Transport Of nZVI Research Articles

Numerical prediction of diffusion and electric field-induced iron nanoparticle transport

Zero valent iron nanoparticles (nZVI) are considered very promising for the remediation of contaminated soils and groundwaters. However, an important issue related to their limited mobility remains unsolved. Direct current can be used to enhance the nanoparticles transport, based on the same principles of electrokinetic remediation. In this work, a generalized physicochemical model was developed and solved numerically to describe the nZVI transport through porous media under electric field, and with different electrolytes (with different ionic strengths). The model consists of the Nernst–Planck coupled system of equations, which accounts for the mass balance of ionic species in a fluid medium, when both the diffusion and electromigration of the ions are considered. The diffusion and electrophoretic transport of the negatively charged nZVI particles were also considered in the system. The contribution of electroosmotic flow to the overall mass transport was included in the model for all cases. The nZVI effective mobility values in the porous medium are very low (10−7–10−4cm2V−1s−1), due to the counterbalance between the positive electroosmotic flow and the electrophoretic transport of the negatively charged nanoparticles. The higher the nZVI concentration is in the matrix, the higher the aggregation; therefore, low concentration of nZVI suspensions must be used for successful field application.

Transport characteristics of nanoscale zero-valent iron carried by three different “vehicles” in porous media

This study investigated the transport properties of nanoscale zero-valent iron (Fe0) (nZVI) carried by three vehicles: water, sodium dodecyl sulfate (SDS) solution, and SDS foam. Batch experiments were conducted to assess the sedimentation capability of nZVI particles in these three vehicles. Column experiments were conducted to investigate the transport properties of nZVI in porous media formed with different sizes of sand (0.25 mm to 0.5 mm, 0.5 mm to 0.9 mm, and 0.9 mm to 1.4 mm). Three main results were obtained. First, the batch experiments revealed that the stabilities of nZVI particles in SDS solution and SDS foam were improved, compared with that of nZVI particles in water. Moreover, the sedimentation of nZVI in foam was closely associated with the foam drainage volume. The nZVI content in foam was similar to that in the original foaming suspension, and the nZVI particle distribution in foam became significantly more uniform at a stirring speed of 3000 r/min. Second, the transport of nZVI was enhanced by foam compared with water and SDS solution for 0.25 mm to 0.5 mm diameter sand. For sand with diameters of 0.5 mm to 0.9 mm and 0.9 mm to 1.4 mm, the mobility of nZVI carried by SDS solution was optimal, followed by that of nZVI carried by foam and water. Thus, the mobility of nZVI in finer sand was significantly enhanced by foam, compared with that in coarse sand. In contrast, compared with the bare nZVI suspension and nZVI-laden foam, the spatial distribution of nZVI particles carried by SDS solution was significantly uniform along the column length. Third, the SDS concentration significantly influenced the migration of nZVI in porous media. The enhancement in the migration of nZVI carried by SDS solution was greater at an SDS dose of 0.25% compared with that at the other three doses (0.2%, 0.5%, and 1%) for sand with a 0.25 mm to 0.5 mm diameter. Increased SDS concentrations positively affected the transport of nZVI by foam for sand with a 0.25 mm to 0.5 mm diameter, and the SDS concentrations for enhancing the mobility of nZVI carried by SDS foam satisfied the following order: 1% > 0.5% > 0.25% > 0.2%. Thus, SDS solution and SDS foam were better vehicles than water for delivering nZVI particles to porous media for contamination remediation.

The influence of humic acid and clay content on the transport of polymer-coated iron nanoparticles through sand

The introduction of nanoscale zero valent iron (nZVI) into the subsurface has recently received significant attention as a potentially effective method for remediation of source zones of chlorinated solvents present as dense nonaqueous phase liquids (DNAPL). One of the challenges in the deployment of nZVI is to achieve good subsurface nZVI mobility to permit delivery of the nZVI to the target treatment zone. Stabilization of nZVI with various polymers has shown promise for enhancing nZVI subsurface mobility, but the impact of subsurface conditions on nZVI mobility has not been fully explored. In this study, the effect of humic acid and kaolinite on the transport of polymer-stabilized nZVI (carboxylmethyl cellulose-surface modified nZVI, CMC90K-RNIP) in sand was investigated using column experiments. In addition, effects of electrolytes on the stability of CMC90K-RNIP in the presence of humic acid, and the stability of humic acid-coated reactive nanoscale iron particles (HA-RNIP) at various humic acid concentrations were investigated. Humic acid enhanced the mobility of bare RNIP, whereas the transport of CMC90K-RNIP was not significantly affected by humic acid injected as a background solution, except at the highest concentration of 500mg/L. At lower pore water velocity, the effect of humic acid on the transport of CMC90K-RNIP was greater than that at high water velocity. Adding kaolinite up to 2% by weight to the sand column reduced the retention of CMC90K-RNIP, but further increases in kaolinite content (to 5%) did not significantly affect nZVI retention. The impact of kaolinite on nZVI retention was more pronounced at lower pore water velocities.

Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media

Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50=2.4μm) are investigated in column tests using columns of 40cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from −62mV to −80mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions.

Investigations on mobility of carbon colloid supported nanoscale zero-valent iron (nZVI) in a column experiment and a laboratory 2D-aquifer test system.

Nanoscale zero-valent iron (nZVI) has recently gained great interest in the scientific community as in situ reagent for installation of permeable reactive barriers in aquifer systems, since nZVI is highly reactive with chlorinated compounds and may render them to harmless substances. However, nZVI has a high tendency to agglomerate and sediment; therefore it shows very limited transport ranges. One new approach to overcome the limited transport of nZVI in porous media is using a suited carrier colloid. In this study we tested mobility of a carbon colloid supported nZVI particle "Carbo-Iron Colloids" (CIC) with a mean size of 0.63 μm in a column experiment of 40 cm length and an experiment in a two-dimensional (2D) aquifer test system with dimensions of 110 × 40 × 5 cm. Results show a breakthrough maximum of 82 % of the input concentration in the column experiment and 58 % in the 2D-aquifer test system. Detected residuals in porous media suggest a strong particle deposition in the first centimeters and few depositions in the porous media in the further travel path. Overall, this suggests a high mobility in porous media which might be a significant enhancement compared to bare or polyanionic stabilized nZVI.

Electro-osmotic transport of nano zero-valent iron in Boom Clay

One of the many problems that impede the successful remediation of soil and groundwater contaminated with chlorinated hydrocarbons occurs when pollutants diffuse into low permeability zones, and become difficultly accessible. Remediation by reductive dechlorination using nanoscale zero-valent iron (nZVI) is possible, but its delivery into contaminated hot spots is difficult using solely hydraulic gradients.Recently, electrokinetics has been proposed to transport nZVI, with the assumption that both electrophoresis and electro-osmosis are involved. However, so far no study has focused solely on transport driven by electro-osmotic flow. This driving force could significantly improve field remediation, allowing nZVI to reach low permeability hotspots.This work describes the experiments carried out to evaluate if nanoscale zero-valent iron can be transported by electro-osmotic advection in a dense clay using a specifically designed laboratory apparatus. It explores how working parameters (such as voltage, injection point and pH) influence transport, and provides an insight into the subsurface behaviour of nanoparticles using micro-XRF.The results confirm the transport of nZVI by electro-osmotic advection, with an electro-osmotic conductivity in the range (0.5-1.0)·10−10 m2V−1s−1. The presence of nZVI decreases electro-osmotic conductivities by approximately half and affects geochemical conditions of the system, inducing sharper pH profiles and enhancing cation exchange in the clay.

Influence of electrolyte and voltage on the direct current enhanced transport of iron nanoparticles in clay

Zero valent iron nanoparticles (nZVI) transport for soil and groundwater remediation is slowed down or halted by aggregation or fast depletion in the soil pores. Direct electric current can enhance the transport of nZVI in low permeability soils. However operational factors, including pH, oxidation–reduction potential (ORP), voltage and ionic strength of the electrolyte can play an important role in the treatment effectiveness. Experiments were conducted to enhance polymer coated nZVI mobility in a model low permeability soil medium (kaolin clay) using low direct current. Different electrolytes of varying ionic strengths and initial pH and high nZVI concentrations were applied. Results showed that the nZVI transport is enhanced by direct current, even considering concentrations typical of field application that favor nanoparticle aggregation. However, the factors considered (pH, ORP, voltage and electrolyte) failed to explain the iron concentration variation. The electrolyte and its ionic strength proved to be significant for pH and ORP measured during the experiments, and therefore will affect aggregation and fast oxidation of the particles.

