Advanced Characterization of Dissolved Organic Matter in Natural Aquatic Environments and Water/Wastewater Treatment Processes

Sudden changes in drinking water quality can cause harmful consequences for end users. Thus, real-time monitoring of drinking water quality can allow early warning and provide crucial gains for securing safe water distribution. This study investigated the advantages of simultaneous real-time measuring of flow cytometry and fluorescence spectroscopy. A contamination event was investigated in a laboratory-scale analysis by spiking drinking water samples with organic nutrients. Flow cytometric data were analyzed by creating fingerprints based on differentiation into high and low nucleic acid cells (HNA/LNA). The detailed characterization of these data showed that an increase in HNA cells indicated an increase in the bacterial growth potential even before actual TCC increases. The fluorescence data was decomposed via the PARAFAC method to reveal seven fluorescent components. Three aromatic protein-like components were associated with the microbiological condition of the drinking water cells; namely, Components 4 (λ_Ex = 279 nm, λ_Em = 351 nm), 6 (λ_Ex = 279 nm, λ_Em = 332 nm), and 7 (λ_Ex = 276 nm, λ_Em = 302 nm). Component 6 was identified as a possible organic variable for appropriate monitoring of TCC, whereas Components 4 and 7 were identified as organic compounds representing nutrients for organisms present in drinking water. Overall, combining both methods for real-time monitoring can be a powerful tool to guarantee drinking water quality.

Although river mixing occurs widely in nature, the corresponding evolution of dissolved organic matter (DOM) composition remains poorly understood. Here, surface water samples were collected at multiple transects in the lower Athabasca River (LAR) under base-flow conditions. Asymmetric flow field-flow fractionation (AF4) coupled to online excitation-emission measurements (EEMs) and parallel factor analysis (PARAFAC) were utilized to investigate the size distribution of fluorescent DOM components during river mixing and the corresponding variation in size-resolved fluorescence. The majority of fluorescent components occurred at 0.810 and 1.170 kDa, reflecting the small size of the DOM molecules with maximum fluorescence. The loadings of fluorescence normalized to absorbance at 254 nm (A₂₅₄) were highest for most terrestrial humic-like components, followed by the microbial humic-like component, and the protein-like components. Differences in size-resolved fluorescence were observed between DOM in humic-rich tributaries and in the mainstem of the LAR upstream of tributary inputs. The trend of variations in the A₂₅₄-normalized PARAFAC loadings of terrestrial humic-like components also illustrates conservative mixing of aromatic-rich terrestrial DOM across size fractions in the LAR. From a molecular point of view, the mixing of fluorescent DOM occurred linearly and simultaneously across sizes without any evidence of aggregation, sedimentation, or changes in the fluorescence or concentration of any size fraction over the >60 km required for complete mixing of the river and its tributaries. Overall, this study provides insights into the size characteristics of fluorescent components of DOM and their conservative mixing behavior in large boreal rivers.