Measurements of black carbon (BC) using either chemical or thermal oxidation methods are generally thought to indicate the amount of char and/or soot present in a sample. In urban environments, however, asphalt and coal-tar particles worn from pavement are ubiquitous and, because of their pyrogenic origin, could contribute to measurements of BC. Here we explored the effect of the presence of asphalt and coal-tar particles on the quantification of BC in a range of urban environmental sample types, and evaluated biases in the different methods used for quantifying BC. Samples evaluated were pavement dust, residential and commercial area soils, lake sediments from a small urban watershed, and reference materials of asphalt and coal tar. Total BC was quantified using chemical treatment through acid dichromate (Cr2O7) oxidation and chemo-thermal oxidation at 375 °C (CTO-375). BC species, including soot and char/charcoal, asphalt, and coal tar, were quantified with organic petrographic analysis. Comparison of results by the two oxidation methods and organic petrography indicates that both coal tar and asphalt contribute to BC quantified by Cr2O7 oxidation, and that coal tar contributes to BC quantified by CTO-375. These results are supported by treatment of asphalt and coal-tar reference samples with Cr2O7 oxidation and CTO-375. The reference asphalt is resistant to Cr2O7 oxidation but not to CTO-375, and the reference coal tar is resistant to both Cr2O7 oxidation and CTO-375. These results indicate that coal tar and/or asphalt can contribute to BC measurements in samples from urban areas using Cr2O7 oxidation or CTO-375, and caution is advised when interpreting BC measurements made with these methods.
Contaminant hydrogeological processes occurring in porous media are typically not amenable to direct observation. As a result, indirect measurements (e.g., contaminant breakthrough at a fixed location) are often used to infer processes occurring at different scales, locations, or times. To overcome this limitation, non-invasive imaging methods are increasingly being used in contaminant hydrogeology research. Four of the most common methods, and the subjects of this review, are optical imaging using UV or visible light, dual-energy gamma radiation, X-ray microtomography, and magnetic resonance imaging (MRI). Non-invasive imaging techniques have provided valuable insights into a variety of complex systems and processes, including porous media characterization, multiphase fluid distribution, fluid flow, solute transport and mixing, colloidal transport and deposition, and reactions. In this paper we review the theory underlying these methods, applications of these methods to contaminant hydrogeology research, and methods' advantages and disadvantages. As expected, there is no perfect method or tool for non-invasive imaging. However, optical methods generally present the least expensive and easiest options for imaging fluid distribution, solute and fluid flow, colloid transport, and reactions in artificial two-dimensional (2D) porous media. Gamma radiation methods present the best opportunity for characterization of fluid distributions in 2D at the Darcy scale. X-ray methods present the highest resolution and flexibility for three-dimensional (3D) natural porous media characterization, and 3D characterization of fluid distributions in natural porous media. And MRI presents the best option for 3D characterization of fluid distribution, fluid flow, colloid transport, and reaction in artificial porous media. Obvious deficiencies ripe for method development are the ability to image transient processes such as fluid flow and colloid transport in natural porous media in three dimensions, the ability to image many reactions of environmental interest in artificial and natural porous media, and the ability to image selected processes over a range of scales in artificial and natural porous media.
A key challenge for predictive modeling of transverse mixing and reaction of solutes in groundwater is to determine values of transverse dispersivity in heterogeneous flow fields that accurately describe mixing and reaction at the pore scale. We evaluated the effects of flow focusing in high permeability zones on mixing enhancement using experimental micromodel flow cells and pore-scale lattice-Boltzmann-finite-volume model (LB-FVM) simulations. Micromodel results were directly compared to LB-FVM simulations using two different pore structures, and excellent agreement was obtained. Six different flow focusing pore structures were then systematically tested using LB-FVM, and both analytical solutions and a two-dimensional (2D) continuum-scale model were used to fit values to pore-scale results. Pore-scale results indicate that the overall rate of mixing-limited reaction increased by up to 40% when flow focusing occurred, and it was greater in pore structures with longer flow focusing regions and greater porosity contrast. For each pore structure, values from analytical solutions of transverse concentration profiles or total product at a given longitudinal location showed good agreement for nonreactive and reactive solutes, and values determined in flow focusing zones were always smaller than those downgradient after the flow focusing zone. Transverse dispersivity values from the 2D continuum model were between values within and downgradient from the flow focusing zone determined from analytical solutions. Also, total product and transverse concentration profiles along the entire pore structure from the 2D continuum model matched pore scale results. These results indicate that accurate quantification of pore-scale flow focusing with transverse dispersion coefficients is possible only when the entire flow and concentration fields are considered.
