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.

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.

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.

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.

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.

Effect of water chemistry and aging on iron-mica interaction forces: implications for iron particle transport.

The transport of particles through groundwater systems is governed by a complex interplay of mechanical and chemical forces that are ultimately responsible for binding to geological substrates. To understand these forces in the context of zero valent iron particles used in the remediation of groundwater, atomic force microscopy (AFM)-based force spectroscopy was employed to characterize the interactions between AFM tips modified with either carbonyl iron particles (CIP) or electrodeposited Fe as a function of counterion valency, temperature, particle morphology, and age. The measured interaction forces were always attractive for both fresh and aged CIP and electrodeposited iron, except in 100 mM NaCl, as a consequence of electrostatic attraction between the negatively charged mica and positively charged iron. In 100 mM NaCl, repulsive hydration forces appeared to dominate. Good agreement was found between the experimental data and predictions based on the extended DLVO (XDLVO) theory. The effect of aging on iron particle composition and morphology was assessed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) revealing that the aged particles comprising a zero valent iron core passivated by a mixture of iron oxides and hydroxides. Force spectroscopy showed that aging caused variations in the adhesive force due to the changes in particle morphology and contact area.

Colloid transport in dolomite rock fractures: effects of fracture characteristics, specific discharge, and ionic strength.

The effects of fracture characteristics, specific discharge, and ionic strength on microsphere transport in variable-aperture dolomite rock fractures were studied in a laboratory-scale system. Fractures with different aperture distributions and mineral compositions were artificially created in two dolomite rock blocks. Transport tests were conducted with bromide and carboxylate-modified latex microspheres (20, 200, and 500 nm diameter). Under overall unfavorable attachment conditions, there was significant retention of the 20 nm microsphere and minimal retention of the 500 nm microsphere for all conditions examined. Aperture variability produced significant spatial variation in colloid transport. Flushing with low ionic strength solution (1 mM) following microsphere transport at 12 mM ionic strength solution produced a spike in effluent microsphere concentrations, consistent with retention of colloids in secondary energy minima. Surface roughness and charge heterogeneity effects may have also contributed to the effect of microsphere size on retention. Matrix diffusion influenced bromide transport but was not a dominant factor in transport for any microsphere size. Calibrated one-dimensional, two-site kinetic model parameters for colloid transport in fractured dolomite were sensitive to the physical and chemical properties of both the fractured dolomite and the colloids, indicating the need for mechanistic modeling for accurate prediction.

Forces of interactions between bare and polymer-coated iron and silica: effect of pH, ionic strength, and humic acids.

The interactions between a silica substrate and iron particles were investigated using atomic force microscopy-based force spectroscopy (AFM). The micrometer- and nanosized iron particles employed were either bare or coated with carboxymethyl cellulose (CMC), a polymer utilized to stabilize iron particle suspensions. The effect of water chemistry on the forces of interaction was probed by varying ionic strength (with 100 mM NaCl and 100 mM CaCl2) or pH (4, 5.5, and 8) or by introducing 10 mg/L of humic acids (HA). When particles were uncoated, the forces upon approach between silica and iron were attractive at pH 4 and 5.5 and in 100 mM CaCl2 at pH 8, but they were negligible in 100 mM NaCl buffered to pH 8 and repulsive in water buffered to pH 8 and in HA solutions. HA produced electrosteric repulsion between iron particles and silica, likely due to its sorption to iron particles. HA sorption to silica was excluded on the basis of experiments conducted with a quartz-crystal microbalance with dissipation monitoring. Repulsion with CMC-coated iron was attributed to electrosteric forces, which were damped at high ionic strength. An extended DLVO model and a modified version of Ohshima's theory were successfully utilized to model AFM data.

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.

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.

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.

A flow cell simulating a subsurface rock fracture for investigations of groundwater-derived biofilms.

