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Title: Distribution and speciation of trace elements in iron and manganese oxide cave deposits

Abstract

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redox conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associatedmore » with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Authors:
;  [1]
  1. (WU)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
OTHERNSF
OSTI Identifier:
1046850
Resource Type:
Journal Article
Journal Name:
Geochim. Cosmochim. Acta
Additional Journal Information:
Journal Volume: 91; Journal Issue: 08, 2012; Journal ID: ISSN 0016-7037
Country of Publication:
United States
Language:
ENGLISH
Subject:
54 ENVIRONMENTAL SCIENCES; ABSORPTION; ADSORPTION; AQUIFERS; COATINGS; DISTRIBUTION; ELECTRON TRANSFER; ELEMENTS; FINE STRUCTURE; FLUORESCENCE; HEAVY METALS; IRON; LAND USE; MANGANESE OXIDES; OXIDE MINERALS; OXIDES; SEDIMENTS; SOILS; SPATIAL DISTRIBUTION; SPECTROSCOPY; TRACE AMOUNTS

Citation Formats

Frierdich, Andrew J., and Catalano, Jeffrey G. Distribution and speciation of trace elements in iron and manganese oxide cave deposits. United States: N. p., 2012. Web. doi:10.1016/j.gca.2012.05.032.
Frierdich, Andrew J., & Catalano, Jeffrey G. Distribution and speciation of trace elements in iron and manganese oxide cave deposits. United States. doi:10.1016/j.gca.2012.05.032.
Frierdich, Andrew J., and Catalano, Jeffrey G. Wed . "Distribution and speciation of trace elements in iron and manganese oxide cave deposits". United States. doi:10.1016/j.gca.2012.05.032.
@article{osti_1046850,
title = {Distribution and speciation of trace elements in iron and manganese oxide cave deposits},
author = {Frierdich, Andrew J. and Catalano, Jeffrey G.},
abstractNote = {Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redox conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.},
doi = {10.1016/j.gca.2012.05.032},
journal = {Geochim. Cosmochim. Acta},
issn = {0016-7037},
number = 08, 2012,
volume = 91,
place = {United States},
year = {2012},
month = {10}
}