Theoretical isotope fractionation of cadmium during complexation with organic ligands

Zhao, Yang; Li, Yongbing; Wiggenhauser, Matthias; Yang, Jun‐Li; Sarret, Géraldine; Cheng, Qi; Liu, Jianming; Shi, Yaolin

doi:10.1016/j.chemgeo.2021.120178

Cited by 36 publications

(39 citation statements)

References 111 publications

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“…In the vacuole, Cd is then sequestered by strong binding to thiols that may contribute further to the retention of light Cd ( Wei et al, 2018 ). This hypothesis is supported by synchrotron X-ray absorption spectroscopy (XAS) results that showed the majority of Cd in rice roots can be bound to S-containing ligands, such as glutathione or phytochelatins, which are expected to preferentially bind light Cd isotopes ( Yan et al, 2016 ; Wiggenhauser et al, 2021a ; Zhao et al, 2021 ). Alternatively, Zhong et al (2022) showed that Δ 114/110 Cd shoot-root in rice can be further impacted by the protein CAL1.…”

Section: Isotope Fractionation In Plantsmentioning

confidence: 83%

“…The isotope shift was ascribed to the dehydration of Cd from Cd(H 2 O) 6 to Cd(H 2 O) 5 prior to binding of Cd to carboxyl groups. The dehydration of Cd favors light isotopes while the opposite is the case for Zn ( Fujii et al, 2014 ; Zhao et al, 2021 ). Hence, the opposing isotope fractionation of Zn and Cd could be induced by dehydration processes that may take place prior to membrane transport or during ligand exchange and/or by the high affinity of Cd to thiols.…”

Section: Discussionmentioning

confidence: 98%

“…Thiol chelators (e.g., phytochelatin) can strongly bind Cd and contribute to the sequestration of light Cd isotopes in vacuoles ( Nocito et al, 2011 ). Based on ab initio calculations, preferentially light Zn and Cd isotopes bind to S chelators at equilibrium (e.g., Fujii et al, 2014 ; Zhao et al, 2021 ). Given that Cd has a higher affinity to thiols than Zn, competition for thiol binding could control the opposing isotope fractionation of these trace metals in cereals.…”

Section: Discussionmentioning

confidence: 99%

“…Given that Cd has a higher affinity to thiols than Zn, competition for thiol binding could control the opposing isotope fractionation of these trace metals in cereals. The second hypothesis is based on Cd sorption experiments on humic acid and ab initio calculations ( Ratié et al, 2021 ; Zhao et al, 2021 ). Binding of ionic Cd to carboxyl groups (Cd-O) leads to a small shift toward light isotopes ( Ratié et al, 2021 ).…”

Section: Discussionmentioning

confidence: 99%

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Stable Isotope Fractionation of Metals and Metalloids in Plants: A Review

et al. 2022

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This work critically reviews stable isotope fractionation of essential (B, Mg, K, Ca, Fe, Ni, Cu, Zn, Mo), beneficial (Si), and non-essential (Cd, Tl) metals and metalloids in plants. The review (i) provides basic principles and methodologies for non-traditional isotope analyses, (ii) compiles isotope fractionation for uptake and translocation for each element and connects them to physiological processes, and (iii) interlinks knowledge from different elements to identify common and contrasting drivers of isotope fractionation. Different biological and physico-chemical processes drive isotope fractionation in plants. During uptake, Ca and Mg fractionate through root apoplast adsorption, Si through diffusion during membrane passage, Fe and Cu through reduction prior to membrane transport in strategy I plants, and Zn, Cu, and Cd through membrane transport. During translocation and utilization, isotopes fractionate through precipitation into insoluble forms, such as phytoliths (Si) or oxalate (Ca), structural binding to cell walls (Ca), and membrane transport and binding to soluble organic ligands (Zn, Cd). These processes can lead to similar (Cu, Fe) and opposing (Ca vs. Mg, Zn vs. Cd) isotope fractionation patterns of chemically similar elements in plants. Isotope fractionation in plants is influenced by biotic factors, such as phenological stages and plant genetics, as well as abiotic factors. Different nutrient supply induced shifts in isotope fractionation patterns for Mg, Cu, and Zn, suggesting that isotope process tracing can be used as a tool to detect and quantify different uptake pathways in response to abiotic stresses. However, the interpretation of isotope fractionation in plants is challenging because many isotope fractionation factors associated with specific processes are unknown and experiments are often exploratory. To overcome these limitations, fundamental geochemical research should expand the database of isotope fractionation factors and disentangle kinetic and equilibrium fractionation. In addition, plant growth studies should further shift toward hypothesis-driven experiments, for example, by integrating contrasting nutrient supplies, using established model plants, genetic approaches, and by combining isotope analyses with complementary speciation techniques. To fully exploit the potential of isotope process tracing in plants, the interdisciplinary expertise of plant and isotope geochemical scientists is required.

