The journey of toluene to complete mineralization via heat-activated peroxydisulfate in water: intermediates analyses, CO2 monitoring, and carbon mass balance.

Our study has thoroughly investigated the complete mineralization of toluene in water via heat-activated peroxydisulfate (PDS) by: (1) monitoring concentrations/peak areas of various intermediates and CO2 throughout the reaction period and (2) identifying water-soluble and methanol-soluble intermediates, including trimers, dimers, and organo-sulfur compounds, via non-target screening using high-resolution mass spectrometry. Increased temperature and PDS dosage enhanced toluene removal/mineralization kinetics and increased the rate/extent of benzaldehyde formation and its further transformation. Artificial groundwater and phosphate buffer minimally impacted toluene removal but significantly decreased benzaldehyde formation, indicating a shift in transformation pathways. The stoichiometric PDS dose (18 mM at 40 °C) was adequate to completely mineralize toluene (1 mM), with < 10% PDS needed to transform toluene to intermediates. Toluene transformation to intermediates occurred in 47 h (kobs,toluene = 0.594 h-1) whereas 564 h were required for complete mineralization (kobs,CO2 = 0.0038 h-1). O2 accumulated once mineralization neared completion. A carbon mass balance, including quantification of nine intermediates and CO2 throughout the transformation period, showed that unquantified/unknown intermediates (including yellowish-white precipitates) reached as high as 80% of total carbon before transformation to CO2. Possible toluene transformation pathways via hydroxylation, sulfate addition, and oxidative coupling are proposed.

A high-throughput and cost-effective microplate reader method for measuring persulfates (peroxydisulfate and peroxymonosulfate).

Frequent use of persulfates as oxidants, for in situ chemical oxidation and advanced oxidation processes, warrants the need for developing a fast and efficient method for measuring persulfate concentrations in aqueous samples in the lab and on site. Here, we propose a modified method, based on Liang et al.'s (2008) spectrophotometric method, for measuring both peroxydisulfate (PDS) and peroxymonosulfate (PMS) in the aqueous samples. Our method involves a deep 96-well plate, multi-channel pipettes, a small orbital shaker, and a microplate reader; allowing the preparation and analysis of up to 96 samples in one run. Our proposed method shortens the time by 10 folds, consumes only ∼2% of the original reagents, and generates only ∼2% of the liquid waste compared to the Liang et al.'s method, thus, making our method high-throughput, time-efficient, and cost-effective with reduced environmental impact. The presented microplate reader method is validated in terms of linearity, LOD, LOQ, accuracy, precision, robustness, and selectivity. All the parameters satisfied the acceptance criteria, according to ICH guidelines. The linearity of calibration curves was evaluated by performing the F-test. In general, our method has linear ranges from 20 to 42,000 and 5 to 40,960 µM for PDS and PMS, respectively. Accuracy (% recovery) results suggested that the LOD and LOQ based on the standard deviation of y-intercepts of the regression lines were the most reliable. The LOD/LOQ values for PDS and PMS were 14.7/44.1 and 4.6/14.4 µM, respectively. The proposed method was also modified to work with a standard cuvette spectrophotometer and was validated. A comparison with the UHPLC analysis of PDS showed that our microplate reader method performed equivalently or even outperformed the UHPLC method, in the presence of common groundwater constituents and organic contaminants.

Effect of low permeability zone location on remediation of Cr(VI)-contaminated media by electrokinetics combined with a modified-zeolite barrier.

Research on electrokinetics-permeable reactive barrier (EK-PRB) remediation to date has mainly focused on homogeneous soils or soils with micro-scale heterogeneities. The potential impact of macro-scale physical heterogeneities, such as stratified layers or lenses, on EK-PRB remediation has not received much attention. This study investigates the effect of a low permeability stratum on EK-PRB remediation of hexavalent chromium (Cr(VI)). Sandbox experiments were conducted to treat Cr(VI)-contaminated kaolinite/sand media, consisting of vertically-layered high permeability (HPZ) and low permeability zones (LPZ), where distance between LPZ and anode (DLA) was 3, 9, or 15 cm. Parameters including current, moisture content (MC), pH, and removal of Cr(VI) were evaluated. With 72 h of EK-PRB treatment, tests with larger DLA (15 cm) had greater Cr(VI) migration from contaminated area to modified-zeolite PRB. Cr(VI), Cr(III), and Cr(Total) removal and energy utilization efficiency followed the trend as: DLA-15 > DLA-9 > DLA-3. MC generally decreased from anode towards cathode and pH was alkaline in all the zones for DLA-3 and DLA-15. In DLA-9 (LPZ in the middle), MC increased and pH was alkaline in HPZs near cathode whereas HPZs near anode were very dry (MC < 1%) and acidic (pH < 5.5). Our results show that the location of LPZ relative to electrode locations has a significant influence on Cr(VI) removal efficiency and macro-scale physical heterogeneity is an important factor to be considered during EK-PRB remediation.

