Effects of nitrate on the treatment of lead contaminated groundwater by nanoscale zerovalent iron

Nanoscale zerovalent iron (nZVI) is efficient for removing Pb(2+) and nitrate from water. However, the influence of nitrate, a common groundwater anion, on Pb(2+) removal by nZVI is not well understood. In this study, we showed that under excess Fe(0) conditions (molar ratio of Fe(0)/nitrate>4), Pb(2+) ions were immobilized more quickly (<5 min) than in nitrate-free systems (∼ 15 min) due to increasing pH. With nitrate in excess (molar ratio of Fe(0)/nitrate<4), nitrate stimulated the formation of crystal PbxFe3-xO4 (ferrite), which provided additional Pb(2+) removal. However, ∼ 7% of immobilized Pb(2+) ions were released into aqueous phase within 2h due to ferrite deformation. Oxidation-reduction potential (ORP) values below -600 mV correlated with excess Fe(0) conditions (complete Pb(2+) immobilization), while ORP values ≥-475 mV characterized excess nitrate conditions (ferrite process and Pb(2+) release occurrence). This study indicates that ORP monitoring is important for proper management of nZVI-based remediation in the subsurface to avoid lead remobilization in the presence of nitrate

Enhancement of Dispersibility of Zero-Valent Iron Nanoparticles for Environmental Remediation: Entrapment and Surface Modification with Polymers

Nanoscale zero-valent iron (NZVI) particles have been surface modified and used for contaminant remediation. NZVI tend to agglomerate due to magnetic and van der Waals forces and form larger particles that settle down in aqeous media. Agglomerated particles increase in size and have decreased specific surface area and that lead to decrease in their reactivity. In this research, polymer-based surface modifiers were used to increase dispersibility of NZVI for environmental remediation applications. Ca-alginate was selected to entrap NZVI in beads and used to remove aqueous nitrate. The two-way ANOVA test indicates that there was no significant difference between reactivities (towards nitrate) of entrapped NZVI and bare NZVI. While the reactivity of entrapped NZVI was comparable to bare NZVI, the NZVI particles were found to remain agglomerated or clustered together within the alginate beads. A novel amphiphilic polysiloxane graft copolymers (APGC) was designed, synthesized and used to coat NZVI in an attempt to overcome the agglomeration problem. APGC was composed of hydrophobic polysilosin, hydrophilic polyethylene glycol (PEG), and carboxylic acid. The APGC was successfully adsorbed onto the NZVI surfaces via the carboxylic acid anchoring groups and PEG grafts provided dispersibility in water. Coating of NZVI particles with APGC was found to enhance their colloidal stability in water. The APGC possessing the highest concentration of carboxylic acid anchoring group (AA) provided the highest colloidal stability. It was also found that the colloidal stability of the APGC coated NZVI remained effectively unchanged up to 12 months. The sedimentation characteristics of APGC coated NZVI (CNZVI) under different ionic strength conditions (0-10 mM NaCl and CaCl2) did not change significantly. Degradation studies were conducted with trichloroethylene (TCE) and arsenic(V) [As(V)] as the model contaminants. TCE degradation rates with CNZVI were determined to be higher as compared to bare NZVI. Shelf-life studies indicated no change on TCE degradation by CNZVI over a 6-month period. As(V) removal batch studies with CNZVI were conducted to in both aerobic and anaerobic conditions. Increase in arsenic removal efficiency was observed with CNZVI as compare to bare NZVI in both aerobic and anaerobic conditions. Ionic strengths showed minimal inhibiting effect on arsenic removal by CNZVI.Department of Civil Engineering, North Dakota State UniversityCenter for Nanoscale Science and EngineeringNorth Dakota Water Resources Research Institut

Iron Nanoparticles Coated with Amphiphilic Polysiloxane Graft Copolymers: Dispersibility and Contaminant Treatability

Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, <i>k</i>_SA (Lm^2– h^–1), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007–0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0–10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation