New insights into the degradation and detoxification of methylene blue using heterogeneous-Fenton catalyzed by sustainable siderite

Abstract

The huge application of synthetic dyes caused a severe impact in the environment. In the present study, a physico-chemical strategy of heterogeneous-Fenton catalyzed by the natural ferrous ore has been established for toxic chemical degradation, of which the complex and high-expense repetitive pH adjustment procedures were escaping. And this natural heterogeneous catalyst also could be recycled and sustainable for toxic substances treatment involved in synergetic adsorption and oxidation. The siderite, served as an adsorbent and catalyst for the degradation of methylene blue (MB). Siderite exhibited a better adsorption capacity with a saturated adsorption capacity of ∼11.08 mg/g. Batch adsorption experiments have verified that adsorption rate and adsorption equilibrium followed pseudo-second-order rate model and Langmuir isotherm equation, respectively. The combination with H2O2, showed significant enhancement of MB degradation without any pH adjustment. The effect of siderite dosage, H2O2 dosage, MB concentration, initial pH, and reaction temperature on MB degradation was investigated, which also has indicated the excellent catalytic performance of siderite. About 99.71% of MB was degraded in 480 min with initial pH of 7.0, reaction temperature of 25 °C, siderite, and H2O2 dosage of 2.5 g/L and 122.38 mM, respectively. It was found that siderite could be reused and remained high degradation efficiency on MB after 5 times reutilization, which also could demonstrate the sustainable and effective process to degrade organic pollution. The generation of reactive species including ·OH and O2·- have been confirmed based on scavenger test and electron spin resonance (ESR) analysis, which was dominated by heterogeneous reaction. The possible degradation mechanisms of MB have been predicted based on spectrum scanning and GC-MS analysis. Moreover, acute toxicity assessment with marine photobacterium Vibrio fisheri was conducted to investigate the toxicity change in the adsorption/oxidation coupled process. This sustainable heterogeneous-Fenton technology has been verified as a promising and applicable process for toxic organic chemicals removal due to effective mineralization and detoxification assisted with the natural ore mineral through the simple operation and mild condtions.