Field-scale demonstration of in situ immobilization of heavy metals by injecting iron oxide nanoparticle adsorption barriers in groundwater.

Remediation of heavy metal-contaminated aquifers is a challenging process because they cannot be degraded by microorganisms. Together with the usually limited effectiveness of technologies applied today for treatment of heavy metal contaminated groundwater, this creates a need for new remediation technologies. We therefore developed a new treatment, in which permeable adsorption barriers are established in situ in aquifers by the injection of colloidal iron oxides. These adsorption barriers aim at the immobilization of heavy metals in aquifers groundwater, which was assessed in a large-scale field study in a brownfield site. Colloidal iron oxide (goethite) nanoparticles were used to install an in situ adsorption barrier in a very heterogeneous, contaminated aquifer of a brownfield in Asturias, Spain. The groundwater contained high concentrations of heavy metals with up to 25 mg/L zinc, 1.3 mg/L lead, 40 mg/L copper, 0.1 mg/L nickel and other minor heavy metal pollutants below 1 mg/L. High amounts of zinc (>900 mg/kg), lead (>2000 mg/kg), nickel (>190 mg/kg) were also present in the sediment. Ca. 1500 kg of goethite nanoparticles of 461 ± 266 nm diameter were injected at low pressure (< 0.6 bar) into the aquifer through nine screened injection wells. For each injection well, a radius of influence of at least 2.5 m was achieved within 8 h, creating an in situ barrier of 22 × 3 × 9 m. Despite the extremely high heavy metal contamination and the strong heterogeneity of the aquifer, successful immobilization of contaminants was observed in the tested area. The contaminant concentrations were strongly reduced immediately after the injection and the abatement of the heavy metals continued for a total post-injection monitoring period of 189 days. The iron oxide particles were found to adsorb heavy metals even at pH-values between 4 and 6, where low adsorption would have been expected. The study demonstrated the applicability of iron oxide nanoparticles for installing adsorption barriers for containment of heavy metals in contaminated groundwater under real conditions.

Non-pumping reactive wells filled with mixing nano and micro zero-valent iron for nitrate removal from groundwater: Vertical, horizontal, and slanted wells.

Non-pumping reactive wells (NPRWs) filled by zero-valent iron (ZVI) can be utilized for the remediation of groundwater contamination of deep aquifers. The efficiency of NPRWs mainly depends on the hydraulic contact time (HCT) of the pollutant with the reactive materials, the extent of the well capture zone (Wcz), and the relative hydraulic conductivity of aquifer and reactive material (Kr). We investigated nitrate removal from groundwater using NPRWs filled by ZVI (in nano and micro scales) and examined the effect of NPRWs orientations (i.e. vertical, slanted, and horizontal) on HCT and Wcz. The dependence of HCT on Wcz for different Kr values was derived theoretically for a homogeneous and isotropic aquifer, and verified using particle tracking simulations performed using the semi-analytical particle tracking and pathlines model (PMPATH). Nine batch experiments were then performed to investigate the impact of mixed nano-ZVI, NZVI (0 to 2 g l-1) and micro-ZVI, MZVI (0 to 4 g l-1) on the nitrate removal rate (with initial [Formula: see text] =132 mg l-1). The NPRWs system was tested in a bench-scale sand medium (60 cm length × 40 cm width × 25 cm height) for three orientations of NPRWs (vertical, horizontal, and slanted with inclination angle of 45°). A mixture of nano/micro ZVI, was used, applying constant conditions of pore water velocity (0.024 mm s-1) and initial nitrate concentration (128 mg l-1) for five pore volumes. The results of the batch tests showed that mixing nano and micro Fe0 outperforms these individual materials in nitrate removal rates. The final products of nitrate degradation in both batch and bench-scale experiments were [Formula: see text] , [Formula: see text] , and N2(gas). The results of sand-box experiments indicated that the slanted NPRWs have a higher nitrate reduction rate (57%) in comparison with vertical (38%) and horizontal (41%) configurations. The results also demonstrated that three factors have pivotal roles in expected HCT and Wcz, namely the contrast between the hydraulic conductivity of aquifer and reactive materials within the wells, the mass of Fe0 in the NPRWs, and the orientation of NPRWs adopted. A trade-off between these factors should be considered to increase the efficiency of remediation using the NPRWs system.

