Organic Matter Occlusion of Mineral Surfaces as a Function of Mineral
Weathering in Volcanic Ash Soils
Abstract
In upland soils in humid climates, mineral stabilization of organic
matter (OM) on millennial scales is often driven by the abundance of
poorly crystalline, metastable chemical weathering products. Studies of
volcanic ash soils have demonstrated that these metastable materials
transform into increasingly crystalline minerals at advanced stages of
weathering, so that the overall affinity of mineral surfaces for OM
declines with time. However, the abundance of clay-sized (<2
𝜇m diameter) particles tends to increase with weathering, enhancing soil
specific surface area (SSA) and potentially compensating for the loss of
mineral affinity for OM. As a first step towards understanding the net
effects of these simultaneous transformations on OM stabilization, we
compared the coverage of SSA by OM in A and B horizons of ash-derived
soils sampled along an elevation gradient in Veracruz, Mexico. N2
adsorption isotherms and Brunauer–Emmett–Teller (BET) theory were used
to estimate SSA of bulk soil versus samples from which OM had been
removed via combustion (muffling) and chemical oxidation (bleaching). In
addition to comparing the effectiveness of the OM removal treatments, we
characterized the extent to which the treatments altered the mineral
matrix and introduced errors into the estimates of mineral SSA. Pore
size distribution was estimated via density functional theory as a
complement to the BET analysis. N2-accessible SSA ranged from 9 to 105
m2 g-1 after removal of OM, with muffling yielding higher values than
bleaching for most samples. The probable loss of SSA associated with
mineral transformations (e.g., of Fe oxides) at high temperatures during
muffling was evidently offset by the more thorough removal of OM by that
treatment. Although SSA tended to increase with weathering status,
relative coverage of SSA by OM was relatively consistent across profiles
and tended to be greater on average in A horizons (bleaching: 45% SSA
covered, muffling: 51%) than in B horizons (bleaching: 28%, muffling:
34%). The apparent lack of OM coverage of SSA in the B horizon of the
most weathered soil (0% of 60 m2 g-1 covered) underscores the overall
importance of mineral reactivity in determining OM stabilization. Future
work will extend these analyses to examine land-use effects on SSA
coverage by OM.