Phosphorus hotspots in pedogenic carbonate coatings determined by zoned microscale arrangement and organo-mineral interactions

Subsoils of calcareous soils are often characterized by pedogenic carbonate precipitates coating soil aggregate and rock surfaces. Numerous studies identified the key mechanisms of pedogenic carbonate formation in calcareous soils. Still, little is known about the ecosystem function of carbonate precipitates for nutrient supply, their microscale structure and the interaction of microscale structure with nutrient distribution such as P. We investigated the mineral composition and P speciation of lithogenic carbonate coated by pedogenic carbonate precipitates. Subsoil horizons of a Rendzic Leptosol (Tuttlingen, C horizon) and a Eutric Cambisol (Benediktenwand, BC horizon) in Central Europe were sampled. We combined wet-chemical methods with X-ray diffraction, synchrotron-based P XANES spectroscopy, and specific surface area analysis (N2-BET). To investigate the spatial arrangement and elemental distribution at the micro-scale, a complementary approach using light microscopy, scanning electron microscopy with energy dis-persive x-ray spectroscopy (SEM-EDX) as well as XANES spectroscopy at the microscale (lXANES) was conducted. In both soils, the pedogenic carbonate coatings showed an intricate porous microstructure and large specific surface area. The d13C values of the coatings were halfway between those of the primary bedrock and soil organic matter (SOM), proving their formation by re-precipitation of dissolved carbonate through organic and inorganic (H2CO3) acids. Compared to the primary rocks, the coatings were enriched in Al, Fe, Mn, and K and in organic C, N, and P; additionally, they contained silicate minerals (muscovite, illite) and quartz. Whereas the P in the rock interior was mainly present as apatite, the P in the coatings was mainly organic P bound to Ca and Al minerals. NanoSIMS and lXANES analyses at Tuttlingen revealed a zoned microstructure of the pedogenic coating: An inner zone with most P co-localized and bound to Al minerals and an outer zone enriched again in Ca and SOM. The formation of these zones indicates the infiltration and residual accumulation of Al minerals which may contribute to mitigate P losses by leach-ing. Intensive penetration by fine plant roots and observations of fungal hyphae within the coatings indi-cate the potential of pedogenically altered carbonates as microbial habitat and ecosystem nutrient source, thus contributing to the scarce ecosystem P nutrition of initial calcareous soils.(c) 2023 Elsevier Ltd. All rights reserved.