Nickel isotope fractionation during intense weathering of basalt: Implications for Ni output from continental weathering

Abstract

Nickel isotope fractionation during continental weathering is not well constrained due to the limited research on Ni isotopes during weathering of mafic rocks such as basalt. This study investigated two weathering profiles (strongly and extremely weathered) derived on basalts in tropical China. The strongly weathered profile was dominated by kaolinite and divided into three layers with depth (soil, saprolite and rock). The extremely weathered profile was mainly composed of Fe- and Al-(oxyhydr)oxides and kaolinite, and included a special ferricrust layer, iron-rich duricrust with ferruginous nodules, between the soil and saprolite. We analysed the Ni speciation (e.g. Fe-oxide phases and residual phase) and isotopic composition of soil, ferricrust, saprolite, rock and water samples in the weathering profiles. Pore water and groundwater were collected underlying the extremely weathered profile, and the size-distribution of particulate Ni (1 kDa–450 nm) in water samples was analysed.Nickel in both profiles was mainly hosted in the residual phase (>71% of total Ni) which included primarily secondary silicates and Al-(oxyhydr)oxides. Weathering intensity controlled the mineral compositions and physico-chemical properties of the weathering profiles as well as Ni isotopic variations. Nickel redistribution (∼30%) and isotope fractionation (Δ60Niregolith-rock = −0.08‰ to 0.07‰) were slight in the strongly weathered profile due to the dominance of secondary silicates in Ni speciation. For the extremely weathered profile, significant Ni depletion (∼67%) and isotope fractionation (Δ60Niregolith-rock = −0.25‰ to 0.32‰) were related to the transformation of secondary silicates into Fe- and Al-(oxyhydr)oxides during lateritic weathering. The positive correlation of δ60Ni and Ni concentrations indicated that Ni isotope fractionation was controlled by Ni adsorption and incorporation of secondary minerals. In the lower saprolite, the calculated isotope fractionation between Ni remaining in the profile and leaching to the solution (Δ60Nisolid-solution = −0.47‰) indicated that Ni isotope fractionation was mainly controlled by the preferential adsorption of isotopically light Ni on Fe- and Al-(oxyhydr)oxides. However, in the soil and ferricrust, acidic pH (∼5.0) might reduce Δ60Nisolid-solution to −0.28‰ by releasing the isotopically light adsorbed Ni, leading to the predominance of incorporated Ni in Fe- and Al-(oxyhydr)oxides. Specifically, the highest δ60Ni value (0.27 ± 0.05‰) and Ni concentration in the upper saprolite indicated that the isotopically heavy Ni leached from the soil and ferricrust was scavenged by precipitating secondary silicates. Finally, the estimated isotopic composition of Ni leached from the extremely weathered profile (δ60Nioutput = 0.02 ± 0.15‰) was close to that of pore water (0.06 ± 0.01‰) where Ni was mainly present in the particulate phase. Compared with groundwater (δ60Ni = 0.33 ± 0.04‰) dominated by dissolved Ni, Ni output from the profile likely consisted of isotopically heavy dissolved Ni and light particulate Ni. Overall, this study provides a comprehensive understanding of Ni redistribution and speciation in basalt weathering profiles, highlighting the significance of weathering intensity in controlling Ni isotope fractionation and its implications for Ni outputs from continental weathering.