In situ evidence of mineral physical protection and carbon stabilization revealed by nanoscale 3-D tomography

Abstract

An approach for nanoscale 3-D tomography of organic carbon (OC) and associated mineral nanoparticles was developed to illustrate their spatial distribution and boundary interplay, using synchrotron-based transmission X-ray microscopy (TXM). The proposed 3-D tomography technique was first applied to in situ observation of a laboratory-made consortium of black carbon (BC) and nanomineral (TiO2, 15 nm), and its performance was evaluated using dual-scan (absorption contrast and phase contrast) modes. This novel tool was then successfully applied to a natural OC–mineral consortium from mountain soil at a spatial resolution of 60 nm, showing the fine structure and boundary of OC, the distribution of abundant nano-sized minerals, and the 3-D organo-mineral association in situ. The stabilization of 3500-year-old natural OC was mainly attributed to the physical protection of nano-sized iron (Fe)-containing minerals (Fe oxyhydroxides including ferrihydrite, goethite, and lepidocrocite), and the strong organo-mineral complexation. In situ evidence revealed an abundance of mineral nanoparticles, in dense thin layers or nano-aggregates/clusters, instead of crystalline clay-sized minerals on or near OC surfaces. The key working minerals for C stabilization were reactive short-range-order (SRO) mineral nanoparticles and poorly crystalline submicron-sized clay minerals. Spectroscopic analyses demonstrated that the studied OC was not merely in crisscross co-localization with reactive SRO minerals; there could be a significant degree of binding between OC and the minerals. The ubiquity and abundance of mineral nanoparticles on the OC surface, and their heterogeneity in the natural environment may have been severely underestimated by traditional research approaches. Our in situ description of organo-mineral interplay at the nanoscale provides direct evidence to substantiate the importance of mineral physical protection for the long-term stabilization of OC. This high-resolution 3-D tomography approach is a promising tool for generating new insight into the interior 3-D structure of micro-aggregates, the in situ interplay between OC and minerals, and the fate of mineral nanoparticles (including heavy metals) in natural environments.