Inhibitory effects and mechanisms of insoluble humic acids on internal phosphorus release from the sediments

Release of phosphorus (P) from the sediments plays a critical role in the eutrophication of aquatic environments. Humic acids (HA), as the main form of carbon storage in the sediments, has essential impacts on the biogeochemical cycle of phosphorus in aquatic systems. Nevertheless, previous studies mainly concentrated on the competitive adsorption of HA solution and P on metal oxides and soils, with little attention paid to the effects of insoluble humic acids (IHA) on P sorption by and release from the sediments. Herein, an investigation on the rivers and lakes in Sichuan Province, China, found that there was a significantly positive correlation between the maximum P adsorption capacity (Q_max) of sediments and IHA contents (p < 0.01), but a significantly negative correlation between the zero equilibrium P concentration (EPC₀) and IHA concentrations (p < 0.01). This indicated that IHA might have an inhibitory effect on the release of P from the sediments, which was verified by batch adsorption experiments and static incubation experiments. Adsorption experiments indicated that IHA can promote P adsorption by sediments. With the increase of IHA addition (from 0 to 20 mg/g) in the sediments, Q_max of sediments increased (from 0.516 to 0.911 mg/g), while EPC₀ decreased greatly (from 0.264 to 0.005 mg/L). Increases in Fe (Ⅲ) bound-P, Al bound-P and humic bound-P caused by IHA were responsible for this promoting effect. Incubation experiments illustrated that IHA addition can efficiently inhibit P release from the sediments. After 32 days incubation, P concentration in the overlying water of control group (without IHA addition) was 0.651 mg/L, which was 13.29-40.69 times higher than those (0.016-0.049 mg/L) in the test groups (with 5 %-20 % IHA addition). The analysis of P species in sediments showed that transformation from loosely adsorbed-P and Fe (Ⅲ) bound-P to Al bound-P and humic bound-P was responsible for this inhibition of P release by IHA. This study demonstrated that IHA, differing from readily degradable or dissolved organic matter, have great inhibitory effects on internal P release, which provided a novel insight into the association between carbon burial and internal P release and even the management of water eutrophication.