Humic acid composition and humification processes in wetland soils of a Mediterranean semiarid wetland

Abstract

The present study focuses on a compositional characterization of the humic acid (HA) fraction of several wetland soils using solid-state 13C NMR spectroscopy. The data were analysed using the molecular mixing model (MMM), based on an empirical approach by Nelson and Baldock. The compositional data from HAs obtained with this model were used to obtain a wider assessment of the process of humification from comparison of total soil wetland organic matter composition and HA composition. Twenty samples of humic acids (HAs) isolated from a Mediterranean semiarid wetland (‘Tablas de Daimiel’, central Spain) were studied using elemental analysis and cross polarization magic angle spinning (CPMAS)13C nuclear magnetic resonance (NMR) spectroscopy. The NMR data were analysed with the molecular mixing model (MMM) considering up to six generic components (carbohydrate, protein, lignin, lipid, char and ‘carbonyl’). HAs are considered a conceptual mixture of these model components, and the MMM determines the proportions of the characteristic biomolecules contributing to HA composition. The composition of the HAs under study depends on local factors such as site vegetation and occurrence of fire. Correlations between the proportions of the six generic components and further comparison with those determined for the unfractionated OM (whole sample, WS), gave information on HA origin and humification mechanisms. In particular, the proportions of char and carbohydrate (R 2 0.637) and contents of lignin and protein (R 2 0.471) in the HAs were negatively correlated (P < 0.05). Significant correlations (R 2 0.439) also existed for char contents in whole sample (WS) compared to HA, and for carbohydrates in WS compared to HA (R 2 0.558). Char proportion grew in HA with respect to the WS, and carbohydrates dropped to a half on average in HA compared to WS. Two different humification mechanisms could be identified for no-fire and fire areas. In the former, HA-char was preserved selectively from char in the sample, whereas in the latter, char was newly formed by fire effect.