Favorable and unfavorable attachment of colloids in a discrete sandstone fracture.

The transport of cationic amine-modified latex (AML) and anionic carboxylate-modified latex (CML) microspheres through a discrete sandstone fracture with mineralogical heterogeneity and roughness was studied. Two microsphere sizes (200 nm and 1000 nm), two ionic strengths (5 mM and 10 mM), and two specific discharges (0.35 mm.s-1 and 0.70 mm.s-1) were tested to observe the impact on transport under favorable and unfavorable conditions. The difference in retention between AML (net favorable) and CML (net unfavorable) microsphere attachment was 25% for the 200 nm microspheres and 13% for the 1000 nm microspheres. Less than 50% of the AML microspheres were retained in the fracture, postulated to be due to the effects of mineralogical heterogeneity and fracture surface roughness. The effect of an increase in ionic strength in increasing retention was significant for unfavorable attachment, but was not significant for favorable attachment conditions. The effect of specific discharge was minor for all but the 200 nm CML microspheres at 10 mM ionic strength. When flushing the fracture first with cationic microspheres, then with anionic microspheres, the recovery of anionic microspheres resembled favorable attachment presumably due to interaction with cationic microspheres that remained attached to the sandstone surface. Colloid breakthrough curves could be fit well with a two site attachment model, with reversible and irreversible sites.

Sequential treatment of nitrate and phosphate in groundwater using a permeable reactive barrier system.

When not properly treated, nitrate and phosphate present in groundwater can damage human health and environments. In this study, laboratory column experiments were performed for sequential treatment of nitrate and phosphate in groundwater. Two columns were set up and connected: one to treat nitrate with organic carbon materials (i.e., woodchips) and the other to treat phosphate with basic oxygen furnace (BOF) slag. The columns were operated for a total of 1.6 years. The results showed that nitrate was removed through denitrification and phosphate was removed by precipitation of the phosphate minerals (e.g., hydroxyapatite). BOF slag was effective at removing phosphate, though the high pH (11-12) of the system's effluent water raised a concern for the downgradient areas. Of the three subsequent experiments performed, pH was near neutral when the effluent of the BOF slag column was passed through local soil. Sparging with CO2 and air, in contrast, resulted in pH levels that were either too low (5 in the case of CO2) or too high (9.5 in the case of air). The study shows that sequential permeable reactive barrier (PRB) systems consisting of woodchips and BOF slag can be effective for removal of nitrate and phosphate in groundwater and they can be a long-term remedial solution for groundwater contaminated with both nitrate and phosphate.

Two distinct Dehalobacter strains sequentially dechlorinate 1,1,1-trichloroethane and 1,1-dichloroethane at a field site treated with granular zero valent iron and guar gum.

Chlorinated ethanes are environmental pollutants found frequently at many contaminated industrial sites. 1,1,1-Trichloroethane (1,1,1-TCA) can be dechlorinated and detoxified via abiotic transformation or biologically by the action of dechlorinating microorganisms such as Dehalobacter (Dhb). At a field site, it is challenging to distinguish abiotic vs. biotic mechanisms as both processes share common transformation products. In this study, we evaluated using the Dhb 16S rRNA gene and specific reductive dehalogenase genes as biomarkers for 1,1,1-TCA and 1,1-dichloroethane (1,1-DCA) dechlorination. We analyzed samples from laboratory groundwater microcosms and from an industrial site where a mixture of granular zero valent iron (ZVI) and guar gum was injected for 1,1,1-TCA remediation. Abiotic and biotic transformation products were monitored and the changes in dechlorinating organisms were tracked using quantitative PCR (qPCR) with primers targeting the Dhb 16S rRNA gene and two functional genes cfrA and dcrA encoding enzymes that dechlorinate 1,1,1-TCA to 1,1-DCA and 1,1-DCA to chloroethane (CA), respectively. The abundance of the cfrA- and dcrA-like genes confirmed that the two dechlorination steps were carried out by two distinct Dhb populations at the site. The biomarkers used in this study proved useful for monitoring different Dhb populations responsible for step-wise dechlorination and tracking biodegradation of 1,1,1-TCA and 1,1-DCA where both abiotic (e.g., with ZVI) and biotic processes co-occur.

