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Selenium isotope fractionation during adsorption by Fe, Mn and Al oxides TEXT SIZE: A A A
Adsorption plays an important role in the biogeochemical cycling of selenium (Se) in natural environments and Se isotope fractionation during adsorption is a significant but poorly studied part of Se isotope system. This paper examined Se(IV) and Se(VI) adsorption onto four naturally occurring metal oxides (hematite, manganese dioxide (beta-MnO2), and alpha and gamma-alumina oxides) and revealed Se isotope fractionation as a function of the absorbents used, Se species adsorbed, exposure time, and pH. The results show that Se(IV)/(VI) adsorption was initially rapid and was accompanied with kinetic isotope fractionations as large as 3 parts per thousand, but slowed down as adsorption equilibrium was approached, eventually approaching isotopic equilibrium. The Se(IV) adsorption onto the studied metal oxides took at least 12 h to reach adsorption equilibrium, longer than Se (VI) adsorption (<60 min). At adsorption equilibrium, Se(IV) adsorption onto Fe and Mn oxides induces significant isotope fractionation, with lighter Se isotopes preferentially adsorbed, whereas Se(IV) adsorption onto Al oxides causes only small fractionation: Delta Se-82/76(dissolved-adsorbed) = delta Se-82/76(dissolved) - delta Se-82/76(adsorbed) is 0.87 +/- 0.12 parts per thousand for hematite, 1.24 +/- 0.05 parts per thousand for beta-MnO(2, )0.08 +/- 0.10 parts per thousand for alpha-alumina, and 0.05 +/- 0.09 parts per thousand for gamma-alumina at pH 5. In contrast to Se(IV) adsorption, Se(VI) adsorption does not induce detectable Se isotope fractionation. The contrasting Se isotope fractionation between Se(IV) and Se(VI) adsorption is likely related to the mechanism of adsorption onto metal oxides, which causes a structural difference between dissolved and adsorbed Se(IV)/Se(VI). In addition, pH had a strong influence on Se isotope fractionation during Se (IV) adsorption onto beta-MnO2: Delta Se-82/76(dissolved-adsorbed) varied from 1.24 parts per thousand to -0.08 parts per thousand as pH increased from 5 to 8. However, there was little pH effect on Se isotope fractionation during adsorption onto Fe (consistently at 0.7-0.9 parts per thousand) and Al oxide (consistently at similar to 0 parts per thousand). Our findings show that, beside abiotic and biotic reduction, Se(IV) adsorption onto Fe-Mn oxides is potentially another important process that can induce Se isotope fractionation in Earth's surface environments. This moves an important step toward correctly reconstructing the Se isotopic composition of seawater using Fe-Mn nodules or crusts. (C) 2020 Elsevier Ltd. All rights reserved.
 

Publication name

 GEOCHIMICA ET COSMOCHIMICA ACTA Volume: 272 Pages: 121-136 DOI: 10.1016/j.gca.2020.01.001 Published: MAR 1 2020

Author(s)

 Xu, Wenpo; Zhu, Jian-Ming; Johnson, Thomas M.; Wang, Xiangli; Lin, Zhi-Qing; Tan, Decan; Qin, Haibo

Corresponding author(s) 

 ZHU Jianming
 jmzhu@cugb.edu.cn
 -China Univ Geosci, State Key Lab Geol Proc & Mineral Resources, Beijing 100083, Peoples R China.
 Johnson, Thomas M.
 tmjohnsn@illinois.edu  
 -Univ Illinois, Dept Geol, Urbana, IL 61801 USA.

Author(s) from IGCAS   XU Wenpo; TAN Decan; QIN Haibo

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