Monitoring the injection of microscale zerovalent iron particles for groundwater remediation by means of complex electrical conductivity imaging.

The injection of microscale zerovalent iron (mZVI) particles for groundwater remediation has received much interest in recent years. However, to date, monitoring of mZVI particle injection is based on chemical analysis of groundwater and soil samples and thus might be limited in its spatiotemporal resolution. To overcome this deficiency, in this study, we investigate the application of complex electrical conductivity imaging, a geophysical method, to monitor the high-pressure injection of mZVI in a field-scale application. The resulting electrical images revealed an increase in the induced electrical polarization (∼20%), upon delivery of ZVI into the targeted area, due to the accumulation of metallic surfaces at which the polarization takes place. Furthermore, larger changes (>50%) occurred in shallow sediments, a few meters away from the injection, suggesting the migration of particles through preferential flowpaths. Correlation of the electrical response and geochemical data, in particular the analysis of recovered cores from drilling after the injection, confirmed the migration of particles (and stabilizing solution) to shallow areas through fractures formed during the injection. Hence, our results demonstrate the suitability of the complex conductivity imaging method to monitor the transport of mZVI during subsurface amendment in quasi real-time.

Guar gum solutions for improved delivery of iron particles in porous media (part 1): porous medium rheology and guar gum-induced clogging.

The present work is the first part of a comprehensive study on the use of guar gum to improve delivery of microscale zero-valent iron particles in contaminated aquifers. Guar gum solutions exhibit peculiar shear thinning properties, with high viscosity in static conditions and lower viscosity in dynamic conditions: this is beneficial both for the storage of MZVI dispersions, and also for the injection in porous media. In the present paper, the processes associated with guar gum injection in porous media are studied performing single-step and multi-step filtration tests in sand-packed columns. The experimental results of single-step tests performed by injecting guar gum solutions prepared at several concentrations and applying different dissolution procedures evidenced that the presence of residual undissolved polymeric particles in the guar gum solution may have a relevant negative impact on the permeability of the porous medium, resulting in evident clogging. The most effective preparation procedure which minimizes the presence of residual particles is dissolution in warm water (60°C) followed by centrifugation (procedure T60C). The multi-step tests (i.e. injection of guar gum at constant concentration with a step increase of flow velocity), performed at three polymer concentrations (1.5, 3 and 4g/l) provided information on the rheological properties of guar gum solutions when flowing through a porous medium at variable discharge rates, which mimic the injection in radial geometry. An experimental protocol was defined for the rheological characterization of the fluids in porous media, and empirical relationships were derived for the quantification of rheological properties and clogging with variable injection rate. These relationships will be implemented in the second companion paper (Part II) in a radial transport model for the simulation of large-scale injection of MZVI-guar gum slurries.

Guar gum solutions for improved delivery of iron particles in porous media (part 2): iron transport tests and modeling in radial geometry.

In the present work column transport tests were performed in order to study the mobility of guar-gum suspensions of microscale zero-valent iron particles (MZVI) in porous media. The results were analyzed with the purpose of implementing a radial model for the design of full scale interventions. The transport tests were performed using several concentrations of shear thinning guar gum solutions as stabilizer (1.5, 3 and 4g/l) and applying different flow rates (Darcy velocity in the range 1·10(-4) to 2·10(-3)m/s), representative of different distances from the injection point in the radial domain. Empirical relationships, expressing the dependence of the deposition and release parameters on the flow velocity, were derived by inverse fitting of the column transport tests using a modified version of E-MNM1D (Tosco and Sethi, 2010) and the user interface MNMs (www.polito.it/groundwater/software). They were used to develop a comprehensive transport model of MZVI suspensions in radial coordinates, called E-MNM1R, which takes into account the non Newtonian (shear thinning) rheological properties of the dispersant fluid and the porous medium clogging associated with filtration and sedimentation in the porous medium of both MZVI and guar gum residual undissolved particles. The radial model was run in forward mode to simulate the injection of MZVI dispersed in guar gum in conditions similar to those applied in the column transport tests. In a second stage, we demonstrated how the model can be used as a valid tool for the design and the optimization of a full scale intervention. The simulation results indicated that several concurrent aspects are to be taken into account for the design of a successful delivery of MZVI/guar gum slurries via permeation injection, and a compromise is necessary between maximizing the radius of influence of the injection and minimizing the injection pressure, to guarantee a sufficiently homogeneous distribution of the particles around the injection point and to prevent preferential flow paths.

