Sulfidated nanoscale zero-valent iron derived from iron sludge for tetracycline removal: Role of sulfur and iron in reactivity and mechanisms.

Iron sludge, produced during the drinking water treatment process, can be recycled as potential iron resource to create environmental functional material. In this study, sulfur-iron composites derived from iron sludge (S-Fe composites) was synthesized through sulfidation and carbonization, and used for the tetracycline (TC) removal under aerobic and anoxic conditions. The reactivities of these as-prepared products were strongly depended on pyrolysis temperatures. In particular, sulfidated nanoscale zero-valent iron loaded on carbon (S-nFe@CIS) carbonized at 800 °C exhibited the highest TC removal efficiency with 86.6% within 30 min at circumneutral pH compared with other S-Fe composites. The crystalline structure of α-Fe, FeS and S as main active sites in S-nFe@CIS promoted the degradation of TC. Moreover, the Fe/S molar ratios significantly affected the TC removal rates, which reached the best value as the optimal S/Fe of 0.27. The results illustrated that the optimized extent of sulfidation could facilitate electron transfer from nFe towards contaminants and accelerate Fe(III)/Fe(II) cycle in reaction system compared to bared nFe@CIS. We revealed that removal of TC by S-nFe@CIS in the presence of dissolved oxygen (DO) is mainly attributed to oxidation, adsorption and reduction pathways. Their contribution to TC removal were 31.6%, 25.2% and 28.8%, respectively. Furthermore, this adsorption-oxygenation with the formation of S-nFe@CIS-TC* complexes was a surface-mediated process, in which DO was transformed by the structural FeS on complex surface to •OH with the generation of HO intermediate. The intermediates of TC and toxicity analysis indicate that less toxicity products generated through degradation process. This study provides a new reclamation of iron sludge and offers a new insight into the TC removal by S-nFe@CIS under aerobic conditions.