A detailed pyrolysis-GC/MS analysis of a black carbon-rich acidic colluvial soil (Atlantic ranker) from NW Spain.

Despite the potentially large contribution of black carbon (BC) to the recalcitrant soil organic matter pool, the molecular-level composition of aged BC has hardly been investigated. Pyrolysis-GC/MS, which provides structural information on complex mixtures of organic matter, was applied to the NaOH-extractable organic matter of an acidic colluvial soil (Atlantic ranker) sampled with high resolution (5 cm) that harbours a fire record of at least 8.5 ka. Additionally, 5 charcoal samples from selected soil layers were characterised using pyrolysis-GC/MS for comparison. Pyrolysis-GC/MS allowed distinguishing between BC and non-charred organic matter. It is argued that a large proportion of the polycyclic aromatic hydrocarbons (PAHs), benzenes and benzonitrile in the pyrolysates of the extractable organic matter, together accounting for 21-54% of total identified peak area, derived from BC. In charcoal samples, these compounds accounted for 60-98% of the pyrolysis products. The large quantity of BC in almost all samples suggested a key role of fire in Holocene soil evolution. The high C content of the soil (up to 136 g C kg(-1) soil) may be attributed to the presence of recalcitrant organic C as BC, in addition to the sorptive preservation processes traditionally held responsible for long-term C storage in acid soils. Interactions between reactive Al hydroxides and BC could explain the longevity of BC in the soil. This work is the first thorough pyrolysis-GC/MS based study on ancient fire-affected organic matter.