Overlooked encounter process that affects physical behaviors of stabilized nanoscale zero-valent iron during in situ groundwater remediation

Dynamic encountering between groundwater matrices and nanoscale zero-valent iron (NZVI) injected for in situ subsurface remediation affects NZVI's mobility and has not been well recognized. Polyacrylic acid (PAA)-stabilized NZVI (NZVI-PAA) and Mg(OH)2-coated NZVI (NZVI@Mg(OH)2) were investigated as representative NZVIs stabilized by enhanced electrostatic repulsion and reduced magnetic attraction, respectively. Encounters with divalent cations and humic acid (HA) induced the drastic aggregation and sedimentation (pre sedimentation) of NZVI-PAA owing to Lewis acid-base interactions and heteroaggregation. In addition, encountered groundwater electrolytes could not effectively provide electrostatic repulsion for NZVI-PAA, resulting in breakthrough ripening dynamics. The presedimentation and ripening behaviors of NZVI-PAA were eliminated and unheeded after mixing the NZVI slurry with groundwater by sonication. In comparison, the encountering process barely impacted NZVI@Mg(OH)2, for which settling was hindered. Although the particle-collector attraction promoted NZVI@Mg(OH)2 adsorption on pristine and hybrid-coated sands, the Langmuirian blocking dynamics of the NZVI@Mg(OH)2 breakthrough demonstrated its high mobility after adsorption sites of sand surface were exhausted. Extended Derjaguin-Landau-Verwey-Overbeek analysis and transport modeling provided insights into overlooked effects of encountering on physical behaviors of different stabilized NZVIs, which should be considered during practical applications under diverse subsurface conditions.