Transport and targeted binding of Pluronic-coated nanoparticles in unsaturated porous media.

The effectiveness of most in situ remedial technologies, including nanoremediation, lies on successful delivery of reagents to a subsurface target treatment zone. Targeted delivery of engineered nanoparticles (NPs) to treat petroleum hydrocarbons present in the unsaturated zone requires an understanding of their transport behaviour in these systems. A series of column experiments explored the effect of initial water saturation, flowrate, input dosage, and porous medium texture on the transport of iron oxide or cobalt ferrite NPs coated with an amphiphilic co-polymer, as well as their targeted attachment to a crude oil zone.

Spatiotemporal geo-electrical sensing of a Pluronic-coated cobalt ferrite nanoparticle slug in natural sand flow-through columns.

Rising industrial interest in the application of nanomaterials for the remediation of contaminated sites has led to concern over the environmental fate of the nanoremediation agents used. A critical requirement in evaluating and understanding nanoparticle (NP) behaviour in porous media is the development of analytical methods capable of in situ monitoring of complex NP transport dynamics. Spectral induced polarization (SIP), a non-invasive geo-electrical technique, offers a promising tool for detecting and quantifying NPs in soil and aquifer media.

Factors affecting pluronic-coated iron oxide nanoparticle binding to petroleum hydrocarbon-impacted sediments.

Effective targeted delivery of nanoparticle agents may enhance the remediation of soils and site characterization efforts. Nanoparticles coated with Pluronic, an amphiphilic block co-polymer, demonstrated targeted binding behaviour toward light non-aqueous phase liquids such as heavy crude oil. Various factors including coating concentration, oil concentration, oil type, temperature, and pH were assessed to determine their effect on nanoparticle binding to heavy crude oil-impacted sandy aquifer material.

Use of steady-state hydraulic tomography to inform the selection of a chaotic advection system.

The concept of chaotic advection is a novel approach that has the potential to overcome some of the challenges associated with mixing of reagents that commonly occur when injection based in situ treatment techniques are used. The rotated potential mixing (RPM) flow system is one configuration which has been theorized to achieve chaotic advection in porous media, and enhance reagent mixing by periodically re-oriented dipole pumping at a series of radial wells. Prior to field implementation of chaotic advection, the selection of an RPM flow protocol will likely require a numerical model that can adequately represent groundwater flow within the zone of interest.

Response of sulfate-reducing bacteria and supporting microbial community to persulfate exposure in a continuous flow system.

Coupling of chemical oxidation using persulfate with bioremediation has been proposed as a method to increase remedial efficacy at petroleum hydrocarbon contaminated sites. To support this integrated treatment approach, an understanding of persulfate impact on the indigenous microbial community is necessary for system design. As sulfate-reducing bacteria (SRB) are active in most aquifer systems and can utilize the sulfate generated from the degradation of persulfate, this study assessed the impact on SRB and the supporting anaerobic microbial community when exposed to persulfate in a continuous flow system.

Intra-NAPL diffusion and dissolution of a MGP NAPL exposed to persulfate in a flow-through system.

Intra-NAPL diffusion is a critical process that can influence NAPL/water mass transfer. A series of physical model experiments was performed to investigate the role of intra-NAPL diffusion on the transient dissolution of a complex multicomponent NAPL subjected to persulfate treatment. To support these observations, a diffusion-based model was developed and calibrated using the experimental data.

Targeted nanoparticle binding & detection in petroleum hydrocarbon impacted porous media.

Targeted nanoparticle binding has become a core feature of experimental pharmaceutical product design which enables more efficient payload delivery and enhances medical imaging by accumulating nanoparticles in specific tissues. Environmental remediation and geophysical monitoring encounter similar challenges which may be addressed in part by the adoption of targeted nanoparticle binding strategies. This study illustrates that engineered nanoparticles can bind to crude oil-impacted silica sand, a selective adsorption driven by active targeting based on an amphiphilic polymer coating.

Realistic expectations for the treatment of FMGP residuals by chemical oxidants.

Methods to remediate soil and groundwater contamination at former manufactured gas plant (FMGP) sites are scarce. The objective of this study was to investigate the ability of two chemical oxidants (persulfate and permanganate) to degrade FMGP residuals in a dynamic system representative of in situ conditions. A series of physical model trials supported by aqueous and slurry batch experiments using impacted sediments collected from a FMGP site were conducted.

The role of intra-NAPL diffusion on mass transfer from MGP residuals.

An experimental and computational study was performed to investigate the role of multi-component intra-NAPL diffusion on NAPL-water mass transfer. Molecular weight and the NAPL component concentrations were determined to be the most important parameters affecting intra-NAPL diffusion coefficients. Four NAPLs with different viscosities but the same quantified mass were simulated.

