Chemical and spectroscopic characteristics of humic acids in marshes from the Iberian Peninsula

Abstract

To characterise soil humic acids (HAs) extracted from Spanish marshes formed under different vegetation types (Spartina maritima (GSp), Juncus maritimus (GJc), Phragmites australis (GPh), and Scirpus maritimus (VSc)), soil depths (0–20, 20–40 and 40–60 cm), physiographic position (low and high marshes), wetland types (salt marshes and lagoons) and environmental conditions (Atlantic and Mediterranean coast). Soil samples were collected in five Spanish marshes, three on the Galicia province and two on the Valencia province. Humic acids were extracted and their elemental composition, semiquinone-type free radical (SFR) content, FTIR and CPMAS 13C NMR spectra determined. Total carbon (TC), total nitrogen (TN), total sulphur (TS), CaCO3 content, and field pH and Eh (mV) in the marsh soils sampled were also measured. The field pH and Eh values were typical of coastal areas submitted to periodic inundations and the highest TC, TN and TS contents were found in the soil of lagoon marshes as an effect of physiographic position and wetland type. The HAs, in general, were highly aliphatic and exhibited a low SFR content, which suggests a low humification degree of the SOM formed in the studied areas. This is a result of the anaerobic decomposition to which SOM is submitted and the high input of plant-derived organic matter (OM) by vegetation. However, among the studied sites low salt marsh and subsurface layer of the high salt marsh showed higher SFR content, simpler FTIR spectra, higher lignin degradation and lower O-alkyl C/alkyl C ratio than the lagoon marshes, thus suggesting the presence of a more humificated SOM in these sites. From the different factors analysed, only physiographic position (low versus high salt marshes) and wetland type (marshes versus lagoons) caused variations in the HAs characteristics, because as the studied soils are under anaerobic conditions, they control the exportation of plant-derived OM and the allochthonous OM contribution in the studied areas.