Effects of hydrogen gas production, trapping and bubble-facilitated transport during nanoscale zero-valent iron (nZVI) injection in porous media.

The injection of nanoscale zero-valent iron (nZVI) can be an effective technique for the treatment of groundwater contaminants, including chlorinated solvents. However, its effectiveness can be limited by natural reductant demand (NRD) reactions, including the reduction of water resulting in the production of hydrogen gas. This study presents results from a series of laboratory experiments to investigate gas production and mobilization following the injection of nZVI solutions, along with sodium borohydride (NaBH4) that is used for nZVI synthesis. Experiments were performed in a thin, two-dimensional flow cell (22 × 34 × 1 cm3) to measure hydrogen gas volumes and local gas saturations, and to investigate the distribution of gas within and above the injection zone. An additional experiment was conducted in a larger flow cell (150 × 150 × 2 cm3) containing dissolved trichloroethene (TCE) to assess changes in aqueous flow pathways and enhanced vertical transport of TCE by mobilized gas. The results showed substantial gas production (60% to 740% of the injected solution volume) resulting in gas mobilization as a network of gas channels above the injection zone, with more gas produced from greater excess NaBH4 used during nZVI synthesis. Trapped gas saturations were sufficient to cause the diversion of aqueous flow around the nZVI injection zone. In addition, gas production and mobilization resulted in the bubble-facilitated transport of TCE, and detectable concentrations of TCE and reaction products (ethane and ethene) above the target treatment zone.

Transport of polymer stabilized nano-scale zero-valent iron in porous media.

This study presents a set of laboratory-scale transport experiments and numerical simulations evaluating carboxymethyl cellulose (CMC) polymer stabilized nano-scale zero-valent iron (nZVI) transport. The experiments, performed in a glass-walled two-dimensional (2D) porous medium system, were conducted to identify the effects of water specific discharge and CMC concentration on nZVI transport and to produce data for model validation. The transport and movement of a tracer lissamine green B® (LGB) dye, CMC, and CMC-nZVI were evaluated through analysis of the breakthrough curves (BTCs) at the outlets, the time-lapsed images of the plume, and retained nZVI in the sandbox. The CMC mass recovery was >95% when injected alone and about 65% when the CMC-nZVI mixture was used. However, the mean residence time of CMC was significantly higher than that of LGB. Of significance for field implementation, viscous fingering was observed in water displacement of previously injected CMC and CMC-nZVI. The mass recovery of nZVI was lower (<50%) than CMC recovery due to attachment onto sand grain surfaces. Consecutive CMC-nZVI injections showed higher nZVI recovery in the second injection, a factor to be considered in field trials with successive CMC-nZVI injections. Transport of LGB, CMC, and nZVI were modeled using a flow and transport model considering LGB and CMC as solutes, and nZVI as a colloid, with variable solution viscosity due to changes in CMC concentrations. The simulation results matched the experimental observations and provided estimates of transport parameters, including attachment efficiency, that can be used to predict CMC stabilized nZVI transport in similar porous media, although the extent of viscous fingering may be underpredicted. The experimental and simulation results indicated that increasing specific discharge had a greater effect on decreasing CMC-nZVI attachment efficiency (corresponding to greater possible travel distances in the field) than increasing CMC concentration.

Rethinking aqueous phase diffusion related isotope fractionation: Contrasting theoretical effects with observations at the field scale.