Laboratory scale continuous-flow-through chambers (flow cells) facilitate the observation of microbes in a controlled, fully hydrated environment, although these systems often do not simulate the environmental conditions under which microorganisms are found. We developed a flow cell that mimics a subsurface groundwater-saturated rock fracture and is amenable to confocal laser scanning microscopy while allowing for the simple removal of the attached biomass. This flow cell was used to investigate the effect of toluene, a representative contaminant for non-aqueous phase liquids, on groundwater-derived biofilms. Reduced average biofilm biomass and thickness, and diminished diversity of amplifiable 16S rRNA sequences were observed for biofilms that developed in the presence of toluene, compared to the biofilms grown in the absence of toluene. The flow cell also allowed the detection of fluorescent protein-labelled cells.

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.

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.

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.

The impact of methanogenesis on flow and transport in coarse sand.

The effects of biofilm growth and methane gas generation on water flow in porous media were investigated in an anaerobic two-dimensional sand-filled cell. Inoculation of the lower portion of the cell with a methanogenic culture and addition of methanol to the bottom of the cell led to biomass growth and formation of a gas phase. Biomass distributions in the water and on the sand in the cell were measured by protein analysis. The biofilm distribution on sand was observed by confocal laser scanning microscopy. The formation, migration, distribution and saturation of gases in the cell were visualized by the charge-coupled device (CCD) camera. The effects of biofilm and gas generation on water flow were separated by performing one tracer test in the presence of both biofilm and a gas phase and a second tracer test after removal of the gas phase through water flushing. The results of tracer tests demonstrated that flow and transport in the two-dimensional cell were significantly affected by both gas generation and biofilm growth. Gas generated at the bottom of the cell in the biologically active zone moved upwards in discrete fingers, so that gas phase saturations (gas-filled fraction of void space) in the biologically active zone at the bottom of the cell did not exceed 40-50%, while gas accumulation at the top of the cell produced gas phase saturations as high as 80%. The greatest reductions in water phase permeability, based on measurements of reductions in water phase saturations, occurred near the top of the box as a result of the gas accumulation. In contrast the greatest reductions in permeability due to biofilm growth, based on measurements of biofilm thickness, occurred in the most biologically active zone at the bottom of the cell, where gas phase saturations were approximately 40-50%, but permeability reductions due to biofilm growth were estimated to be 80-95%.

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.

The spatial distribution of eubacteria and archaea in sand-clay columns degrading carbon tetrachloride and methanol.

The spatial distribution of microbial communities was investigated in anaerobic sand-clay columns fed methanol and carbon tetrachloride (CT). Microbial communities were characterized through analysis of soil samples with denaturing gradient gel electrophoresis (DGGE) and quantitative polymerase chain reaction (qPCR) for archaea and eubacteria. Increasing CT inlet concentrations to 29 microM lead to complete inhibition of methanol consumption in both columns. Although low levels of eubacteria and archaea were initially present in the clay soils in both columns, there was no significant microbial growth over 400 days in the clays beyond the interface with the sand zone. Thus, the potential for increased contaminant attenuation in heterogeneous sand-clay systems through biodegradation in the clay matrix zones may be limited in many systems.

Hot water flushing for immiscible displacement of a viscous NAPL.

Thermal remediation techniques, such as hot water flooding, are emerging technologies that have been proposed for the removal of nonaqueous phase liquids (NAPLs) from the subsurface. In this study a combined laboratory and modeling investigation was conducted to determine if hot water flooding techniques would improve NAPL mass removal compared to ambient temperature water flushing. Two experiments were conducted in a bench scale two-dimensional sandbox (55 cmx45 cmx1.3 cm) and NAPL saturations were quantified using a light transmission apparatus. In these immiscible displacement experiments the aqueous phase, at 22 degrees C and 50 degrees C, displaced a zone with initial NAPL saturations on the order of 85%. The interfacial tension and viscosity of the selected light NAPL, Voltesso 35, are strongly temperature-dependent. Experimental results suggest that hot water flooding reduced the size of the high NAPL saturation zone, in comparison to the cold water flood, and yielded greater NAPL mass recovery (75% NAPL removal vs. 64%). Hot water flooding did not, however, result in lower residual NAPL saturations. A numerical simulator was modified to include simultaneous flow of water and organic phases, energy transport, temperature and pressure. Model predictions of mass removal and NAPL saturation profiles compared well with observed behavior. A sensitivity analysis indicates that the utility of hot water flooding improves with the increasing temperature dependence of NAPL hydraulic properties.

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.