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Characteristics of the transport of zero-valent iron nanoparticles (nZVI) in an aquifer were investigated to evaluate an application of nZVI-based reactive zone technology. Main flow direction of groundwater was north. Preferential flow paths of the groundwater identified by natural gradient tracer test were shown northeast and northwest. The highest groundwater velocity was <TEX>$4.86{\times}10^{-5}$</TEX> m/s toward northwest. When the breakthrough curves obtained from the gravity injection of nZVI were compared with the tracer curves, the transport of nZVI was retarded and retardation factors were 1.17 and 1.34 at monitoring wells located on the northeast and northwest, respectively. The ratios of the amount of nZVI delivered to the amount of tracer delivered at the two wells mentioned above were 24 and 28 times greater than that of the well on the main flow direction, respectively. Attachment efficiency based on a filtration theory was <TEX>$4.08{\times}10^{-2}$</TEX> along the northwest direction that was the main migration route of nZVI. Our results, compared to attachment efficiencies obtained in other studies, demonstrate that the mobility of nZVI was higher than that of results reported in previous studies, regardless of large iron particle sizes of the current study. Based on distribution of nZVI estimated by the attachment efficiency, it was found that nZVI present within 1.05 m from injection well could remove 99% of TCE within 6 months.

A Field-Validated Model for In Situ Transport of Polymer-Stabilized nZVI and Implications for Subsurface Injection

Nanoscale zerovalent iron (nZVI) particles have significant potential to remediate contaminated source zones. However, the transport of these particles through porous media is not well understood, especially at the field scale. This paper describes the simulation of a field injection of carboxylmethyl cellulose (CMC) stabilized nZVI using a 3D compositional simulator, modified to include colloidal filtration theory (CFT). The model includes composition dependent viscosity and spatially and temporally variable velocity, appropriate for the simulation of push-pull tests (PPTs) with CMC stabilized nZVI. Using only attachment efficiency as a fitting parameter, model results were in good agreement with field observations when spatially variable viscosity effects on collision efficiency were included in the transport modeling. This implies that CFT-modified transport equations can be used to simulate stabilized nZVI field transport. Model results show that an increase in solution viscosity, resulting from injection of CMC stabilized nZVI suspension, affects nZVI mobility by decreasing attachment as well as changing the hydraulics of the system. This effect is especially noticeable with intermittent pumping during PPTs. Results from this study suggest that careful consideration of nZVI suspension formulation is important for optimal delivery of nZVI which can be facilitated with the use of a compositional simulator.

Carbonate minerals in porous media decrease mobility of polyacrylic acid modified zero-valent iron nanoparticles used for groundwater remediation

The limited transport of nanoscale zero-valent iron (nZVI) in porous media is a major obstacle to its widespread application for in situ groundwater remediation. Previous studies on nZVI transport have mainly been carried out in quartz porous media. The effect of carbonate minerals, which often predominate in aquifers, has not been evaluated to date. This study assessed the influence of the carbonate minerals in porous media on the transport of polyacrylic acid modified nZVI (PAA-nZVI). Increasing the proportion of carbonate sand in the porous media resulted in less transport of PAA-nZVI. Predicted travel distances were reduced to a few centimeters in pure carbonate sand compared to approximately 1.6 m in quartz sand. Transport modeling showed that the attachment efficiency and deposition rate coefficient increased linearly with increasing proportion of carbonate sand.

Foam-Assisted Delivery of Nanoscale Zero Valent Iron in Porous Media

AbstractFoam is potentially a promising vehicle to deliver nanoparticles for vadose-zone remediation because foam can overcome the intrinsic problems associated with solution-based delivery, such as preferential flow and contaminant mobilization and spreading. In this work, the feasibility of using foam to deliver nanoscale zero valent iron (nZVI) in unsaturated porous media was investigated. Foam generated using the surfactant sodium lauryl ether sulfate (SLES) showed excellent ability to carry nZVI. SLES and nZVI concentrations in the foaming solutions did not affect the percentages of nZVI concentrations in foam relative to nZVI concentrations in the solutions. When foams carrying nZVI were injected through the unsaturated columns, the fractions of nZVI exiting the column were much higher than those when nZVI was injected with liquid. The enhanced nZVI transport implies that foam delivery could significantly increase the radius of influence of injected nZVI. The type and concentrations of surfactants a...

