Enhanced chemodiversity, distinctive molecular signature and diurnal dynamics of dissolved organic matter in streams of two headwater catchments, Southeastern China.

• High DOM chemodiversity is ubiquitous in all headwater streams and a large river. • S-containing and aliphatic compounds originate from rural domestic effluent. • Ecosystem respiration can be controlled by anthropogenic sources of DOM. • H/C of 1.07 and O/C of 0.37 were typical precursors of DBPs. • DOM with 151 to 635 Da was the main part that was hard to remove through degradation. Dissolved organic matter (DOM) is a complicated assembly of organic molecules, including thousands of molecules with various structures and properties. However, how the stream DOM sources respond to carbon compositions and the transformation processes remains unclear. In this study, the chemical characteristics and spectral and mass spectrometry (FT-ICR MS) of DOM were analyzed. Six sampling points of headwater stream (HWSs) were sampled, and an effluent polluted stream (WSR) and a main stream of the Changjiang River (DT) were also sampled for comparison. In situ degradation experiments and FT-ICR MS analysis were also performed to observe the dynamic processes of DOM in HWS. The results showed that the anthropogenic markers of sewage (i.e. sulfur (S) compounds and marker from antibiotics and estrogen) in HWS were higher than those in DT. The molecular weight decreased while the degradation products (S-containing compounds and unsaturated compounds (HU)) increased after in situ degradation due to the influence of both the photodegradation and biodegradation process. In addition, the KMD plots showed that the DOM homologue intensities in range 400–600 Da changed significantly after demethylation by biodegradation. The components of highly refractory substances and the degradation degree of DOM in DT was higher than that in HWS. We extracted the refractory DOM pool in HWS, which was mainly small molecular with molecular weights < 600 Da. These molecular will be difficult to remove in traditional drinking water treatment processes and easily produced disinfection byproducts (DBPs). This study emphasized the necessity of identifying the sources and transformation processes of DOM in HWS and clarified the types and characteristics of DOM that should be considered in future drinking water treatment. [Display omitted] [ABSTRACT FROM AUTHOR]