ISSN 0253-2778

CN 34-1054/N

Open AccessOpen Access JUSTC Earth and Space 22 November 2022

Chromium isotope fractionation during adsorption of chromium(III) by soils and river sediments

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https://doi.org/10.52396/JUSTC-2022-0085
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  • Author Bio:

    Ziyao Fang is an Associate Research Fellow at the University of Science and Technology of China (USTC). He received his Ph.D. degree from USTC in 2020. His research interests include metal stable isotope geochemistry, paleoenvironment reconstruction, and astrobiology

    Xiaoqing He is a Postdoctoral Researcher at the University of Science and Technology of China (USTC). She received her Ph.D. degree in Geology from USTC in 2020. Her research interests include metal stable isotope geochemistry, Earth’s surface processes, and paleoenvironment reconstruction

  • Corresponding author: E-mail: xqhe@ustc.edu.cn
  • Received Date: 26 May 2022
  • Accepted Date: 15 August 2022
  • Available Online: 22 November 2022
  • Chromium (Cr) isotope compositions of sedimentary rocks have been widely used to unravel fluctuations in atmospheric oxygen levels during geologic history. A fundamental framework of this application is that any Cr isotope fractionation in natural environments should be related to the redox transformation of Cr species [Cr(VI) and Cr(III)]. However, the behavior of Cr isotopes during non-redox Cr cycling is not yet well understood. Here, we present laboratory experimental results which show that redox-independent adsorption of Cr(III) by natural river sediments and soils can be accompanied by obvious Cr isotope fractionation. The observed Cr isotope fractionation factors (−0.06‰ – −0.95‰, expressed as 103lnα) are much smaller than those caused by redox processes. Combined with previous studies on redox-independent Cr isotope fractionation induced by ligand-promoted dissolution, we suggest that the systematic shift to highly fractionated Cr isotope compositions of sedimentary rocks is likely to represent atmospheric oxygenation, but muted signals observed in some geologic periods may be attributed to non-redox Cr cycling and should be interpreted with caution.
    Adsorption of Cr(III) by soils and river sediments during non-redox Cr cycling can cause Cr isotope fractionation.
    Chromium (Cr) isotope compositions of sedimentary rocks have been widely used to unravel fluctuations in atmospheric oxygen levels during geologic history. A fundamental framework of this application is that any Cr isotope fractionation in natural environments should be related to the redox transformation of Cr species [Cr(VI) and Cr(III)]. However, the behavior of Cr isotopes during non-redox Cr cycling is not yet well understood. Here, we present laboratory experimental results which show that redox-independent adsorption of Cr(III) by natural river sediments and soils can be accompanied by obvious Cr isotope fractionation. The observed Cr isotope fractionation factors (−0.06‰ – −0.95‰, expressed as 103lnα) are much smaller than those caused by redox processes. Combined with previous studies on redox-independent Cr isotope fractionation induced by ligand-promoted dissolution, we suggest that the systematic shift to highly fractionated Cr isotope compositions of sedimentary rocks is likely to represent atmospheric oxygenation, but muted signals observed in some geologic periods may be attributed to non-redox Cr cycling and should be interpreted with caution.
    • Non-redox adsorption of Cr(III) can result in Cr isotope fractionation.
    • The magnitudes of Cr isotope fractionation during non-redox processes are smaller than those during redox processes.
    • Slightly positively fractionated Cr isotope compositions of some sedimentary rocks cannot be exclusively linked to atmospheric oxygenation.

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Catalog

    Figure  1.  Schematic of non-redox Cr cycling. Stage I: Liberation of Cr(III) in the terrestrial silicate reservoir induced by biogenic organic ligands, acid or $ {\rm HCO}^{-}_3 $. Stage II: The soluble Cr(III) will be partly adsorbed during its transportation in rivers or underground streams. Stage III: Cr(III) in the ocean can be scavenged by multiple processes and preserved in sedimentary rocks such as IFs, carbonates, and shales.

    Figure  2.  Schematic for flow-through adsorption experiments (left) and bottle-incubation adsorption experiments (right).

    Figure  3.  XRD patterns of the soil and river sediment samples.

    Figure  4.  Cr isotope compositions of remaining Cr in solution versus the fraction of Cr adsorbed during Cr(III) adsorption experiments by soil (green symbols) and river sediments (blue symbols). Squares represent results from flow-through experiments, and circles represent results from bottle-incubation experiments. The gray solid line denotes the Cr isotope composition of the initial solution, and the gray dashed lines denote the measurement uncertainty (2SD). The yellow lines are the modelling results for isotope fractionation using the Rayleigh fractionation model with different isotope fractionation factors α, and the violet lines are the calculation results assuming equilibrium fractionation.

    Figure  5.  (a) Compilation of Cr isotope compositions of sedimentary rocks throughout Earth history from the literature[4, 18, 22, 3680]. The gray band indicates the range for igneous reservoir[13]. (b) Boxplot of the Cr isotope data at 100 million-year intervals. The box comprises the 25th and 75th percentiles, the black square in the box denotes the mean value, the line in the box represents the median value, the whiskers are the 2.5th and 97.5th percentiles, and the hollow dots are outliers.

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