Tracking transport and transformation of dissolved organic matter using fluorescence spectroscopy at Rifle vadose zone, Colorado

Abstract:

Dissolved organic matter (DOM) represents the most mobile and active form of natural organic matter. It plays important roles in terrestrial C transport and biogeochemical cycles. Its reactivity makes it sensitive to seasonal variations and climate change. The objective of this study is to investigate the transport and transformation of DOM by tracking the spatial and seasonal variations of DOM concentrations and characteristics throughout the vadose zone and groundwater within a semi-arid floodplain at Rifle, Colorado. Three sets of vertically stratified pore water samplers were installed along a groundwater flow transect, and allowed collection of temporally resolved pore water samples from different depths. Fluorescence excitation-emission matrix (EEM) spectroscopy was used to trace changes in DOM characteristics. The humification index (HIX) was applied to evaluate variations in humification extent of DOM. EEM analysis identified fulvic-like, humic-like, tryptophan-like and tyrosine-like substances as the major fluorescent components of DOM in pore waters. Tryptophan-like and tyrosine-like compounds are typically considered as the recent microbial by-products, and they showed higher concentrations in the deeper vadose zone in late spring, and decrease from spring to winter. HIX values are smaller within the deeper vadose zone (1.5 ̶ 3.5 m) than in the overlying 1.0 m soil water and underlying groundwater samples (≥ 3.5 m), suggesting that some non- or less-humified DOM (or “fresh” microbial-derived DOM) was transferred during late spring. HIX value at each depth increased continuously from late spring to winter, with rapid humification occurring in late spring to early summer. These results suggest an annual cycle in which less humified soil organic matter is transferred into the deeper vadose zone during snowmelt/rainfall events, and then humified further through microbial transformation.