In the present work fluid flow and solute transport through porous media are described by solving the governing equations at the pore scale with finite-volume discretization. Instead of solving the ...simplified Stokes equation (very often employed in this context) the full Navier-Stokes equation is used here. The realistic three-dimensional porous medium is created in this work by packing together, with standard ballistic physics, irregular and polydisperse objects. Emphasis is placed on numerical issues related to mesh generation and spatial discretization, which play an important role in determining the final accuracy of the finite-volume scheme and are often overlooked. The simulations performed are then analyzed in terms of velocity distributions and dispersion rates in a wider range of operating conditions, when compared with other works carried out by solving the Stokes equation. Results show that dispersion within the analyzed porous medium is adequately described by classical power laws obtained by analytic homogenization. Eventually the validity of Fickian diffusion to treat dispersion in porous media is also assessed.
Pump and treat (P&T) systems are still widely employed for the hydraulic containment of contaminated groundwater despite the fact that their usage is decreasing due to their high operational costs. A ...way to partially mitigate such costs, both in monetary and environmental terms, is to perform heat exchange (directly or with a heat pump) on the groundwater extracted by these systems, thus providing low-carbon and low-cost heating and/or cooling to buildings or industrial processes. This opportunity should be carefully evaluated in view of preserving (or even improving) the removal efficiency of the remediation process. Therefore, the heat exchange should be placed upstream or downstream of all treatments, or in an intermediate position, depending on the effect of water temperature change on the removal efficiency of each treatment step. This article provides an overview of such effects and is meant to serve as a starting reference for a case-by-case evaluation. Finally, the potentiality of geothermal use of P&T systems is assessed in the Italian contaminated Sites of National Interest (SIN), i.e., the 41 priority contaminated sites in Italy. At least 29 of these sites use pumping wells as hydraulic barriers or P&T systems. The total discharge rate treated by these plants exceeds 7000 m3/h and can potentially provide about 33 MW of heating and/or cooling power.
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 1.5m3 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.
•mZVI slurries stabilized with guar gum (GG) can be prepared at pilot scale.•Highly concentrated GG-mZVI slurries can be injected via direct push technique.•A heterogeneous distribution of the GG stabilized mZVI was observed.•Abiotic degradation of 1,1,1-TCA was proven 1m from injection at 4.5m bgs.
Humic acid-coated goethite nanoparticles (HA-GoeNPs) have been recently proposed as an effective reagent for the in situ nanoremediation of contaminated aquifers. However, the effective dosage of ...these particles has been studied only at laboratory scale to date. This study investigates the possibility of using HA-GoeNPs in remediation of real field sites by mimicking the injection and transport of HA-GoeNPs under realistic conditions. To this purpose, a three-dimensional (3D) transport experiment was conducted in a large-scale container representing a heterogeneous unconfined aquifer. Monitoring data, including particle size distribution, total iron (Fetot) content and turbidity measurements, revealed a good subsurface mobility of the HA-GoeNP suspension, especially within the higher permeability zones. A radius of influence of 2 m was achieved, proving that HA-GoeNPs delivery is feasible for aquifer restoration. A flow and transport model of the container was built using the numerical code Micro and Nanoparticle transport Model in 3D geometries (MNM3D) to predict the particle behavior during the experiment. The agreement between modeling and experimental results validated the capability of the model to reproduce the HA-GoeNP transport in a 3D heterogeneous aquifer. Such result confirms MNM3D as a valuable tool to support the design of field-scale applications of goethite-based nanoremediation.
Nanosized particles (NPs), such as TiO2, Silver, graphene NPs, nanoscale zero-valent iron, carbon nanotubes, etc., are increasingly used in industrial processes, and releases at production plants and ...from landfills are likely scenarios for the next years. As a consequence, appropriate procedures and tools to quantify the risks for human health associated to these releases are needed.
The tiered approach of the standard ASTM procedure (ASTM-E2081-00) is today the most applied for human health risk assessment at sites contaminated by chemical substances, but it cannot be directly applied to nanoparticles: NP transport along migration pathways follows mechanisms significantly different from those of chemicals; moreover, also toxicity indicators (namely, reference dose and slope factor) are NP-specific. In this work a risk assessment approach modified for NPs is proposed, with a specific application at Tier 2 to migration in groundwater. The standard ASTM equations are modified to include NP-specific transport mechanisms. NPs in natural environments are typically characterized by a heterogeneous set of NPs having different size, shape, coating, etc. (all properties having a significant impact on both mobility and toxicity). To take into account this heterogeneity, the proposed approach divides the NP population into classes, each having specific transport and toxicity properties, and simulates them as independent species. The approach is finally applied to a test case simulating the release of heterogeneous Silver NPs from a landfill. The results show that taking into account the size-dependent mobility of the particles provides a more accurate result compared to the direct application of the standard ASTM procedure. In particular, the latter tends to underestimate the overall toxic risk associated to the nP release.
