Self-diagnosis of model suitability for continuous measurements of stream-dissolved organic carbon derived from in situ UV–visible spectroscopy

Application of high-frequency monitoring of dissolved organic carbon (DOC) is difficult in instances where training datasets are challenging to develop (e.g., remote locations) and the relationship between optical features and DOC concentration changes due to environmental or landscape shifts (e.g., climate or land-use change). We developed and compared three partial least squares (PLS) models using in situ water level measurements, conductivity, and UV–Vis spectral attenuation to predict DOC. Two site-specific models were developed using data from a hillslope-dominated forest or a low-relief wetland-pond-dominated stream catchment. The third model, using data from both sites, exhibited the best performance (DOC range = 4–15.5 mg C L⁻¹, mean = 8.38 mg C L⁻¹, training RMSE = 0.34 mg C L⁻¹, internal validation RMSE = 0.50 mg C L⁻¹, external validation RMSE = 2.43 mg C L⁻¹). We further demonstrate using PLS model statistics to monitor performance and elucidate when and how models should be updated. These statistics, Hotelling's T² and squared prediction errors, are useful consistency checks for the predictions made and detect underlying inconsistencies that, if undetected, can reduce the robustness of DOC prediction. For example, via the T² statistic, we identified the summer–autumn transition as a period when DOC composition differed from what was represented in the training dataset. We also determined that elevated SUVA₂₅₄ values contributed to the overall bias observed in predictions made during the subsequent year as part of the external validation. This enabled the application of a bias correction that reduced the RMSE from 2.43 to 0.89 mg C L⁻¹. The method presented here could be applied to future monitoring programs enabling model updates to monitor DOC fluxes accurately from optical datasets (e.g., attenuance or fluorescence) in the face of developing datasets in remote locations or environmental change. Implementation of this approach may also identify possible regime shifts or landscape and hydrologic change associated with climate and other environmental changes relevant to terrestrial to aquatic fluxes.