Distinctive roles of two aggregate binding agents in allophanic andisols: Young carbon and poorly-crystalline metal phases with old carbon

Abstract

Interaction of organic matter (OM) with soil mineral components plays a critical role in biophysical organization (aggregate structure) as well as in biogeochemical cycling of major elements. Of the mineral components, poorly-crystalline phases rich in iron (Fe) and aluminum (Al) are highly reactive and thus contribute to both OM stabilization and aggregation. However, the functional relationship among the reactive metal phases, C stability, and aggregation remains elusive. We hypothesized that relatively young C acts as a binding agent to form the aggregates of weak physical stability, whereas the reactive metal phases and older C bound to them contribute to stronger aggregation. Using four surface horizons of Andisols having a gradient of soil C concentration due to decadal OM management, we conducted sequential density fractionation to isolate six fractions (from <1.6 to >2.5 g cm−3) with mechanical shaking, followed by selective dissolution and radiocarbon analysis. After 28 years of no-till with litter compost addition, not only C and N but inorganic materials including the reactive metal phases (pyrophosphate-, oxalate-, and dithionite-extractable metals) showed clear shifts in their concentrations towards lower-density fractions (especially <2.0 g cm−3) on a ground-area basis. This result was explained by the binding of compost-derived OM with soil particles. Major portions of the reactive metal phases in bulk samples were distributed in mid-density fractions (2.0–2.5 g cm−3) largely as sonication-resistant aggregates. Theoretical density calculations, together with depletion in radiocarbon (∆14C: −82 to −170‰) and lower C:N ratio, implied that the sorptive capacity of the reactive metal phases in these fractions were roughly saturated with pre-existing OM. However, the influx of the compost-derived, modern C into the mid-density fractions detected by the paired-plot comparison suggests decadal C sink in association with the reactive metal phase. Our results supported the concept of aggregate hierarchy and further provided the following new insights. At the high hierarchy level where shaking-resistant aggregates form, soil organo-mineral particles appeared to be under a dynamic equilibrium and the changes in OM input regime controlled (dis)aggregation behavior due to the binding effect of relatively young C. At a lower hierarchy level, the reactive metal phases were bound to N-rich,14C-depleted OM and together functioned as persistent binding agent. Our study suggests that the recognition of binding agents and aggregate hierarchy level would help to untangle the complex organo-mineral interactions and to better understand soil C stability.