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•Risk assessment standard procedures are extended to nanoparticle releases.•Particle size distribution significantly impacts on nanoparticle transport in groundwater.•Particle size distribution significantly impacts on human health risk.
A risk assessment procedure for nanoparticle releases at contaminated sites is proposed. The standard human health risk assessment models for subsurface migration are adapted to nanoparticles.
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.
One of the main technical problems faced during field-scale injections of iron microparticles (mZVI) for groundwater nanoremediation is related to their poor colloidal stability and mobility in ...porous media. In this study, a shear-thinning gel, composed of a mixture of two environmentally friendly biopolymers, i.e., guar gum and xanthan gum, was employed to overcome these limitations. The slurry rheology and particle mobility were characterized by column transport tests. Then, a radial transport experiment was performed to mimic the particle delivery in more realistic conditions. The gel, even at a low polymeric content (1.75 g/L), proved effective in enhancing the mobility of high concentrated mZVI suspensions (20 g/L) in field-like conditions. The high radius of influence (73 cm) and homogeneous iron distribution were achieved by maintaining a low injection overpressure (<0.4 bar). Based only on the information derived from column tests, the MNMs 2018 software (Micro- and Nanoparticle transport, filtration, and clogging Model-Suite) was able to predict the particle distribution and pressure build-up measured in the radial domain. Experimental and simulated results showed good agreement, thus proving that a simplified experimental-modeling procedure based on 1D column tests could be used to effectively upscale the slurry behavior to more representative scales, e.g., radial domains.
Nanoscale zero-valent iron particles (nZVI) have been studied in recent years as a promising technology for the remediation of contaminated aquifers. Specific positive features of nZVI are the high ...reactivity towards a broad range of contaminants and the possibility of injecting in aqueous slurries for a targeted remediation of contaminated areas. However, crucial points to be addressed are stability against aggregation, mobility in subsurface environments, and longevity. In this work a review is presented on the current knowledge on the properties, reactivity and mobility in porous media of nZVI and their application to groundwater remediation. A specific focus is devoted to the methodologies to the colloidal stability of the nZVI slurries and to the available numerical tools for the simulation of laboratory and field scale mobility of the particles when injected in porous media.
•Nanoscale zero-valent iron particles for groundwater remediation are reviewed.•Nanoscale iron can be injected in aqueous suspensions to the contaminated area.•Colloidal stabilization is required to improve mobility in porous media.•Modelling tools and approaches for injection simulation are reviewed.
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•The shell in PHSNs resulted in significantly different particle physicochemical properties compared to SSNs of similar size.•Higher surface roughness in PHSNs than in SSNs was ...responsible for the reduced transport and deviations from DLVO theory.•High IS and low pH decreased mobility and increased retention for both particle populations.•Retention was 3-fold higher for PHSNs compared to SSNs at the highest IS and lowest pH.
Silica nanoparticles (SiO2 NPs) are of increasing interest in nano-enabled agriculture, particularly as nanocarriers for the targeted delivery of agrochemicals. Their direct application in agricultural soils may lead to the release of SiO2 NPs in the environment. Although some studies have investigated transport of solid SiO2 NPs in porous media, there is a knowledge gap on how different SiO2 NP structures incorporating significant porosities can affect the mobility of such particles under different conditions. Herein, we investigated the effect of pH and ionic strength (IS) on the transport of two distinct structures of SiO2 NPs, namely solid SiO2 NPs (SSNs) and porous hollow SiO2 NPs (PHSNs), of comparable sizes (~200 nm). Decreasing pH and increasing ionic strength reduced the mobility of PHSNs in sand-packed columns more significantly than for SSNs. The deposition of PHSNs was approximately 3 times greater than that of SSNs at pH 4.5 and IS 100 mM. The results are non-intuitive given that PHSNs have a lower density and the same chemical composition of SSNs but can be explained by the greater surface roughness and ten-fold greater specific surface area of PHSNs, and their impacts on van der Waals and electrostatic interaction energies.