Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).

► Cr(VI) removal by Fe0 was faster in humic acid (HA) compared to fulvic acid (FA).
► As(V) removal by Fe0 was inhibited in HA compared to FA.
► Fluorescence spectroscopy showed no redox reaction occurring in FA and HA.
► Metal binding sites of NOM can affect Cr(VI) and As(V) removal by Fe0.
► Aggregation of iron corrosion products was induced by gel-bridging of metal-NOM.