A set of bimetallic Pd−Cu/PVP (PVP = poly(N-vinylpyrrolidone)) colloids, with copper proportions ranging from 0 to 50 atom %, has been examined as catalysts in a batch reactor with flowing hydrogen for the reduction of aqueous nitrate and/or nitrite. The encapsulated Pd−Cu nanoparticles were characterized by powder XRD, TEM, EDX, and IR of adsorbed CO. A significant decrease in average particle diameter and changes in the Pd−Cu crystallinity occurred above ca. 30% copper content, and this transition corresponded with a significant increase in observed nitrate reduction rates. The strong dependence on composition suggests that specific Cun ensembles on the surface of the Pd−Cu nanoparticles are needed for effective nitrate-to-nitrite conversion. In contrast, nitrite reduction rates were only minimally enhanced by the presence of copper. Increasing pH had little effect on the nitrate reduction rates, but it strongly inhibited the rate of nitrite reduction. The requisite protonation of a palladium−nitrite surface intermediate is proposed.
Knowledge of IFT values for chemical mixtures helps guide the design and analysis of various processes, including NAPL remediation with surfactants or alcohol flushing, enhanced oil recovery, and chemical separation technologies, yet available literature values are sparse. A comprehensive comparison of thermodynamic and empirical models for estimating interfacial tension (IFT) of organic chemical mixtures with water is conducted, mainly focusing on chlorinated organic compounds for 14 ternary, three quaternary, and one quinary systems. Emphasis is placed on novel results for systems with three and four organic chemical compounds, and for systems with composite organic compounds like lard oil and mineral oil. Seven models are evaluated: the ideal and nonideal monolayer models (MLID and MLNID), the ideal and nonideal mutual solubility models (MSID and MSNID), an empirical model for ternary systems (EM), a linear mixing model based on mole fractions (LMMM), and a newly developed linear mixing model based on volume fractions of organic mixtures (LMMV) for higher order systems. The two ideal models (MLID and MSID) fit ternary systems of chlorinated organic compounds without surface active compounds relatively well. However, both ideal models did not perform well for the mixtures containing a surface active compound. However, for these systems, both the MLNID and MSNID models matched the IFT data well. It is shown that the MLNID model with a surface coverage value (0.00341 mmol/m2) obtained in this study can practically be used for chlorinated organic compounds. The LMMM results in poorer estimates of the IFT as the difference in IFT values of individual organic compounds in a mixture increases. The EM, with two fitting parameters, provided accurate results for all 14 ternary systems including composite organic compounds. The new LMMV method for quaternary and higher component systems was successfully tested. This study shows that the LMMV may be able to be used for higher component systems and it can be easily incorporated into compositional multiphase flow models using only parameters from ternary systems.
This study tested the stability, activity, and selectivity of an alumina-supported Pd–In bimetallic catalyst during repetitive sulfide fouling and oxidative regeneration conditions. Nitrate reduction with hydrogen was used as the probe reaction in a continuous-flow packed-bed reactor to assess changes in the catalyst structure as a result of the fouling and regeneration processes. Partial regeneration of a severely sulfide-fouled Pd–In catalyst was achieved with a NaOCl/NaHCO3 solution. However, the regenerated catalyst had a reduced activity for NO3 − reduction and increased selectivity towards NH3. Analysis of the catalyst bed after regeneration experiments using XPS, ICP-MS, and BET surface area revealed that bulk structural transformations of the Pd–In bimetallic catalyst occurred, as a result of preferential Pd dissolution near the column influent. The dissolved Pd showed limited mobility in the column, and was re-deposited on the catalyst, resulting in Pd enrichment on the catalyst surface and redistribution of Pd towards the end of the column. These changes along with residual sulfur content on the catalyst surface were likely responsible for the increased selectivity towards NH3. These results indicate the importance of limiting the exposure of reduced sulfur species to Pd-based catalysts, especially when treating contaminants like NO3 −, where product selectivity is a priority.
