Fluorescent substances are used as good tracers in dissolved organic matter (DOM) to identify the source of DOM and its geochemical behavior in a hydrological system. However, there are few studies on the karst aquifer system. Many parameters in karst systems affect the DOM spectral information. A typical karst watershed in Northern China was selected in this research. Excitation-emission matrices (EEMs), parallel factor analysis (PARAFAC), and hydrochemical data were applied to reveal the relationship between the composition and transformation of DOM fluorescent substances in different karst water-bearing spaces. The source of DOM and the effect of water chemistry on DOM transfer were also discussed. The results showed that DOM in exogenous surface water and karst surface water in the Yufu River watershed were mainly composed of tryptophan-like substances, while the DOM in shallow karst water and deep karst water consisted of tryptophan-like and tyrosine-like substances. A comprehensive analysis by fluorescence index (FI), biological index (BIX), and humification index (HIX) displayed that the DOM in shallow and deep karst water resulted from microbial decomposition. In contrast, the DOM in karst surface water and exogenous surface water resulted from land-based input and endogenous microbial decomposition, in which endogenous contributions occupy a large proportion. Due to the chemical parameters of karst water, these three kinds of fluorescent substances extracted by PARAFAC had obviously different characteristics, i.e., ① the tyrosine-like substances had a strong adaptability to Ca2+ and HCO3-, and the proportion of the tyrosine in karst water was relatively large; ② the tryptophan substance followed an opposite trend; and ③ there was a significant positive correlation between fulvic acid and TDS, turbidity, Cl-, and SO42-. Observations of the watershed runoff revealed that the DOM in shallow karst water in the upper reaches came mainly from the soil and microbial degradation. The organic matter underwent a large amount of microbial decomposition and exogenous input when the water was rejuvenated with springs. After infiltration to the deep karst water in the lower reaches, the DOM gradually were converted to low aromatic hydrocarbon organic compounds and decreased macromolecules of DOM. Subsequently, the fluorescence intensity was weakened. The principal component analysis (PCA) extracted three principal components. They were the water mineralization index, soil leaching index, and hydrochemical/biochemical process index. The water mineralization index consists of hydrochemical parameters reflecting the water infiltration, transformation, and flow conditions in the karst system. The soil leaching index contains TOC, NO3-, and protein-like indicators relating to the relationship between protein-like substances and soil and natural leaching. The hydrochemical/biochemical process index is composed of Ca2+, HCO3-, FI, and fulvic acid indicators that illustrate the water chemistry and biochemical processes in the karst water system. In addition, the study also showed that total fluorescence intensity, fulvate-like substances, and protein-like substances can be used as a tracer for rapid seepage, transformation, and aquifer fragility for karst water, respectively. The results of the study are important in understanding the biogeochemical cycle of DOM in the karst water system and also helpful for controlling organic pollution. It also provides a new tool for characterizing the geochemical processes of organic matter in karst system.
Keywords: dissolved organic matter (DOM); karst aquifer system; karst catchment; migration and transformation; three-dimensional fluorescence spectroscopy.