Aqueous phase diffusion-related isotope fractionation (DRIF) was investigated through modelling to determine under what subsurface conditions carbon isotope DRIF effects would be observable using typical sampling approaches. A dispersive enrichment factor was defined based on heavy and light isotopologue dispersion coefficients. For a given ratio of source concentration (C0) to method detection limit (MDL), the maximum DRIF in a system increased linearly with transverse dispersive enrichment factor. Using this linear relationship, the critical dispersion enrichment factor for which DRIF would not be observable was quantified. Dispersive enrichment factors for various contaminants (benzene, toluene, chlorinated compounds) were estimated using field scale transverse dispersion coefficients upscaled from compound specific or non-compound specific local scale dispersivity. All predicted dispersive enrichment factors with non-compound specific dispersivity are smaller than critical values even for high C0/MDL ratios (e.g. 25,000), indicating DRIF would generally not be observable in systems where soil dispersivity is non-compound specific. To date, this finding has not been clearly articulated in the DRIF literature. While the calculated dispersive enrichment factors for some compounds with compound specific transverse dispersivity exceeded the critical values at which DRIF might become significant, the zones in which DRIF could potentially be observable were limited to bands below 0.5m wide on lateral plume edges. In aquifer-aquitard systems, DRIF was theoretically detectable only in thin aquifers (e.g. 0.5m) bounded by thick (e.g. meters) aquitards. DRIF due to back diffusion from aquitards would not be observable regardless of aquifer thickness. Simulations addressing the mixing effect in wells demonstrated that DRIF effects would be difficult to identify in the field without a sampling strategy (including smaller than industry norm well screen lengths, and fine sampling scales) expressly targeted towards that goal. The results of this study help identify what the required characteristics of such a field strategy might be.

Electrokinetic-enhanced permanganate delivery and remediation of contaminated low permeability porous media.

Back diffusion of contaminants from low permeability strata has inhibited site remediation and closure due to an inability to deliver remediants into these strata. This study demonstrates the potential of electrokinetics (EK) to significantly reduce back diffusion of chlorinated compounds from low permeability porous media. Experiments were conducted in a two-dimensional sandbox packed with vertical layers of coarse sand and silt contaminated with aqueous trichloroethene (TCE). Three experiments, each approximately 41 days in duration, compared EK-enhanced in situ chemical oxidation (EK-ISCO) to EK or ISCO alone. EK-ISCO successfully delivered the oxidant (permanganate, PM) throughout the silt cross-section while ISCO without EK resulted only in PM delivery to the edges of the silt layer fringes. EK-ISCO resulted in a 4.4-fold reduction in TCE concentrations in the coarse sand compared to a 3.5-fold reduction from ISCO alone. EK-ISCO with a 25 mA current was found to be more effective than with 300 mA current. Overall, this study suggests that electrokinetics coupled with an appropriate in situ remediation technique, such as ISCO, can enhance remediation of lower permeability strata and limit the extent of contaminant back diffusion.

Long-Term Field Study of Microbial Community and Dechlorinating Activity Following Carboxymethyl Cellulose-Stabilized Nanoscale Zero-Valent Iron Injection.

Nanoscale zerovalent iron (nZVI) is an emerging technology for the remediation of contaminated sites. However, there are concerns related to the impact of nZVI on in situ microbial communities. In this study, the microbial community composition at a contaminated site was monitored over two years following the injection of nZVI stabilized with carboxymethyl cellulose (nZVI-CMC). Enhanced dechlorination of chlorinated ethenes to nontoxic ethene was observed long after the expected nZVI oxidation. The abundance of Dehalococcoides (Dhc) and vinyl chloride reductase (vcrA) genes, monitored using qPCR, increased by over an order of magnitude in nZVI-CMC-impacted wells. The entire microbial community was tracked using 16S rRNA gene amplicon pyrosequencing. Following nZVI-CMC injection, a clear shift in microbial community was observed, with most notable increases in the dechlorinating genera Dehalococcoides and Dehalogenimonas. This study suggests that coupled abiotic degradation (i.e., from reaction with nZVI) and biotic degradation fueled by CMC led to the long-term degradation of chlorinated ethenes at this field site. Furthermore, nZVI-CMC addition stimulated dehalogenator growth (e.g., Dehalococcoides) and biotic degradation of chlorinated ethenes.

Evaluation of peat and sawdust as permeable reactive barrier materials for stimulating in situ biodegradation of trichloroethene.

Two low cost solid organic materials, sawdust and peat, were tested in laboratory batch microcosm and flow-through column experiments to determine their suitability for application in permeable reactive barriers (PRBs) supporting biodegradation of trichloroethene (TCE). In microcosms with peat, TCE (∼30µM) was sequentially and completely degraded to cis-dichloroethene (cDCE), vinyl chloride, and ethene through reductive dechlorination. In microcosms with sawdust, reductive dechlorination of TCE stopped at cDCE and high methane production (up to 3000µM) was observed. 16S rRNA gene copy numbers of Dehalobacter and Archaea were higher (1000 and 10 times, respectively) in sawdust microcosms than those in peat microcosms. Dehalococcoides and vcrA gene copy numbers were 10 times higher in peat microcosms than in sawdust microcosms. These gene copy number differences are consistent with the extent of TCE degradation and production of methane in the microcosms. Flow-through column experiments showed that hydraulic conductivity reduction with time was consistently greater in the sawdust column compared to the peat column. The greater conductivity reduction was likely due to biofouling and methane gas bubble formation. The experimental observations indicate that peat has potential to be a better solid organic material than sawdust to support reductive dechlorination of TCE in PRB applications.