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Section: Isotope Fractionation In Plantsmentioning

confidence: 83%

Section: Discussionmentioning

confidence: 98%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Stable Isotope Fractionation of Metals and Metalloids in Plants: A Review

et al. 2022

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“…Finally, results from DFT revealed that while lighter Cd isotopes bind to sulfur donor atoms of organic ligands, heavier Cd isotopes preferably bind to oxygen and nitrogen donor atoms (Zhao et al, 2021). However, these results are in opposition with those demonstrating that Cd complexation with humic acid led to a light Cd isotopes enrichment in the complexed form (Rati e et al, 2021).…”

Section: Complexationmentioning

confidence: 85%

Metal isotope complexation with environmentally relevant surfaces: Opening the isotope fractionation black box

Komárek

Ratié

Vaňková

et al. 2021

Critical Reviews in Environmental Science and Technology

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The number of studies using various stable isotope systems for tracing contamination sources and various biogeochemical processes is rapidly rising due to the increased availability of the techniques used for isotope analyses. However, in most cases, the resulting isotope data are influenced by many processes occurring within reactive environmental compartments, e.g., soils and sediments, such as sorption, precipitation, redox changes, interactions with plants and microorganisms, etc. Therefore, isotope tracing becomes challenging as it is crucial to identify and quantify the isotope fractionation extent during separate processes in this so-called "isotope fractionation black box". The main aim of this review is to (i) summarize literature data on fractionation of selected metal isotopes (Cd, Cu, Hg, Ni, Zn) after complexation with relevant environmental surfaces, e.g., oxyhydroxides, clay minerals, natural organic matter etc., (ii) briefly describe the analytical techniques and key procedures used for the determination of such data and (iii) provide suggestions and perspectives for future research, including a critical evaluation of specific issues related to isotope analyses and especially the interpretation of results. For example, concentration equilibrium usually differs from isotope fractionation equilibrium, metal coordination chemistry in solution is crucial to decipher metal isotopic fractionation, spectroscopic data are missing, different experimental conditions are often and potential precipitation and desorption reactions are not always considered, etc. Consistent presentation of adsorption/complexation data would also be highly beneficial in future studies.

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Translocation of elements and fractionation of Mg, Cu, Zn, and Cd stable isotopes in a penny bun mushroom (Boletus edulis) from western Czech Republic

Andronikov

Andronikova

Martínková

et al. 2023

Environ Sci Pollut Res

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Boletus edulis mushroom behaved as an accumulating biosystem with respect to Ag, Rb, Zn, and K. The mushroom was not an efficient accumulator of toxic As, Pb, and Cr, but Se and Cd displayed much higher concentrations in the mushroom than in the substrate samples. Other elements were bioexclusive. Different elements had different within-mushroom mobilities. The highest mobilities were displayed by Zn and Ag, and the lowest by Ti. The mushroom’s fruiting body preferentially took up lighter Mg, Cu, and Cd isotopes (Δ26MgFB-soil = −0.75‰; Δ65CuFB-soil = −0.96‰; Δ114CdFB-soil = −0.63‰), and the heavier 66Zn isotope (Δ66ZnFB-soil = 0.92‰). Positive within-mushroom Zn isotope fractionation resulted in accumulation of the heavier 66Zn (Δ66Zncap-stipe = 0.12‰) in the mushroom’s upper parts. Cadmium displayed virtually no within-mushroom isotope fractionation. Different parts of the fruiting body fractionated Mg and Cu isotopes differently. The middle part of the stipe (3–6 cm) was strongly depleted in the heavier 26 Mg with respect to the 0–3 cm (Δ26Mgstipe(3–6)-stipe(0–3) = −0.73‰) and 6–9 cm (Δ26Mgstipe(6–9)-stipe(3–6) = 0.28‰) sections. The same stipe part was strongly enriched in the heavier 65Cu with respect to the 0–3 cm (Δ65Custipe(3–6)-stipe(0–3) = 0.63‰) and 6–9 cm (Δ65Custipe(6–9)-stipe(3–6) = −0.42‰) sections. An overall tendency for the upper mushroom’s parts to accumulate heavier isotopes was noted for Mg (Δ26Mgcap-stipe = 0.20‰), Zn (Δ66Zncap-stipe = 0.12‰), and Cd (Δ114Cdcap-stipe = 0.04‰), whereas Cu showed the opposite trend (Δ65Cucap-stipe = −0.08‰).

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Theoretical isotope fractionation of cadmium during complexation with organic ligands

Cited by 36 publications

References 111 publications

Stable Isotope Fractionation of Metals and Metalloids in Plants: A Review

Stable Isotope Fractionation of Metals and Metalloids in Plants: A Review

Metal isotope complexation with environmentally relevant surfaces: Opening the isotope fractionation black box

Translocation of elements and fractionation of Mg, Cu, Zn, and Cd stable isotopes in a penny bun mushroom (Boletus edulis) from western Czech Republic

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