Magnesium Isotope Fractionation During Arid Pedogenesis on the Island of Hawaii (USA)

We combines Mg isotopic analyses with soil characterization methods to determine Mg isotopic compositions of bulk soils, basalts, and carbonate fractions at an arid (∼30 cm MAP) soil chronosequence on the Island of Hawaii. This chronosequence is developed on Pololu (350 ka) and Hawi (170 ka) lava flows. Both profiles contain pedogenic carbonates and secondary alumino- silicate and sequioxide phases. Bulk soil horizons at these sites range in δ26Mg from -0.21±0.31 ‰ to -1.75±0.22 ‰ for the Hawi and -0.01±0.31 ‰ to -0.21±0.31 ‰ for the Pololu. Basalts underlying the soil profiles have average δ26Mg values of - 0.25±0.06 ‰. Pedogenic carbonate δ26Mg values at these sites vary from -1.05±0.22‰ to -2.31±0.22‰. Integrating the soils as a whole yields bulk soil isotopic compositions of -1.35±0.16 ‰ for the Hawi and -0.12±0.12 ‰ for the Pololu. These differences in overall δ26Mg between total soils may be explained by the relative abundance of Mg in carbonate; in the Hawi soil 69±11% of Mg is hosted by carbonate phases, while in the Pololu soil 16±2% of Mg is in carbonate phases. Estimates of Mg input to the soils through time, through rainfall estimates as well as rock weathering estimates provided by the immobile index element Zr, allows the calculation of the δ26Mg of Mg exported from these systems. The isotopic composition Mg exported from the Hawi soil is not tightly constrained but must be significantly isotopically heavier than the basalt parent material. The Pololu soil is much better constrained and has exported Mg with a δ26Mg of -0.36±0.26 ‰, close to the weighted mean value of inputs to the soil from weathering and atmospheric deposition. The evolution of the soil mineralogy and morphology during progressive development of the weathering profile result in significant changes in the isotopic composition of Mg exported through time.