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The influence of organic complexation on Ni isotopic fractionation and Ni recycling in the upper soil layers

The quantification of Ni isotopic fractionation induced by Ni binding to organic acids is a preliminary step to better constrain the mechanisms determining Ni isotopic fingerprint observed in surface soils, waters and plants, as well as the contribution of metal recycling during plant litter degrada...

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Published in:Chemical geology 2018-04, Vol.483, p.47-55
Main Authors: Zelano, I.O., Cloquet, C., Fraysse, F., Dong, S., Janot, N., Echevarria, G., Montargès-Pelletier, E.
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description The quantification of Ni isotopic fractionation induced by Ni binding to organic acids is a preliminary step to better constrain the mechanisms determining Ni isotopic fingerprint observed in surface soils, waters and plants, as well as the contribution of metal recycling during plant litter degradation. In this study, Ni isotopic fraction induced by reaction with small organic acids, e.g. citric and oxalic acids, and with soil purified humic acids (PHA) was investigated at different Ni-L ratio and pH conditions. The Donnan Membrane Technique was used to separate Ni bound to organic ligands from the free metal. Obtained results highlighted that Ni binding with carboxylic groups produces, in the adopted experimental conditions, a Δ60Nibond-free 
doi_str_mv 10.1016/j.chemgeo.2018.02.023
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In this study, Ni isotopic fraction induced by reaction with small organic acids, e.g. citric and oxalic acids, and with soil purified humic acids (PHA) was investigated at different Ni-L ratio and pH conditions. The Donnan Membrane Technique was used to separate Ni bound to organic ligands from the free metal. Obtained results highlighted that Ni binding with carboxylic groups produces, in the adopted experimental conditions, a Δ60Nibond-free &lt; 0.2‰. This value is not high enough to justify neither metal fractionation previously observed between soil and hyperaccumulators, nor the fractionation between different plant parts, e.g. roots and leaves. In parallel, leaf degradation experiments of two hyperaccumulating plants, where Ni is mainly present as Ni-citrate, were performed to simulate litter decomposition and to highlight the contribution of plants on Ni isotopic composition in surface soils and waters. In the case of the hyperaccumulator Alyssum murale, the degradation process did not induce any observable fractionation. On the contrary, during Rinorea bengalensis degradation experiment, a fractionation between Ni leached out in the first 10 days and between 10 and 30 days was observed (Δ60Ni10–30day = 0.20 ± 0.05‰). The observed fractionation evidenced a heterogeneous distribution of Ni within the leaves, and/or distinct chemical bonding to the leaf cells, and finally suggested the influence of the chemical bonding on Ni isotopic signature. Although a precise quantification of plant contribution on Ni isotopic signature in surface soils and waters is still not reached, our results produced important progress to elucidate the role of organic matter in regulating Ni isotopic fingerprint in surface layers. 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In the case of the hyperaccumulator Alyssum murale, the degradation process did not induce any observable fractionation. On the contrary, during Rinorea bengalensis degradation experiment, a fractionation between Ni leached out in the first 10 days and between 10 and 30 days was observed (Δ60Ni10–30day = 0.20 ± 0.05‰). The observed fractionation evidenced a heterogeneous distribution of Ni within the leaves, and/or distinct chemical bonding to the leaf cells, and finally suggested the influence of the chemical bonding on Ni isotopic signature. Although a precise quantification of plant contribution on Ni isotopic signature in surface soils and waters is still not reached, our results produced important progress to elucidate the role of organic matter in regulating Ni isotopic fingerprint in surface layers. 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In this study, Ni isotopic fraction induced by reaction with small organic acids, e.g. citric and oxalic acids, and with soil purified humic acids (PHA) was investigated at different Ni-L ratio and pH conditions. The Donnan Membrane Technique was used to separate Ni bound to organic ligands from the free metal. Obtained results highlighted that Ni binding with carboxylic groups produces, in the adopted experimental conditions, a Δ60Nibond-free &lt; 0.2‰. This value is not high enough to justify neither metal fractionation previously observed between soil and hyperaccumulators, nor the fractionation between different plant parts, e.g. roots and leaves. In parallel, leaf degradation experiments of two hyperaccumulating plants, where Ni is mainly present as Ni-citrate, were performed to simulate litter decomposition and to highlight the contribution of plants on Ni isotopic composition in surface soils and waters. In the case of the hyperaccumulator Alyssum murale, the degradation process did not induce any observable fractionation. On the contrary, during Rinorea bengalensis degradation experiment, a fractionation between Ni leached out in the first 10 days and between 10 and 30 days was observed (Δ60Ni10–30day = 0.20 ± 0.05‰). The observed fractionation evidenced a heterogeneous distribution of Ni within the leaves, and/or distinct chemical bonding to the leaf cells, and finally suggested the influence of the chemical bonding on Ni isotopic signature. Although a precise quantification of plant contribution on Ni isotopic signature in surface soils and waters is still not reached, our results produced important progress to elucidate the role of organic matter in regulating Ni isotopic fingerprint in surface layers. 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subjects Complexation
Continental interfaces, environment
Earth Sciences
Geochemistry
Hyperaccumulating plants
Isotopic fractionation
Organic matter
Sciences of the Universe
title The influence of organic complexation on Ni isotopic fractionation and Ni recycling in the upper soil layers
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