Competition by aquifer materials in a bimetallic nanoparticle/persulfate system for the treatment of trichloroethylene.

It has been suggested in the literature that aquifer materials can compete with the target organic compounds in an activated peroxygen system. In this study, we employed a rapid treatment method using persulfate activated with bimetallic nanoparticles to investigate the competition between aquifer materials and the dissolved phase of a target organic compound. The concentration of dissolved trichloroethylene (TCE) remaining after using the activated persulfate system was two- to three-fold higher in a soil slurry batch system than in an aqueous batch system.

Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment.

The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S₂O₈(2-)) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S₂O₈(2-) molar ratio from 0.

Persulfate injection into a gasoline source zone.

One pore volume of unactivated sodium persulfate was delivered into an emplaced gasoline residual source zone at CFB Borden. Concentrations of inorganic species (S2O8(2-), SO4(2-), Na(+), dissolved inorganic carbon (DIC)) and selected gasoline compounds (benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene) were monitored across a transect equipped with 90 multilevel sampling points for >10months post-injection. Mass loading (M˙) of compounds constructed from the transect data was used for assessment purposes.

Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe2+ activated persulfate.

The increased use of persulfate (S(2)O(8)(2-)) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe(2+)).

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate.

The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics.

Persistence of persulfate in uncontaminated aquifer materials.

Batch and stop-flow column experiments were performed to estimate persulfate decomposition kinetic parameters in the presence of seven well-characterized aquifer materials. Push-pull tests were conducted in a sandy aquifer to represent persulfate decomposition under in situ conditions. The decomposition of persulfate followed a first-order rate law for all aquifer materials investigated.

A long-term bench-scale investigation of permanganate consumption by aquifer materials.

In situ chemical oxidation (ISCO) applications using permanganate involve the injection or release of permanganate into the subsurface to destroy various target contaminants. Naturally occurring reduced components associated with aquifer materials can exert a significant oxidant demand thereby reducing the amount of permanganate available for the destruction of contaminants as well as reducing the overall rate of oxidation. Quantification of this natural oxidant demand (NOD) is a requirement for site-specific assessment and the design of cost-effective oxidant delivery systems.

An evaluation of the green chelant EDDS to enhance the stability of hydrogen peroxide in the presence of aquifer solids.

Hydrogen peroxide is a widely used in situ chemical oxidation reagent which relies on catalysts to generate the suite of reactive species that are required to aggressively remediate contaminated soils and groundwater. In the subsurface environment these catalysts are usually transition metals that are added to the injected solution, or are naturally occurring. Chelating agents are widely used to maintain an adequate dissolved transition metal concentration in near-neutral pH conditions; however, they can also be used to improve the persistence of H(2)O(2) in situations when the aquifer solids have sufficient transition metal content.

Channel flow and trichloroethylene treatment in a partly iron-filled fracture: experimental and model results.

Technical developments have now made it possible to emplace granular zero-valent iron (Fe(0)) in fractured media to create a Fe(0) fracture reactive barrier (Fe(0) FRB) for the treatment of contaminated groundwater. To evaluate this concept, we conducted a laboratory experiment in which trichloroethylene (TCE) contaminated water was flushed through a single uniform fracture created between two sandstone blocks. This fracture was partly filled with what was intended to be a uniform thickness of iron.

Bench-scale investigation of permanganate natural oxidant demand kinetics.

A vital design parameter for any in situ chemical oxidation system using permanganate (MnO4-) is the natural oxidant demand (NOD), a concept that represents the consumption of MnO4- by the naturally present reduced species in the aquifer solids. The data suggest that the NOD of the aquifer material from Canadian Forces Base Borden used in our study is controlled by a fast or instantaneous reaction captured by the column experiments, and a slower reaction as demonstrated by both column and batch test data. These two reaction rates may be the result of the reaction of MnO4- with at least two different reduced species exhibiting widely different rates of permanganate consumption (fast rate >7 g of MnO4- as KMnO4/kg/day and slow rate of approximately 0.

Dissolution of entrapped DNAPLs in variable aperture fractures: experimental data and empirical model.

An appreciation of the dissolution from entrapped nonaqueous phase liquids (NAPLs) in fractures is essential as we attempt to understand and predict the fate of NAPLs present in fractured rock systems. Eight long-term dissolution experiments using 1,1,1-trichloroethane and trichloroethylene were conducted in two laboratory-scale dolomitic limestone variable aperture fractures under various conditions. Between 560 and 2600 fracture volumes of water were passed through the fractures resulting in the removal of 10-60% of the initial mass trapped.