Diffusion related isotopic fractionation effects with one-dimensional advective-dispersive transport.

Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining "observable" DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C0), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (Dmech/Deff). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective-dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C0/MDL ratios of 50 or higher. Much larger C0/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1m) for a relatively young diffusive plume (<100years), and DRIF will not easily be detected by using the conventional sampling approach with "typical" well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where Dmech/Deff is larger than 10, DRIF effects will likely not be observable for common groundwater contaminants. Importantly, under most field conditions, Dmech/Deff≥10 is usually satisfied in the longitudinal direction, suggesting that DRIF is not likely to be observable in most groundwater systems in which contaminant transport is predominantly one-dimensional. Given the importance in the MDL it is recommended that MDL should always be explicitly reported in both modeling and field studies.

nZVI injection into variably saturated soils: Field and modeling study.

Nano-scale zero valent iron (nZVI) has been used at a number of contaminated sites over the last decade. At most of these sites, significant decreases in contaminant concentrations have resulted from the application of nZVI. However, limited work has been completed investigating nZVI field-scale mobility. In this study, a field test was combined with numerical modeling to examine nZVI reactivity along with transport properties in variably saturated soils. The field test consisted of 142L of carboxymethyle cellulose (CMC) stabilized monometallic nZVI synthesized onsite and injected into a variably saturated zone. Periodic groundwater samples were collected from the injection well, as well as, from two monitoring wells to analyze for chlorinated solvents and other geochemistry indicators. This study showed that CMC stabilized monometallic nZVI was able to decrease tricholorethene (TCE) concentrations in groundwater by more than 99% from the historical TCE concentrations. A three dimensional, three phase, finite difference numerical simulator, (CompSim) was used to further investigate nZVI and polymer transport at the variably saturated site. The model was able to accurately predict the field observed head data without parameter fitting. In addition, the numerical simulator estimated the mass of nZVI delivered to the saturated and unsaturated zones and distinguished the nZVI phase (i.e. aqueous or attached). The simulation results showed that the injected slurry migrated radially outward from the injection well, and therefore nZVI transport was governed by injection velocity and viscosity of the injected solution. A suite of sensitivity analyses was performed to investigate the impact of different injection scenarios (e.g. different volume and injection rate) on nZVI migration. Simulation results showed that injection of a higher nZVI volume delivered more iron particles at a given distance; however, the travel distance was not proportional to the increase in volume. Moreover, simulation results showed that using a 1D transport equation to simulate nZVI migration in the subsurface may overestimate the travel distance. This is because the 1D transport equation assumes a constant velocity while pore water velocity radially decreases from the well during injection. This study suggests that on-site synthesized nZVI particles are mobile in the subsurface and that a numerical simulator can be a valuable tool for optimal design of nZVI field applications.

Contributions of Abiotic and Biotic Dechlorination Following Carboxymethyl Cellulose Stabilized Nanoscale Zero Valent Iron Injection.

A pilot scale injection of nanoscale zerovalent iron (nZVI) stabilized with carboxymethyl cellulose (CMC) was performed at an active field site contaminated with a range of chlorinated volatile organic compounds (cVOC). The cVOC concentrations and microbial populations were monitored at the site before and after nZVI injection. The remedial injection successfully reduced parent compound concentrations on site. A period of abiotic degradation was followed by a period of enhanced biotic degradation. Results suggest that the nZVI/CMC injection created conditions that stimulated the native populations of organohalide-respiring microorganisms. The abundance of Dehalococcoides spp. immediately following the nZVI/CMC injection increased by 1 order of magnitude throughout the nZVI/CMC affected area relative to preinjection abundance. Distinctly higher cVOC degradation occurred as a result of the nZVI/CMC injection over a 3 week evaluation period when compared to control wells. This suggests that both abiotic and biotic degradation occurred following injection.

An analysis of a mixed convection associated with thermal heating in contaminated porous media.

