Thermal oxidation of carbon in organic matter rich volcanic soils: insights into SOC age differentiation and mineral stabilization

摘要

Radiocarbon ages and thermal stability measurements can be used to estimate the stability of soil organic carbon (OC). Soil OC is a complex reservoir that contains a range of compounds with different sources, reactivities, and residence times. This heterogeneity can shift bulk radiocarbon values and impact assessment of OC stability and turnover in soils. Four soil horizons (Oa, Bhs, Bs, Bg) were sampled from highly weathered 350 ka Pololu basaltic volcanics on the Island of Hawaii and analyzed by Ramped PyrOX (RPO) in both the pyrolysis (PY) and oxidation (OX) modes to separate a complex mixture of OC into thermally defined fractions. Fractions were characterized for carbon stable isotope and radiocarbon composition. PY and OX modes yielded similar results. Bulk radiocarbon measurements were modern in the Oa horizon (Fm = 1.013) and got progressively older with depth: the Bg horizon had an Fm value of 0.73. Activation energy distributions (p(E)) calculated using the 'rampedpyrox' model yielded consistent mean E values of 140 kJ mol(-1) below the Oa horizon. The 'rampedpyrox' model outputs showed a mostly bimodal distribution in the p(E) below the Oa, with a primary peak at 135 kJ mol(-1) and a secondary peak at 148 kJ mol(-1), while the Oa was dominated by a single, higher E peak at 157 kJ mol(-1). We suggest that mineral-carbon interaction, either through mineral surface-OC or metal-OC interactions, is the stabilization mechanism contributing to the observed mean E of 140 kJ mol(-1) below the Oa horizon. In the Oa horizon, within individual RPO analyses, radiocarbon ages in the individual thermal fractions were indistinguishable (p > 0.1). The flat age distributions indicate there is no relationship between age and thermal stability (E) in the upper horizon (> 25 cm). Deeper in the soil profile higher mu E-f values were associated with older radiocarbon ages, with slopes progressively steepening with depth. In the deepest (Bg) horizon, there was the largest, yet modest change in Fm of 0.06 (626 radiocarbon years), indicating that older OC is slightly more thermally stable.