Pesticide residues from agriculture pose persistent threats to ecosystems and human health. Precipitation and surface runoff facilitate the transport of pesticide residues, leading to their subsequent accumulation in lakes and rivers. Microalgae-based bioremediation offers a promising and environmentally friendly approach for degrading and detoxifying these residues. This study employed liquid chromatography–mass spectrometry (LC-MS) to determine pesticide residues in various microalgal solutions. Using three-dimensional excitation-emission matrix (3D-EEM) spectroscopy and fluorescence regional integration (FRI), we quantified the dynamics of dissolved organic matter (DOM) and its relationship with pesticide degradation in the microalgal system. Over time, Tolypothrix tenuis exhibited the highest degradation rate for THX (95.7%), while Anabaena showed the most effective degradation for ATZ (53.8%). Based on structural analysis of degradation products, three potential degradation pathways for THX and ATZ under microalgae action were proposed. Moreover, the degradation process may also involve reactive oxygen species and intracellular enzymes. Hydroxylation and carboxylation were the primary reactions involved in THX degradation, leading to ring opening and subsequent mineralization. In ATZ, the initially removed groups included methyl and carbonyl groups, with the final products undergoing hydroxylation and subsequent mineralization to water and carbon dioxide. This study, conducted within the context of aquatic environmental protection, investigates the threat of pesticide residues to aquatic ecosystems. It further elucidates the associated environmental impacts and degradation mechanisms from a microalgal perspective.
This work focused on the Xinghua River, a typical urbanizing river, to investigate how different anthropogenic activities affect the composition, sources, and environmental impact of dissolved organic matter (DOM) during urbanization. Using fluorescence spectroscopy combined with multivariate statistics, we systematically explored DOM characteristics and their response to urbanization. A total of four fluorescent components were identified, including protein-like components C1 and C3, and humic-like components C2 and C4, with protein-like substances constituting the major fraction of DOM. Fluorescence indices indicated that DOM in the Xinghua River was primarily derived from autochthonous sources (FI > 1.9), with a low degree of humification reflecting the dominance of fresh organic matter input during urbanization. Spatial analysis revealed that from upstream to downstream, the source of DOM gradually shifted from autochthonous dominance to increased allochthonous input, accompanied by increasing trends in both protein-like and humic-like components, indicating an accumulative effect of anthropogenic activities along the river. 2D-COS further revealed that the transformation sequence of DOM components along the flow direction was C3 → C1 → C4 → C2, suggesting that tyrosine/tryptophan-like substances were the most sensitive to anthropogenic disturbance. Redundancy analysis identified total phosphorus (TP), total dissolved solids (TDS), and permanganate index (CODMn) as the key environmental factors influencing DOM distribution, highlighting the synergistic regulatory roles of nitrogen and phosphorus nutrients and organic pollution loads on DOM composition. This study not only elucidates the gradient effects of human activities on DOM in the Xinghua River but also provides a scientific basis for water management in urban rivers worldwide, particularly for zone-based control and source-oriented management.