Factors affecting the molecular structure and mean residence time of occluded organics in a lithosequence of soils under ponderosa pine

Occluded, or intra-aggregate, soil organic matter (SOM) comprises a significant portion of the total C pool in forest soils and often has very long mean residence times (MRTs). However, occluded C characteristics vary widely among soils and the genesis and composition of the occluded organic matter pool are not well understood. This work sought to define the major controls on the composition and MRT of occluded SOM in western U.S. conifer forest soils with specific focus on the influence of soil mineral assemblage and aggregate stability. We sampled soils from a lithosequence of four parent materials (rhyolite, granite, basalt, and dolostone) under Pinus ponderosa. Three pedons were excavated to the depth of refusal at each site and sampled by genetic horizon. After density separation at 1.8gcm^-3 into free/light, occluded and mineral fractions, the chemical nature and mean residence time of organics in each fraction were compared. SOM chemistry was explored through the use of stable isotope analyses, ¹³C NMR, and pyrolysis GC/MS. Soil charcoal content estimates were based on ¹³C NMR analyses. Estimates of SOM MRT were based on steady-state modeling of SOM radiocarbon abundance measurements. Across all soils, the occluded fraction was 0.5-5 times enriched in charcoal in comparison to the bulk soil and had a substantially longer MRT than either the mineral fraction or the free/light fraction. These results suggest that charcoal from periodic burning is the primary source of occluded organics in these soils, and that the structural properties of charcoal promote its aggregation and long-term preservation. Surprisingly, aggregate stability, as measured through ultrasonic dispersion, was not correlated with occluded SOM abundance or MRT, perhaps raising questions of how well laboratory measurements of aggregate stability capture the dynamics of aggregate turnover under field conditions. Examination of the molecular characteristics of the occluded fraction was more conclusive. Occluded fraction composition did not change substantially with soil mineral assemblage, but was increasingly enriched in charcoal with depth relative to bulk SOM. Enrichment levels of ¹³C and ¹⁵N suggested a similar degree of microbial processing for the free/light and occluded fractions, and molecular structure of occluded and free/light fractions were also similar aside from charcoal enrichment in the occluded fraction. Results highlight the importance of both fire and aggregate formation to the long-term preservation of organics in western U.S. conifer forests which experience periodic burning, and suggest that the composition of occluded SOM in these soils is dependent on fire and the selective occlusion of charcoal.