The chemistry and nature of protected carbon in soil

The nature of organic carbon in the 2, 2–20, 20–53, 53–200, and 200–2000 mu m fractions of four surface soils was determined using solid state 13C nuclear magnetic resonance (n.m.r.) spectroscopy with cross polarisation and magic angle spinning (CP/MAS). Analyses were repeated after high energy ultraviolet photo-oxidation was performed on the three finest fractions. All four soils, studied contained appreciable amounts of physically protected carbon while three of the soils contained even higher amounts of charcoal. It was not possible to measure the charcoal content of soils directly, however, after photo-oxidation, charcoal remained and was identified by its wood-like morphology revealed by scanning electron microscopy (SEM) together with a highly aromatic chemistry determined by solid state 13C n.m.r. Charcoal appears to be the major contributor to the 130 ppm band seen in the n.m.r. spectra of many Australian soils. By using the aromatic region in the n.m.r. spectra, an approximate assessment of the charcoal distribution through the size fractions demonstrated that more than 88% of the charcoal present in two of the soils occurred in the 53 µm fractions. These soils contained up to 0.8 g C as charcoal per 100 g of soil and up to 30% of the soil carbon as charcoal. Humic acid extractions performed on soil fractions before and after photo-oxidation suggest that charcoal or charcoal-derived material may also contribute significantly to the aromatic signals found in the n.m.r. spectra of humic acids. Finely divided charcoal appears to be a major constituent of many Australian soils and probably contributes significantly to the inert or passive organic carbon pool recognised in carbon turnover models.