A Review of the Development of Cr, Se, U, Sb, and Te Isotopes as Indicators of Redox Reactions, Contaminant Fate, and Contaminant Transport in Aqueous Systems

Druhan, Jennifer L.; Basu, Amiya K.; Jemison, Noah; Wang, Xiangli; Schilling, Kathrin; Wasserman, Naomi L.

doi:10.1002/9781119595007.ch10

Cited by 9 publications

(10 citation statements)

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“…HG is the preferred method for precise Se isotope ratio measurements in complex matrices, 24 relying on quantitative Se recovery, reduced interference, and Se concentration preservation. 1 Selenium recovery and matrix composition were evaluated during each step of the sample preparation procedure (Figure S2).…”

Section: Resultsmentioning

confidence: 99%

“…The lack of studies on Se isotopic composition in biological matrices could be attributed to the multiple analytical difficulties associated with measuring accurate and precise Se isotopic ratios. Nowadays, hydride generation (HG) coupled to multicollector inductively coupled plasma mass spectrometry (HG-MC-ICP-MS) is recognized as the technique of choice for Se stable isotope measurements. , However, multiple isobaric interferences of Se stable isotopes can occur in plasma, such as 40 Ar 40 Ar and 38 Ar 40 Ar, that could hamper the measurement precision. In addition, for complex biological matrices such as animal tissues, nonspectral interferences due to some transition metals (e.g., Cu, Co, Fe, and Ni) or hydride-forming elements (e.g., As, Ge, and Sb) are expected to occur. , Therefore, the sample preparation and sample introduction methods should be carefully optimized to minimize these drawbacks.…”

Section: Introductionmentioning

confidence: 99%

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First-Time Isotopic Characterization of Seleno-Compounds in Biota: A Pilot Study of Selenium Isotopic Composition in Top Predator Seabirds

Marchán-Moreno,

Louvat,

Bueno

et al. 2024

Environ. Sci. Technol.

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This study pioneers the reporting of Se isotopes in marine top predators and represents the most extensive Se isotopic characterization in animals to date. A methodology based on hydride generation�multicollector inductively coupled plasma mass spectrometry�was established for such samples. The study was conducted on various internal organs of giant petrels (Macronectes spp.), encompassing bulk tissues (δ 82/78 Se bulk ), distinct Se-specific fractions such as selenoneine (δ 82/78 Se SEN ), and HgSe nanoparticles (δ 82/78 Se NPs ). The δ 82/78 Se bulk results (2.0−5.6‰) offer preliminary insights into the fate of Se in key internal organs of seabirds, including the liver, the kidneys, the muscle, and the brain. Notably, the liver of all individuals was enriched in heavier Se isotopes compared to other examined tissues. In nanoparticle fraction, δ 82/78 Se varies significantly across individuals (δ 82/78 Se NPs from 0.6 to 5.7‰, n = 8), whereas it exhibits remarkable consistency among tissues and individuals for selenoneine (δ 82/78 Se SEN , 1.7 ± 0.3‰, n = 8). Significantly, there was a positive correlation between the shift from δ 82/78 Se bulk to δ 82/78 Se SEN and the proportion of Se present as selenoneine in the internal organs. This pilot study proves that Se species-specific isotopic composition is a promising tool for a better understanding of Se species fate, sources, and dynamics in animals.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

First-Time Isotopic Characterization of Seleno-Compounds in Biota: A Pilot Study of Selenium Isotopic Composition in Top Predator Seabirds

Marchán-Moreno,

Louvat,

Bueno

et al. 2024

Environ. Sci. Technol.

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“…The large difference between the ε value observed in the pH 1 and 0.009 to 0.02 mM sulfide experiment (−1.42‰) and the values observed in the experiments at pH 5 to 8 and sulfide concentrations between 1 to 6 mM (−0.46 to −0.62‰) must be related to differences in the kinetics and/or mechanism of the reaction. Isotopic fractionation is controlled by changes to the local bonding environment of elements, and the changes in coordination and valence that accompany redox reactions often produce relatively strong isotopic fractionation . During mass-dependent kinetic isotope effects, bonds with lighter isotopes have higher zero-point energies than bonds with heavier isotopes .…”

Section: Discussionmentioning

confidence: 99%

“…Isotopic fractionation is controlled by changes to the local bonding environment of elements, and the changes in coordination and valence that accompany redox reactions often produce relatively strong isotopic fractionation. 25 During mass-dependent kinetic isotope effects, bonds with lighter isotopes have higher zero-point energies than bonds with heavier isotopes. 26 When a single-step reaction with no back reaction occurs, bonds involving lighter isotopes are more easily broken, and the lighter isotopes react faster.…”

Section: Dependence Of Sb Isotopementioning

confidence: 99%

Kinetic Fractionation of Antimony Isotopes during Reduction by Sulfide

Veldhuizen,

MacKinney,

Johnson

2023

ACS Earth Space Chem.

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“…Isotopic fractionation is controlled by changes to the local bonding environment of elements, and the changes in coordination and valence that accompany redox reactions often produce relatively strong isotopic fractionation. 22 During massdependent kinetic isotope effects, bonds with lighter isotopes have higher zero-point energies than bonds with heavier isotopes. 23 When a single-step reaction with no back reaction occurs, bonds involving lighter isotopes are more easily broken and the lighter isotopes react faster.…”

Section: Dependence Of Sb Isotope Fractionation On Reaction Kineticsmentioning

confidence: 99%

Kinetic Fractionation of Antimony Isotopes during Reduction by Sulfide

Veldhuizen,

MacKinney,

Johnson

2023

Preprint

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Stable isotope ratios of antimony (Sb) in the environment can provide valuable information on sources and processes such as redox transformations. To investigate the fractionation when Sb(V) is chemically reduced by sulfide to Sb(III), experiments with 0.008 to 0.01 mM Sb(V) and 0.009 to 6 mM sulfide at a pH of 1 to 8 were performed. Experiments at pH 1 to 6 precipitated Sb2S3, while at pH 7 to 8 Sb(III) remained in solution. The Sb(III) product was enriched in the lighter isotope. The isotopic fractionation (ε ≈ δinstantaneous product – δreactant) for the pH 1 experiment was -1.42 ± 0.04‰ while the pH 5 to 8 experiments ranged from -0.46 ± 0.04‰ to -0.62 ± 0.04‰. The small magnitude of fractionation observed in experiments at circumneutral pH may decrease the utility of Sb isotope measurement as reduction indicators in natural systems, as adsorption of Sb has been shown to fractionate isotopes in the same direction and similar magnitude (up to 1.14‰) (Wasserman, 2020; Zhou et al., 2023).

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A Review of the Development of Cr, Se, U, Sb, and Te Isotopes as Indicators of Redox Reactions, Contaminant Fate, and Contaminant Transport in Aqueous Systems

Cited by 9 publications

References 257 publications

First-Time Isotopic Characterization of Seleno-Compounds in Biota: A Pilot Study of Selenium Isotopic Composition in Top Predator Seabirds

First-Time Isotopic Characterization of Seleno-Compounds in Biota: A Pilot Study of Selenium Isotopic Composition in Top Predator Seabirds

Kinetic Fractionation of Antimony Isotopes during Reduction by Sulfide

Kinetic Fractionation of Antimony Isotopes during Reduction by Sulfide

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