Influences of Humic Acid on Cr(VI) Removal by Zero-Valent Iron From Groundwater with Various Constituents: Implication for Long-Term PRB Performance

Abstract

A 9-month-long continuous flow column study was carried out to investigate Cr(VI) removal by Fe0 with the presence of humic acid. The study focused on the influences of humic acid promoted dissolved iron release and humic acid aggregation in Fe0 columns receiving synthetic Cr(VI) contaminated groundwater containing various components such as bicarbonate and Ca. The effects of humic acid varied significantly depending on the presence of Ca. In Ca-free columns, the presence of humic acid promoted the release of dissolved iron in the forms of soluble Fe-humic acid complexes and stabilized fine Fe (hydr)oxide colloids. As a result, the precipitation of iron corrosion products was suppressed and the accumulation of secondary minerals on Fe0 surfaces was diminished, and a slight increase in Cr(VI) removal capacity by 18% was record compared with that of humic acid-free column. In contrast, in the presence of Ca, as evidenced by the SEM and FTIR results, humic acid greatly co-aggregated with Fe (hydr)oxides and deposited on Fe0 surfaces. This largely inhibited electron transfer from Fe0 surfaces to Cr(VI) and reduced the drainable porosity of the Fe0 matrix, resulting in a significant decrease in Cr(VI) removal capacity of Fe0. The Cr(VI) removal capacity was decreased by 24.4% and 42.7% in humic acid and Ca receiving columns, with and without bicarbonate respectively, compared with that of Ca and humic acid-free column. This study yields new considerations for the performance prediction and design of Fe0 PRBs in the environments rich in natural organic matter (NOM).