Algal-derived dissolved organic matter (ADOM) is a critical component of endogenous dissolved organic matter (DOM) in aquatic systems, distinguished by its characteristic fluorescence response and high photochemical reactivity. Hulun Lake, the fifth largest lake in China, has experienced recurrent algal blooms accompanied by elevated iron (Fe) concentrations, providing an ideal natural setting to investigate the coupled photochemical roles of ADOM and Fe. This study examines the dual photochemical effects, both upward (emission of gas-phase substance) and downward (release of dissolved or particulate matter), during iron-mediated photodegradation of ADOM. Using ADOM extracted from Hulun Lake algae, we conducted simulated photodegradation experiments to investigate how Fe influences reactive intermediates formation and ADOM degradation, and to elucidate the mechanisms governing greenhouse gases (GHGs) emissions and nutrient release, particularly phosphorus. Our results reveal that both Fe(III) and Fe(II) enhance hydroxyl radical (•OH) generation and ADOM mineralization. At low concentrations (0.3 mg·L-1), Fe(III) saturates in quenching triplet-state ADOM (3ADOM*), while Fe(II) exhibits concentration-dependent inhibition. Fe(III) primarily drives free radical generation via complexation with ADOM, while Fe(II) mainly promotes the Fenton reaction, highlighting distinct photochemical pathways. Notably, the release rate of dissolved inorganic phosphorus (DIP) showed a significant positive correlation with •OH concentration (p < 0.001), indicating •OH-mediated oxidative transformation of dissolved organic phosphorus (DOP) to DIP. At an ADOM level of 10 mgC·L-1, the directly released DIP exceeds the eutrophication threshold for surface water (>0.02 mg·L-1). Furthermore, both Fe ions and ADOM concentration significantly enhance photochemical GHGs emissions, dominated by CO2. The relative contributions of CH4 and N2O to global warming potential decreased initially before stabilizing under radical-driven reactions, a pattern linked to ADOM chemical structure. These findings provide a new perspective for in-depth understanding of the carbon-iron-phosphorus interaction and climatic effects, offering a scientific basis for ecological protection and sustainable management.