Field-Scale Transport and Transformation of Carboxymethylcellulose-Stabilized Nano Zero-Valent Iron

The fate of nano zerovalent iron (nZVI) during subsurface injection was examined using carboxymethylcellulose (CMC) stabilized nZVI in a very large three-dimensional physical model aquifer with detailed monitoring using multiple, complementary detection methods. A fluorescein tracer test in the aquifer plus laboratory column data suggested that the very-aggressive flow conditions necessary to achieve 2.5 m of nZVI transport could be obtained using a hydraulically constrained flow path between injection and extraction wells. However, total unoxidized nZVI was transported only about 1 m and <2% of the injected nZVI concentration reached that distance. The experimental data also indicated that groundwater flow changed during injection, likely due to hydrogen bubble formation, which diverted the nZVI away from the targeted flow path. The leading edge of the iron plume became fully oxidized during transport. However, within the plume, oxidation of nZVI decreased in a fashion consistent with progressive depletion of aquifer "reductant demand". To directly quantify the extent of nZVI transport, a spectrophotometric method was developed, and the results indicated that deployment of unoxidized nZVI for groundwater remediation will likely be difficult.

Reclamation of unconventional water using nano zero-valent iron particles: an application for groundwater

Nano zero-valent iron (nZVI) is one of the most prominent examples of a rapidly emerging technology for the treatment of contaminated soil and groundwater. These particles were used successfully to absorb various heavy metals (e.g., Pb2+, Ba2+, As5+, As3+, Cr6+, Co2+, Cd2+, Cu2+), chlorinated organic contaminants (e.g., solvents, pesticides), nitrate and so on. nZVI particles have a large surface area and high surface reactivity. However, the agglomeration, oxidation by non-target compounds and high mobility in the aqueous solutions are the major challenges of nZVI use in environmental remediation. In general, there are several gaps concerning fate, transport and toxicity of nZVI. In recent years, considerable efforts have been made to overcome these problems. These efforts include synthetic methods, surface property modification, trapping of nZVI in different beads and enhancement for field delivery and reactions. This paper provides an overview of research on reclamation of unconventional water with nZVI.

Impact of size and sorption on degradation of trichloroethylene and polychlorinated biphenyls by nano-scale zerovalent iron

Nano-scale zerovalent iron (nZVI) has been studied in recent years for environmental remediation applications such as the degradation of chlorinated organic contaminants. To overcome limitations related to the transport of nZVI, it is becoming common to add a polymer stabilizer to limit aggregation and enhance the particle reactivity. Another method investigated to enhance particle reactivity has been to limit particle size through novel synthesis techniques. However, the relative impacts of particle size and interactions of the chemicals with the coatings are not yet well understood. The purpose of this study was to investigate the mechanisms of particle size and polymer coating or polyelectrolyte multilayer (PEM) synthesis conditions on degradation of two common chlorinated contaminants: trichloroethylene (TCE) and polychlorinated biphenyls (PCBs). This was accomplished using two different synthesis techniques, a layer-by-layer approach at different pH values or iron reduction in the presence of varying concentrations of poly(acrylic acid). nZVI produced by both techniques yielded higher degradation rates than a traditional approach. The mechanistic investigation indicated that hydrophobicity and sorption to the multilayer impacts the availability of the hydrophobic compound to the nZVI and that particle size also had a large role with smaller particles having stronger dechlorination rates.

Electrokinetic Enhanced Transport of Zero Valent Iron Nanoparticles for Chromium (vi) Reduction in Soils

Zero valent iron nanoparticles (nZVI) are a promising technology that could provide cost-effective solutions to soil and groundwater remediation. However, transport of nZVI is normally limited by their aggregation and settling, and with mobility being normally less than a few meters.The main research objective of this study is to find out if coupling electrokinetics and reactive iron nanoparticles can be an effective method for treating chromium contaminated clay soils. Direct current was used to enhance poly(acrylic acid), sodium salt (PAA) coated iron nanoparticles (PAA-nZVI) mobility in Cr(VI) spiked kaolin.A commercially available electrophoretic cell was modified for these experiments and equipped with internal auxiliary electrodes that allow to measure the redox potential directly in the clay. A constant potential of 5.0 V wasapplied across the test bed. Experimental results show that electrokinetics can enhance the delivery of nanoscale iron particles for the reduction of hexavalent chromium to the less toxic trivalent chromium. Direct current enhanced nZVI transport up to 74 % when compared with diffusion, maximum value found when comparing iron concentrations ratios. Activation of nZVI was also observed with a decrease in the redox potential of 531 mV, in average, after the injection point.