Travel distance and transformation of injected emulsified zerovalent iron nanoparticles in the subsurface during two and half years.

Nanoscale zerovalent iron (NZVI) such as Toda Kogyo RNIP-10DS has been used for site remediation, yet information is lacking regarding how far injected NZVI can travel, how long it lasts, and how it transforms to other minerals in a groundwater system. Previously we reported effective mass destruction of chlorinated ethenes dominated by tetrachloroethene (PCE) using emulsified zerovalent iron (EZVI) nanoparticles of RNIP-10DS in a shallow aquifer (1-6 m below ground surface, BGS) at Site 45, Marine Corps Recruit Depot, Parris Island, South Carolina, USA. Here we report test results on transport and transformation of injected EZVI in the subsurface. We employed two EZVI delivery methods: pneumatic injection and direct injection. Effective delivery of EZVI to the targeted zone was achieved with pneumatic injection showing a travel distance from injection points of up to 2.1 m and direct injection showing a travel distance up to 0.89 m. X-ray diffraction and scanning electron microscopy studies on particles harvested from well purge waters indicated that injected black colored NZVI (α-Fe(0)) was transformed largely to black colored cube-like and plate-like magnetites (Fe3O4, 0.1-1 µm, 0-9 months), then to orange colored irregularly shaped lepidocrocite (γ-FeOOH, 0.1-1 µm, 9 months to 2.5 years), then to yellowish lath-like goethite (α-FeOOH, 2-5 µm, 2.5 years) and ferrihydrite-like spherical particles (0.05-0.1 µm) in the top portion of the aquifer (1-2 m BGS). No α-Fe(0) was found in most monitoring wells three months after injection. The formed iron oxides appeared to have a wider range of particle size (submicron to 5 µm) than the pristine NZVI (35-140 nm). Injected NZVI was largely transformed to magnetite (0.1-1 µm) during two and half years in the lower portion of the aquifer (3-6 m).

A two and half-year-performance evaluation of a field test on treatment of source zone tetrachloroethene and its chlorinated daughter products using emulsified zero valent iron nanoparticles.

A field test of emulsified zero valent iron (EZVI) nanoparticles was conducted at Parris Island, SC, USA and was monitored for two and half years to assess the treatment of subsurface-source zone chlorinated volatile organic compounds (CVOCs) dominated by tetrachloroethene (PCE) and its chlorinated daughter products. Two EZVI delivery methods were used: pneumatic injection and direct injection. In the pneumatic injection plot, 2180 L of EZVI containing 225 kg of iron (Toda RNIP-10DS), 856 kg of corn oil, and 22.5 kg of surfactant were injected to remedy an estimated 38 kg of CVOCs. In the direct injection plot, 572 L of EZVI were injected to treat an estimated 0.155 kg of CVOCs. After injection of the EZVI, significant reductions in PCE and trichloroethene (TCE) concentrations were observed in downgradient wells with corresponding increases in degradation products including significant increases in ethene. In the pneumatic injection plot, there were significant reductions in the downgradient groundwater mass flux values for PCE (>85%) and TCE (>85%) and a significant increase in the mass flux of ethene. There were significant reductions in total CVOC mass (86%); an estimated reduction of 63% in the sorbed and dissolved phases and 93% reduction in the PCE DNAPL mass. There are uncertainties in these estimates because DNAPL may have been mobilized during and after injection. Following injection, significant increases in dissolved sulfide, volatile fatty acids (VFA), and total organic carbon (TOC) were observed. In contrast, dissolved sulfate and pH decreased in many wells. The apparent effective remediation seems to have been accomplished by direct abiotic dechlorination by nanoiron followed by biological reductive dechlorination stimulated by the corn oil in the emulsion.