Using Chromium Stable Isotope Ratios To Quantify Cr(VI) Reduction: Lack of Sorption Effects
Abstract
Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr(VI) and Cr(VI) adsorbed onto gamma-Al2O3 and goethite is less than 0.04 per thousand (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO4(2-) was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in delta53Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.
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Cr isotope fractionation from non-redox processes such as mineral precipitation or adsorption is currently considered negligible.
“Cr isotope fractionations associated with non-redox-dependent processes such as precipitation of mineral phases (e.g., oxides) or adsorption onto mineral surfaces are currently thought to be negligible”
From The chromium isotope composition of reducing and oxic marine sediments (2016) · cites this paper as Ellis et al., 2004
Chromium sorption onto iron and aluminum oxides is not accompanied by isotope fractionation.
“experimental data showing that Cr sorption onto Fe-and Al-oxides (i.e., the primary mineral phases that host Cr in oxic sediments) is not accompanied by isotope fractionation (Ellis et al., 2004).”
From The chromium isotope composition of reducing and oxic marine sediments (2016) · cites this paper as Ellis et al., 2004
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- Authors
- Ellis, A. S., Johnson, T. M., & Bullen, T. D.
- Affiliations
- United States Geological Survey (US)
- Venue
- Environmental Science & Technology
- Publisher
- American Chemical Society (ACS)
- Published
- 2004-05-21
- Volume
- 38
- Issue
- 13
- Pages
- 3604-3607
- ISSN
- 0013-936X (ISSN-L)
- 1520-5851
- OpenAlex
- W1963978426
- Cited by
- 169
- References
- 28
- Citations by year
- 2026: 7 · 2025: 3 · 2024: 3 · 2023: 8 · 2022: 5 · 2021: 7 · 2020: 6 · 2019: 14 · 2018: 17 · 2017: 14 · 2016: 11 · 2015: 12 · 2014: 12 · 2013: 6 · 2012: 11
- FWCI
- 1.04
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Environmental Science & Technology (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Bayer
- Division of Earth Sciences
- Topics
- Physical Sciences › Environmental Science › Health, Toxicology and Mutagenesis › Chromium effects and bioremediation
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Groundwater and Isotope Geochemistry
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Keywords
- hexavalent chromium reduction, isotope fractionation, sorption, goethite, gamma-alumina, transport modeling, kinetic isotope effects
- MeSH terms
- Absorption, Chromium, Chromium Isotopes, Chemical Fractionation, Fresh Water, Hydrogen-Ion Concentration, Kinetics, Minerals, Models, Chemical, Oxidation-Reduction, Water Pollutants, Chemical, Iron Compounds
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