Insights into the effects of natural pyrite-activated sodium percarbonate on tetracycline removal from groundwater: Mechanism, pathways, and column studies

In-situ chemical oxidation based on sodium percarbonate (SPC) has received much attention for remediation of groundwater contaminated with organic pollutants due to the high efficiency, stable reaction, and sustainability of SPC. Currently, metal ions and their composite materials, are mainly employed for the activation of SPC. However, due to its narrow pH range, slow Fe3+/Fe2+ circulation, and generation of refractory sludge, its application in groundwater is limited. In this study, SPC was activated with natural pyrite (FeS2) to remove tetracycline, which was selected as the target pollutant. FeS2 exhibited excellent catalytic activity and stability towards the degradation of tetracycline. The tetracycline degradation efficiency of SPC/FeS2 system reached 70 % within 10 min, and nearly half of the tetracycline was degraded in the first 5 min of the reaction. The optimum SPC dosage for the tetracycline removal was 8 mM, with FeS2 dosage of 0.5 g/L. The tetracycline removal efficiency remained above 60 % after 4 cycles, indicating its good recycling efficiency of the system. SPC/FeS2 system was not significantly affected by the initial pH or the presence of Cl-, SO42-, NO3- while, HCO3-, Ca2+, Mg2+, and humid acid suppressed the reaction. The electron paramagnetic resonance spectroscopy and quenching experiments demonstrated that OH and O2- played a dominant role in tetracycline removal by the system. S22-, as an electron donor, was able to participate in the Fe3+/Fe2+ cycle. In addition, the 13 transformation products were determined by liquid chromatography-mass spectrometry predicted that the degradation pathway of tetracycline consisted of hydroxylation, demethylation, and decarbonylation reactions. Finally, the dynamic simulation experiments of SPC/FeS2 sand column showed that FeS2 effectively activated SPC and significantly reduced the toxicity in groundwater after the packed column treatment. This study reveals that FeS2 can efficiently activate SPC and has good prospects for tetracycline-contaminated groundwater remediation applications.