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  4. Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II)
 
research article

Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II)

Schwab, Lorenz  
•
Gallati, Niklas
•
Reiter, Sofie M.
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September 25, 2023
Environmental Science & Technology

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 +/- 0.16% (epsilon Hg-202) and 0.21 +/- 0.02% ((EHg)-Hg-199). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 +/- 0.17%(epsilon Hg-202) and 0.34 +/- 0.02% ((EHg)-Hg-199). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 +/- 0.07 and 0.13 +/- 0.01%), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 +/- 0.003% ((EHg)-Hg-200) and approximate to -0.02 +/- 0.01% ((EHg)-Hg-204) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger epsilon compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

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Type
research article
DOI
10.1021/acs.est.3c03703
Web of Science ID

WOS:001071975700001

Author(s)
Schwab, Lorenz  
Gallati, Niklas
Reiter, Sofie M.
Kimber, Richard L.
Kumar, Naresh
McLagan, David S.
Biester, Harald
Kraemer, Stephan M.
Wiederhold, Jan G.
Date Issued

2023-09-25

Publisher

Amer Chemical Soc

Published in
Environmental Science & Technology
Volume

57

Issue

40

Start page

15243

End page

15254

Subjects

Technology

•

Life Sciences & Biomedicine

•

Mercury

•

Isotopes

•

Redox Processes

•

Reduction

•

Process Tracing

•

Rayleigh Fractionation

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
SOIL  
FunderGrant Number

Austrian Science Fund (FWF)

I-3489-N28

German Research Foundation (DFG)

BI 734/17-1

Austrian Science Fund (FWF)

Available on Infoscience
February 14, 2024
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/203689
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