Field assessment of guar gum stabilized microscale zerovalent iron particles for in-situ remediation of 1,1,1-trichloroethane.

A pilot injection test with guar gum stabilized microscale zerovalent iron (mZVI) particles was performed at test site V (Belgium) where different chlorinated aliphatic hydrocarbons (CAHs) were present as pollutants in the subsurface. One hundred kilograms of 56µm-diameter mZVI (~70gL(-1)) was suspended in 1.5m(3) of guar gum (~7gL(-1)) solution and injected into the test area. In order to deliver the guar gum stabilized mZVI slurry, one direct push bottom-up injection (Geoprobe) was performed with injections at 5 depths between 10.5 and 8.5m bgs. The direct push technique was preferred above others (e.g. injection at low flow rate via screened wells) because of the limited hydraulic conductivity of the aquifer, and to the large size of the mZVI particles. A final heterogeneous distribution of the mZVI in the porous medium was observed explicable by preferential flow paths created during the high pressure injection. The maximum observed delivery distance was 2.5m. A significant decrease in 1,1,1-TCA concentrations was observed in close vicinity of spots where the highest concentration of mZVI was observed. Carbon stable isotope analysis (CSIA) yielded information on the success of the abiotic degradation of 1,1,1-TCA and indicated a heterogeneous spatio-temporal pattern of degradation. Finally, the obtained results show that mZVI slurries stabilized by guar gum can be prepared at pilot scale and directly injected into low permeable aquifers, indicating a significant removal of 1,1,1-TCA.

Green stabilization of microscale iron particles using guar gum: bulk rheology, sedimentation rate and enzymatic degradation.

Guar gum can be used to effectively improve stability and mobility of microscale zerovalent iron particles (MZVI) used in groundwater remediation. Guar gum is a food-grade, environment friendly natural polysaccharide, which is often used as thickening agent in a broad range of food, pharmaceutical and industrial applications. Guar gum solutions are non-Newtonian, shear thinning fluids, characterized by high viscosity in static conditions and low viscosity in dynamic conditions. In particular, the high zero shear viscosity guarantees the MZVI dispersion stability, reducing the sedimentation rate of the particles thus enabling its storage and field operations. In this work, a comprehensive rheological characterization of guar gum-based slurries of MZVI particles is provided. First, we derived a model to link the bulk shear viscosity to the concentration of guar gum and then we applied it for the derivation of a modified Stokes law for the prediction of the sedimentation rate of the iron particles. The influence of the preparation procedure (cold or hot dissolution and high shear processing) on the viscosity and on the stability of the suspensions was then assessed. Finally, the dosage and concentration of enzymes - an environment friendly breaker--were studied for enhancing and controlling the degradation kinetics of the suspensions. The derived empirical relationships can be used for the implementation of an iron slurry flow and transport model and for the design of full scale injection interventions.

Transport of non-newtonian suspensions of highly concentrated micro- and nanoscale iron particles in porous media: a modeling approach.

The use of zerovalent iron micro- and nanoparticles (MZVI and NZVI) for groundwater remediation is hindered by colloidal instability, causing aggregation (for NZVI) and sedimentation (for MZVI) of the particles. Transportability of MZVI and NZVI in porous media was previously shown to be significantly increased if viscous shear-thinning fluids (xanthan gum solutions) are used as carrier fluids. In this work, a novel modeling approach is proposed and applied for the simulation of 1D flow and transport of highly concentrated (20 g/L) non-newtonian suspensions of MZVI and NZVI, amended with xanthan gum (3 g/L). The coupled model is able to simulate the flow of a shear thinning fluid including the variable apparent viscosity arising from changes in xanthan and suspended iron particle concentrations. The transport of iron particles is modeled using a dual-site approach accounting for straining and physicochemical deposition/release phenomena. A general formulation for reversible deposition is herein proposed, that includes all commonly applied dynamics (linear attachment, blocking, ripening). Clogging of the porous medium due to deposition of iron particles is modeled by tying porosity and permeability to deposited iron particles. The numerical model proved to adequately fit the transport tests conducted using both MZVI and NZVI and can develop into a powerful tool for the design and the implementation of full scale zerovalent iron applications.