species, Sb is surrounded solely by other Sb atoms at radial distances of 2.90, 3.35, 4.30 and 4.51 Angstroms, indicative of metallic Sb(0). While part of this Sb(0) may be hosted by unweathered bullet fragments consisting of PbSb alloy, Pb L{sub III}-edge XAS of the soil with the highest fraction (0.75) of Sb(0) showed no metallic Pb, but only Pb{sup 2+} bound to soil organic matter. This suggests a preferential oxidation of Pb in the alloy, driven by the higher standard reduction potential of Sb. In the second species, Sb is coordinated to 6 O-atoms at a distance of 1.98 Angstroms, indicative of Sb(V). This oxidation state is further supported by an edge energy of 30,496-30,497 eV for the soil samples with <10% Sb(0). Ironmore » atoms at radial distances of 3.10 and 3.56 Angstroms from Sb atoms are in line with edge-sharing and bidentate corner-sharing linkages between Sb(O,OH)6 and Fe(O,OH)6 octahedra. While similar structural units exist in tripuhyite, the absence of Sb neighbors contradicts formation of this Fe antimonate. Hence the second species most likely consists of inner-sphere sorption complexes on Fe oxides, with edge and corner-sharing configuration occurring simultaneously. This pentavalent Sb species was present in all samples, suggesting that it is the prevailing species after weathering of metallic Sb(0) in oxic soils. No indication of Sb(III) was found.« less

Authors:
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Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
914126
Report Number(s):
BNL-78694-2007-JA
Journal ID: ISSN 0016-7037; GCACAK; TRN: US200804%%530
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Geochim. Cosmochim. Acta
Additional Journal Information:
Journal Volume: 70; Journal Issue: 13; Journal ID: ISSN 0016-7037
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION SPECTROSCOPY; ANTIMONY; ATOMS; CONFIGURATION; GEOLOGY; IRON; ORGANIC MATTER; OXIDATION; OXIDES; SOILS; SORPTION; SPECTROSCOPY; STATISTICAL DATA; TRANSFORMATIONS; WEATHERING; national synchrotron light source

Citation Formats

Scheinost, A, Rossberg, A, Vantelon, D, Xifra, I, Kretzschmar, R, Leuz, A, Funke, H, and Johnson, C. Quantitative Antimony Speciation in Shooting-Range Soils by EXAFS Spectroscopy. United States: N. p., 2006. Web. doi:10.1016/j.gca.2006.03.020.
Scheinost, A, Rossberg, A, Vantelon, D, Xifra, I, Kretzschmar, R, Leuz, A, Funke, H, & Johnson, C. Quantitative Antimony Speciation in Shooting-Range Soils by EXAFS Spectroscopy. United States. https://doi.org/10.1016/j.gca.2006.03.020
Scheinost, A, Rossberg, A, Vantelon, D, Xifra, I, Kretzschmar, R, Leuz, A, Funke, H, and Johnson, C. 2006. "Quantitative Antimony Speciation in Shooting-Range Soils by EXAFS Spectroscopy". United States. https://doi.org/10.1016/j.gca.2006.03.020.
@article{osti_914126,
title = {Quantitative Antimony Speciation in Shooting-Range Soils by EXAFS Spectroscopy},
author = {Scheinost, A and Rossberg, A and Vantelon, D and Xifra, I and Kretzschmar, R and Leuz, A and Funke, H and Johnson, C},
abstractNote = {The Sb speciation in soil samples from Swiss shooting ranges was determined using Sb K-edge X-ray absorption spectroscopy (XAS) and advanced statistical data analysis methods (iterative transformation factor analysis, ITFA). The XAS analysis was supported by a spectral data set of 13 Sb minerals and 4 sorption complexes. In spite of a high variability in geology, soil pH (3.1-7.5), Sb concentrations (1000-17,000 mg/kg) and shooting-range history, only two Sb species were identified. In the first species, Sb is surrounded solely by other Sb atoms at radial distances of 2.90, 3.35, 4.30 and 4.51 Angstroms, indicative of metallic Sb(0). While part of this Sb(0) may be hosted by unweathered bullet fragments consisting of PbSb alloy, Pb L{sub III}-edge XAS of the soil with the highest fraction (0.75) of Sb(0) showed no metallic Pb, but only Pb{sup 2+} bound to soil organic matter. This suggests a preferential oxidation of Pb in the alloy, driven by the higher standard reduction potential of Sb. In the second species, Sb is coordinated to 6 O-atoms at a distance of 1.98 Angstroms, indicative of Sb(V). This oxidation state is further supported by an edge energy of 30,496-30,497 eV for the soil samples with <10% Sb(0). Iron atoms at radial distances of 3.10 and 3.56 Angstroms from Sb atoms are in line with edge-sharing and bidentate corner-sharing linkages between Sb(O,OH)6 and Fe(O,OH)6 octahedra. While similar structural units exist in tripuhyite, the absence of Sb neighbors contradicts formation of this Fe antimonate. Hence the second species most likely consists of inner-sphere sorption complexes on Fe oxides, with edge and corner-sharing configuration occurring simultaneously. This pentavalent Sb species was present in all samples, suggesting that it is the prevailing species after weathering of metallic Sb(0) in oxic soils. No indication of Sb(III) was found.},
doi = {10.1016/j.gca.2006.03.020},
url = {https://www.osti.gov/biblio/914126}, journal = {Geochim. Cosmochim. Acta},
issn = {0016-7037},
number = 13,
volume = 70,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}