Millot,R., Vigier,N. and Gaillardet,J.(2010): Behaviour of lithium and its isotopes during weathering in the Mackenzie Basin, Canada. Geochimica et Cosmochimica Acta, 74, 3897-3912.

『カナダのマッケンジー盆地における風化中のリチウムとその同位体の挙動』


Abstract
 We report Li isotopic compositions, for river waters and suspended sediments, of about 40 rivers sampled within the Mackenzie River Basin in northwestern Canada. The aim of this study is to characterize the behaviour of Li and its isotopes during weathering at the scale of a large mixed lithology basin. The Mackenzie River waters display systematically heavier Li isotopic compositions relative to source rocks and suspended sediments. The range of δ7Li is larger in dissolved load (from +9.3‰ to +29.0‰) compared to suspended sediments (from -1.7‰ to +3.2‰), which are not significantly different from δ7Li values in bedrocks. Our study shows that dissolved Li is essentially derived from the weathering of silicates and that its isotopic composition in the dissolved load is inversely correlated with its relative mobility when compared to Na. The highest enrichment of 7Li in the dissolved load is reported when Li is not or poorly incorporated in secondary phases after its release into solution by mineral dissolution. This counterintuitive observation is interpreted by the mixing of water types derived from two different weathering regimes producing different Li isotopic compositions within the Mackenzie River Basin. The incipient weathering regime characterizing the Rocky Mountains and the Shield areas produces 7Li enrichment in the fluid phase that is most simply explained by the precipitation of oxyhydroxide phases fractionating Li isotopes. The second weathering regime is found in the lowland area and produces the lower δ7Li waters (but still enriched in 7Li compared to bedrocks) and the most Li-depleted waters (compared to Na). Fractionation factors suggest that the incorporation of Li in clay minerals is the mechanism that explains the isotopic composition of the lowland rivers. The correlation of boron and lithium concentrations found in the dissolved load of the Mackenzie Rivers suggests that precipitation of clay minerals is favoured by the relatively high residence time of water in groundwater. In the Shield and Rocky Mountains, Li isotopes suggest that clay minerals are not forming and that secondary minerals with stronger affinity for 7Li appear.
 Although the weathering mechanisms operating in the Mackenzie Basin need to be characterized more precisely, the Li isotope data reported here clearly show the control of Li isotopes by the weathering intensity. The spatial diversity of weathering regimes, resulting from a complex combination of factors such as topography, geology, climate and hydrology explains, in fine, the spatial distribution of Li isotopic ratios in the large drainage basin of the Mackenzie River. There is no simple relationship between Li isotopic composition and chemical denudation fluxes in the Mackenzie River Basin.』

1. Introduction
2. Geological setting and sample locations
3. Analytical methods
 3.1. Sampling methodology, major and trace element concentration measurements
 3.2. Lithium isotope measurements
4. Results
 4.1. Dissolved phase
 4.2. River sediments and bedrocks
5. Discussion
 5.1. Sources of dissolved lithium
 5.2. Li isotopes and silicate weathering regimes
  5.2.1. Evidence for isotope fractionation during chemical weathering
  5.2.2. Influence of the weathering regime
6. Conclusions
Acknowledgments
References


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