Characterising changes in fluorescence properties of dissolved organic matter and links to N cycling in agricultural floodplains

Sand and gravel aquifer systems are common features below and adjacent to river networks and are important in providing a hydrological link between terrestrial and aquatic ecosystems. They are often used for intensive agriculture and therefore provide a conduit for the transport of nutrients to aquatic systems. Understanding the biogeochemical cycles of C and N in such systems is essential in efforts to improve water quality, with a major link being the transfer and properties of DOM which drives microbial processing of nutrients. In this work undertaken in the Trent Valley, U.K., the differences in dissolved organic matter (DOM) properties in the soil, aquifer ground water and river water are examined using excitation-emission matrix fluorescence spectroscopy (EEM), in addition to chemical analysis. In the aquifer system studied the water table is ∼1.5 m below the land surface, suggesting that DOM and nutrient transfer would occur between the soil and groundwater. Nitrate levels in the ground water were ∼50 mg L−1 NO3-N. Soil DOM properties were measured in KCl extracts used to extract inorganic and organic N so that further information could be obtained regarding possible sources and properties of the DON and the biodegradability of the DOC pool. Within the soils tested, fulvic-like properties and the humification index (HI) were significantly (P < 0.05) higher in sandy soils suggesting that microbial accessibility to organic matter was greater. The applicability of assessing DOM characteristics in the different matrices were assessed and quantitative or qualitative comparisons made. Properties of DOM in both the soils and aquifer waters all showed a typical terrestrial source with principal component analysis (PCA) showing strong correlations between DOC, fulvic-like properties, the HI and tryptophan-like properties. A major finding was that the HI was generally higher in the groundwater, suggesting continued processing of DOM within the aquifer whilst qualitative comparisons showed the groundwater possessed a higher fluorescence index (FI). Whilst DON and the tyrosine-like proteins were correlated in the soil, the tryptophan-like proteins were strongly correlated to fulvic-like substances in both the soil and groundwater. This suggested that phenolic compounds were also being identified in this part of the EEM matrix, emphasising the need for additional compound analysis to fully understand the nature of DOM in these systems.