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Potassium isotopic compositions of profiles through saprolites developed on a diabase in South Carolina, U.S.A., and on a granite in Guangdong, China, allow characterization of the behavior of K isotopes during continental weathering. Saprolites from the diabase profile are heavily weathered with chemical index of alteration (CIA) values up to 95; however, their K isotopic variation is limited, with δ41K ranging from −0.475 ± 0.028‰ in the unweathered diabase to −0.407 ± 0.021‰ for the saprolites. The lack of significant K isotope fractionation mainly reflects the conservative behavior of K in the diabase weathering profile, with >50% of the original K remaining in the saprolites. By contrast, K isotopes are fractionated during granite weathering and correlate with sample depth, CIA, and kaolinite abundance, with δ41K decreasing from −0.493 ± 0.030‰ in the unweathered granites at the bottom to −0.628 ± 0.021‰ in the most weathered saprolite close to the surface. These observations suggest the preference of light K isotopes in saprolites relative to fluids, which is further supported by the overall isotopically heavy nearby stream water samples (δ41K = −0.709 ± 0.017 to −0.339 ± 0.018‰). These results demonstrate that continental weathering plays an important role in the global K isotopic budget through the formation of isotopically heterogeneous rivers and weathered regolith. Recycling of K-rich crustal materials with distinct K isotopic signatures may produce distinct mantle K isotopic end members. [ABSTRACT FROM AUTHOR]

Abstract: Magnesium isotopic compositions of a profile through saprolites developed on a diabase dike from South Carolina have been measured in order to study the behavior of Mg isotopes during continental weathering. As weathering progresses, Mg isotopes are greatly fractionated and are correlated with Mg concentration, clay mineral proportions and density of the saprolites. δ26Mg values increase from −0.22 in the unweathered diabase to +0.65 in the most weathered saprolite. These observations are consistent with the release of light Mg to the hydrosphere and formation of isotopically heavy Mg in the weathered products. The loss of Mg during weathering can be modeled by Rayleigh distillation with an apparent fractionation factor between the saprolite and fluid (α) of 1.00005 to 1.0004, i.e., up to 0.4‰ fractionation in the 26Mg/24Mg ratio between the saprolite and fluid. The large variation in α value reflects a mineralogical control on Mg isotope fractionation during primary dissolution of Mg-rich minerals and formation of secondary minerals during continental weathering. Like Mg isotopes, Li isotopes in the saprolite profile are also greatly fractionated, with δ7Li values ranging from −6.7 down to −20. The large Li isotope fractionation and variation in Li concentration, as well as irregularities in the δ7Li profile with depth, however, cannot be explained by Li loss during weathering alone. Instead, Li can be modeled by a two-step process: (1) equilibrium isotope fractionation during continental weathering, which lowered δ7Li and Li concentrations and produced a Li concentration gradient in the saprolites like that seen in Mg, and (2) subsequent kinetic isotope fractionation produced by diffusion of Li in the saprolites, possibly across a paleo-water table. The results presented here suggest that continental weathering will shift the Mg isotopic composition of the continental crust to values higher than the mantle value, whereas crustal recycling over the history of the Earth will have no discernible effect on the Mg isotopic composition of the mantle. [Copyright &y& Elsevier]

Zinc isotopes have been increasingly utilized as a proxy for (bio)geochemical cycles of nutrient Zn in the ecosystem like soils, but the behavior and mechanism of Zn isotope fractionation during weathering and soil formation remain to be constrained. Here we reported zinc contents and isotope data for saprolites and laterites from two well-characterized mafic-rock weathering profiles, formed under a subtropical climate (South Carolina, USA) and a tropical climate (Hainan Island, China), respectively. Leaching experiments with basalt and andesite as the starting materials were also performed for comparison. The leaching results revealed no resolvable Zn isotope fractionation during dissolution of silicate minerals in the absence of organic ligands in solutions. The Hainan laterites show strong Zn depletion and have lower δ66Zn Lyon values (0.10‰ to 0.27‰) relative to the parent rock (0.31 ± 0.04‰), which are coupled with light copper isotope compositions in the same samples. These observations suggest that Zn mobilization was achieved via metal-organic complexation and Fe-colloids transportation. By contrast, saprolites from the South Carolina are extremely Zn-rich (ten-fold higher concentration than the parent rock) and most samples have higher δ66Zn values (0.10‰ to 0.65‰) compared with the parent rock (0.24 ± 0.04‰). Zinc isotope ratios of the South Carolina profile are positively correlated with iron isotope ratios (δ56Fe) and Fe3+/Fe Total , the latter of which is related to secondary Fe (hydr)oxide formation. These relationships link the high Zn contents and δ66Zn values of saprolites from the South Carolina profile to the substantial adsorption of Zn onto or isomorphic substitution into Fe (hydr)oxides that prefers heavier Zn isotopes. Our study highlights that Fe (hydr)oxides exert a strong influence on the re-distribution of nutrient Zn in natural soils and the (bio)geochemical cycling in natural soil systems. [ABSTRACT FROM AUTHOR]