Temporal and spatial changes in dissolved organic carbon concentration and fluorescence intensity of fulvic acid like materials in mountainous headwater catchments

Abstract

Dissolved organic carbon (DOC) such as humic substances are key to understanding the aquatic environment in catchments, because they, containing a large number of phenolic and carboxylic acid groups, adsorb many kinds of inorganic materials and also affect nutrition and carbon transport in catchments. To understand the detailed DOC dynamics, we conducted hydrological observations at mountainous headwater catchments dominated by different vegetation types (planted evergreen coniferous forest of 1.29 ha and natural deciduous broadleaf forest of 1.28 ha). The relationship between DOC concentrations and fluorescence intensity of fulvic acid-like materials (F-FAM) were positively correlated in both catchments but different between soil extracts, baseflow, and near surface flow represented by biomat flow. The ratios of change in F-FAM to that in DOC concentration (F-FAM/DOC) were higher in the baseflow (about 6 in both catchments) and lower in the soil extracts (about 4.5 in both catchments, respectively). However, the relationship in stormflow was distributed between the trends of baseflow and soil extracts. The higher F-FAM/DOC in baseflow may thus indicate that DOC (and FAM) in groundwater discharge mainly contributed to the stream flow, and the stormflow mainly reflect subsurface flow through soil during most rainstorms. In contrast, a high F-FAM/DOC ratio (>6) appeared in the stormflow of both catchments especially during large storms of short duration and high intensity following a dry antecedent period. The F-FAM/DOC in biomat flow developing distinctly in the coniferous catchment was high (about 6.5). Thus, rapid shallow subsurface flow through the biomat or near-surface of slopes might explain the unique transport dynamics of DOC and FAM in stormflows with the high F-FAM/DOC ratio. These results imply that the DOC and FAM relationship responds variably depending on both the distribution of soil organic matter and rainwater flow paths in steep slopes as well as on storm size and characteristics.