In-situ fluorometers reveal high frequency dynamics in dissolved organic matter for urban rivers

To-date Dissolved Organic Matter (DOM) dynamics have been quantified poorly in urban rivers, despite the substantial water quality issues linked to urbanisation. Research has been hindered by the low temporal resolution of observations and over-reliance on manual sampling which often fail to capture precipitation events and diurnal dynamics. High frequency data are essential to estimate more accurately DOM fluxes/loads and to understand DOM furnishing and transport processes. Recent advances in optical sensor technology, including field deployable in-situ fluorometers, are yielding new high resolution DOM information. However, no consensus regarding the monitoring resolution required for urban systems exists, with no studies monitoring at <15 min time steps. High-frequency monitoring (5 min resolution; 4 week duration) was conducted on a headwater urban stream in Birmingham, UK (N 52.447430 W -1.936715) to determine the optimum temporal resolution for characterization of DOM event dynamics. A through-flow GGNU-30 monitored wavelengths corresponding to tryptophan-like fluorescence (TLF; Peak T1) (Ex 285 nm/ Em 345 nm) and humic-like fluorescence (HLF; Peak C) (Ex 365 nm/Em 490 nm). The results suggest that at base flow TLF and HLF are relatively stable, though episodic DOM inputs can pulse through the system, which may be missed during lower temporal resolution monitoring. High temporal variation occurs during storm events in TLF and HLF intensity: TLF intensity is highest during the rising limb of the hydrograph and can rapidly decline thereafter, indicating the importance of fast flow-path and close proximity sources to TLF dynamics. HLF intensity tracks discharge more closely, but can also quickly decline during high flow events due to dilution effects. Furthermore, the ratio of TLF:HLF when derived at high-frequency provides a useful indication of the presence and type of organic effluents in stream, which aids in the identification of Combined Sewage Overflow releases. Our work highlights the need for future studies to utilise shorter temporal scales than previously used to monitor urban DOM dynamics. The application of higher frequency monitoring enables the identification of finer-scale patterns and subsequently aids in deciphering the sources and pathways controlling urban DOM dynamics.