The occurrence of subsurface buoyant flow during thermal remediation was investigated using a two dimensional electro-thermal model (ETM). The model incorporated electrical current flow associated with electrical resistance heating, energy and mass transport, and density dependent water flow. The model was used to examine the effects of heating on sixteen subsurface scenarios with different applied groundwater fluxes and soil permeabilities. The results were analyzed in terms of the ratio of Rayleigh to thermal Peclet numbers (the buoyancy ratio). It was found that when the buoyancy number was greater than unity and the soil permeability greater than 10(-12) m(2), buoyant flow and contaminant transport were significant. The effects of low permeability layers and electrode placement on heat and mass transport were also investigated. Heating under a clay layer led to flow stagnation zones resulting in the accumulation of contaminant mass and transport into the low permeability layer. The results of this study can be used to develop dimensionless number-based guidelines for site management during subsurface thermal activities.

Characterization of nZVI mobility in a field scale test.

Nanoscale zerovalent iron (nZVI) particles were injected into a contaminated sandy subsurface area in Sarnia, Ontario. The nZVI was synthesized on site, creating a slurry of 1 g/L nanoparticles using the chemical precipitation method with sodium borohydride (NaBH4) as the reductant in the presence of 0.8% wt. sodium carboxymethylcellulose (CMC) polymer to form a stable suspension. Individual nZVI particles formed during synthesis had a transmission electron microscopy (TEM) quantified particle size of 86.0 nm and dynamic light scattering (DLS) quantified hydrodynamic diameter for the CMC and nZVI of 624.8 nm. The nZVI was delivered to the subsurface via gravity injection. Peak normalized total Fe breakthrough of 71% was observed 1m from the injection well and remained above 50% for the 24 h injection period. Samples collected from a monitoring well 1 m from the injection contained nanoparticles with TEM-measured particle diameter of 80.2 nm and hydrodynamic diameter of 562.9 nm. No morphological changes were discernible between the injected nanoparticles and nanoparticles recovered from the monitoring well. Energy dispersive X-ray spectroscopy (EDS) was used to confirm the elemental composition of the iron nanoparticles sampled from the downstream monitoring well, verifying the successful transport of nZVI particles. This study suggests that CMC stabilized nZVI can be transported at least 1 m to the contaminated source zone at significant Fe(0) concentrations for reaction with target contaminants.

Forces of interactions between iron and aluminum silicates: effect of water chemistry and polymer coatings.

Atomic force microscopy-based force spectroscopy (AFM) was employed to investigate the forces of interaction between aluminum silicates (mica and a synthetic aluminum-silicate) and iron particles, both bare and coated with carboxymethyl cellulose (CMC) polymer. Experiments were conducted in water and salt solutions (100mM NaCl and 100mM CaCl2) at pH 5.5, in water at pH 4 and 8, and in 10mg/l humic acid solutions. In addition, humic acid sorption onto the synthetic aluminum-silicate was probed with a quartz crystal microbalance with dissipation monitoring (QCM-D). Interactions between bare iron particles and aluminum silicate were attractive except at pH 8 and in the presence of humic acids in which case forces upon approach were repulsive. Interactions between bare iron and mica were similar, except that repulsive forces upon approach were measured in 100mM NaCl solutions, possibly due to increased hydration of mica compared to aluminum silicate. Interactions between CMC coated iron particles and aluminum-silicates were either repulsive or at most weakly attractive, likely due to repulsive electro-steric forces associated with the CMC. QCM-D results indicated that humic acids adsorbed to aluminum silicate, producing electro-steric repulsion to coated and uncoated iron. AFM data were successfully modeled using extended DLVO theory and a modified Ohshima's model. This modeling provided insights into the contributions of various processes to the measured interaction forces, highlighting the importance of van der Waals and hydration forces.

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.

Carboxymethyl cellulose binding to mineral substrates: characterization by atomic force microscopy-based force spectroscopy and quartz-crystal microbalance with dissipation monitoring.

The attachment of the sodium salt of carboxymethyl cellulose (CMC) onto iron oxide and various silicate substrates in aqueous solution as a function of salt concentration and pH was studied by atomic force microscopy-based force spectroscopy (AFM) and quartz-crystal microbalance with dissipation monitoring (QCM-D). Both ionic strength and cation valency were found to influence substrate binding. Notably, QCM-D experiments strongly suggested that the solubility of CMC is directly impacted by the presence of CaCl2. Such data are critical for the design of new molecules for stabilizing mineral floc dispersions and for assessing the mobility of CMC-coated particles in the subsurface. Modeling of AFM data with an extended Ohshima theory showed that van der Waals and steric forces played a major role in the interactions between CMC and mineral substrates, and that hydration forces were also important.