Characteristics of zero-valent iron surface oxide films under the catalytic interface reactions by assisting ligands in nitrate-contaminated groundwater
Wen Zhang, Liang Qi, Ling Li, Chengchen Guo, Liwen Xiao
Abstract
The surface passivation layer coating on zero-valent iron (ZVI) particles impedes the electron transfer from ZVI to nitrate. To enhance the efficiency of nitrate reduction by Fe(0), we tested the chemical process and the thickness of the iron oxide film on the surface of Fe(0) particles, utilizing Fe 2+ aq in aqueous solution and wheat straw as ligands. A novel principal surface catalyzing reaction was formulated as follows: NO 3 − + 0.67 Fe 2 + + 2.2 Fe 0 + 2.33 H 2 O → NH 4 + + 1.18 Fe 3 O 4 + 0.64 OH − . When Fe 2+ aq concentration increased from 0 - 200 mg·L −1 , the NO 3 - removal rate increased from 6.95% to 82.6% respectively during 12 h and it was 48%, 72%, 79% and 94% respectively in Fe 0 /WS ratio of 0, 0.25, 0.5 and 1 system. Uniform surface iron oxide films formed around the Fe(0) particles within 12 h after the adding Fe 2+ aq or wheat straw to the Fe(0) system. The composition and thickness of these films were dependent on the quantity of added materials. X-ray diffraction (XRD) analysis revealed that surface oxide iron mainly consisted of Fe 2+ or Fe 3+ oxides, with Fe 3 O 4 being predominant. The X-ray photoelectron spectroscopy (XPS) etching indicated that the addition of Fe(0)/straw at mass ratios of 1 or system with 20 mg·L −1 Fe 2+ aq resulted in the thinnest surface iron oxide layer. The study demonstrated that reducing the oxide layer’s thickness was achieved through partial catalysis and enhanced complexation capacity. This reduction was facilitated by the introduction of Fe 2+ aq or wheat straw into the Fe(0) system, potentially improving proton dissociation and promoting the ligand-assisted dissolution of Fe 3+ oxides. The Journal of Hazardous Materials focuses on novel and urgent research in environmental science. This manuscript aligns well with the journal's standards for scientific merit, as our research offers a fresh perspective on surface interface reactions for the treatment of groundwater. Nitrate (NO 3 − ) is a toxic environmental contaminant. The reduction of nitrate using zero-valent iron (Fe 0 ) is a primary technique for treating groundwater. The surface passivation layer coating on Fe 0 particles hinders the transfer of electrons from iron to nitrate. The study is to enhance the efficiency of nitrate reduction through Fe 0 and alleviate the adverse effects of iron oxides. • Increased dosage of Fe 2+ aq enhances dissolution of passivated oxide layers. • Reduction in oxide layer thickness with Fe 2+ aq and wheat straw. • Fresh Fe(0) was typically observed within 15 s by etching the surface oxide. • Fe 2+ aq promotes corrosion of passivation film on iron particles. • Wheat straw as a viable alternative to Fe 2+ aq for enhanced NO 3 - Removal.