A data-driven approach for understanding the structure dependence of redox activity in humic substances

Humic substances (HS) can facilitate electron transfer during biogeochemical processes due to their redox properties, but the structure-redox activity relationships are still difficult to describe and poorly understood. Herein, the linear (Partial Least Squares regressions; PLS) and nonlinear (artificial neural network; ANN) models were applied to monitor the structure dependence of HS redox activities in terms of electron accepting (EAC), electron donating (EDC) and overall electron transfer capacities (ETC) using its physicochemical features as input variables. The PLS model exhibited a moderate ability with R² values of 0.60, 0.53 and 0.65 to evaluate EAC, EDC and ETC, respectively. The variable influence in the projection (VIP) scores of the PLS identified that the phenols, quinones and aromatic systems were particularly important for describing the redox activities of HS. Compared with the PLS model, the back-propagation ANN model achieved higher performance with R² values of 0.81, 0.65 and 0.78 for monitoring the EAC, EDC and ETC, respectively. Sensitivity analysis of the ANN separately identified that the EAC highly depended on quinones, aromatics and protein-like fluorophores, while the EDC depended on phenols, aromatics and humic-like fluorophores (or stable free radicals). Additionally, carboxylic groups were the best indicator for evaluating both the EAC and EDC. Good model performances were obtained from the selected features via the PLS and sensitivity analysis, further confirming the accuracy of describing the structure-redox activity relationships with these analyses. This study provides a potential approach for identifying the structure-activity relationships of HS and an efficient machine-learning model for predicting HS redox activities.