Diurnal variability in riverine dissolved organic matter composition determined by in situ optical measurement in the San Joaquin River (California, USA)

Dissolved organic matter (DOM) concentration and composition in riverine and stream systems are known to vary with hydrological and productivity cycles over the annual and interannual time scales. Rivers are commonly perceived as homogeneous with respect to DOM concentration and composition, particularly under steady flow conditions over short time periods. However, few studies have evaluated the impact of short term variability (<1 day) on DOM dynamics. This study examined whether diurnal processes measurably altered DOM concentration and composition in the hypereutrophic San Joaquin River (California) during a relatively quiescent period. We evaluated the efficacy of using optical in situ measurements to reveal changes in DOM which may not be evident from bulk dissolved organic carbon (DOC) measurement alone. The in situ optical measurements described in this study clearly showed for the first time diurnal variations in DOM measurements, which have previously been related to both composition and concentration, even though diurnal changes were not well reflected in bulk DOC concentrations. An apparent asynchronous trend of DOM absorbance and chlorophyll-a in comparison to chromophoric dissolved organic matter (CDOM) fluorescence and spectral slope S₂₉₀₋₃₅₀ suggests that no one specific CDOM spectrophotometric measurement explains absolutely DOM diurnal variation in this system; the measurement of multiple optical parameters is therefore recommended. The observed diurnal changes in DOM composition, measured by in situ optical instrumentation likely reflect both photochemical and biologically-mediated processes. The results of this study highlight that short-term variability in DOM composition may complicate trends for studies aiming to distinguish different DOM sources in riverine systems and emphasizes the importance of sampling specific study sites to be compared at the same time of day. The utilization of in situ optical technology allows short-term variability in DOM dynamics to be monitored and serves to increase our understanding of its processing and fundamental role in the aquatic environment.