H. Yoon, Werth, C. J., Barkan, C. P. L., Schaeffer, D. J., and Anand, P., “
North American railroads transport a wide variety of chemicals, chemical mixtures and solutions in railroad tank cars. In the event of an accident, these materials may be spilled and impact the environment. Among the chemicals commonly transported are a number of light non-aqueous phase liquids (LNAPLs). If these are spilled they can contaminate soil and groundwater and result in costly cleanups. Railroads need a means of objectively assessing the relative risk to the environment due to spills of these different materials. Environmental models are often used to determine the extent of contamination, and the associated environmental risks. For LNAPL spills, these models must account for NAPL infiltration and redistribution, NAPL dissolution and volatilization, and remediation systems such as pump and treat. This study presents the development and application of an environmental screening model to assess NAPL infiltration and redistribution in soils and groundwater, and to assess groundwater cleanup time using a pumping system. Model simulations use parameters and conditions representing LNAPL releases from railroad tank cars. To take into account unique features of railroad-tank-car spill sites, the hydrocarbon spill screening model (HSSM), which assumes a circular surface spill area and a circular NAPL lens, was modified to account for a rectangular spill area and corresponding lens shape at the groundwater table, as well as the effects of excavation and NAPL evaporation to the atmosphere. The modified HSSM was first used to simulate NAPL infiltration and redistribution. A NAPL dissolution and groundwater transport module, and a pumping system module were then implemented and used to simulate the effects of chemical properties, excavation, and free NAPL removal on NAPL redistribution and cleanup time. The amount of NAPL that reached the groundwater table was greater in coarse sand with high permeability than in fine sand or silt with lower permeabilities. Excavation can reduce the amount of NAPL that reaches the groundwater more effectively in lower permeability soils. The effect of chemical properties including vapor pressure and the ratio of density to viscosity become more important in fine sand and silt soil due to slow NAPL movement in the vadose zone. As expected, a pumping system was effective for high solubility chemicals, but it was not effective for low solubility chemicals due to rate-limited mass transfer by transverse dispersion and flow bypassing. Free NAPL removal can improve the removal efficiency for moderately low solubility chemicals like benzene, but cleanup times even after free NAPL removal can be prolonged for very low solubility chemicals like cyclohexane and styrene.
This study tested the selectivity and sustainability of an alumina-supported Pd–In bimetallic catalyst for nitrate reduction with H2 in a continuous-flow packed-bed reactor in the presence of: (i) dissolved oxygen (DO), an alternative electron acceptor to nitrate, (ii) variable NO3 −:H2 influent loadings, and (iii) the presence of a known foulant, sulfide. The sustainability of the catalyst was promising, as the catalyst was found to be stable under all conditions tested with respect to metal leaching. The presence of DO at concentrations typical of treatment conditions will increase H2 demand for NO3 − reduction, but has no negative impact on the selectivity of the catalyst. Under optimal conditions, i.e., a pH of 5.0 and a high NO3 −:H2 influent loading, low NH3 selectivity (5%) was achieved for extended periods (36 days), resulting in sustained levels of NH3 that approached the European legal limit. The biggest challenge to the sustainability of the catalyst was the addition of sulfide, that initially increased NH3 selectivity and ultimately resulted in complete deactivation of the catalyst. Further work is required to identify regeneration methods to restore sulfide-fouled catalyst activity and selectivity; however, the most effective use would be to remove sulfide prior to catalytic treatment.
Nonaqueous phase liquid (NAPL) dissolution was studied in three-dimensional (3D) heterogeneous experimental aquifers (25.5 cm × 9 cm × 8.5 cm) with two different longitudinal correlation lengths (2.1 cm and 1.1 cm) and initial spill volumes (22.5 ml and 10.5 ml). Spatial and temporal distributions of NAPL during dissolution were measured using magnetic resonance imaging (MRI). At high NAPL spill volume, average effluent concentrations initially increased during dissolution, as NAPL pools transitioned to NAPL ganglia, and then decreased as the total NAPL–water interfacial area decreased over time. Experimental results were used to test six dissolution models: (i and ii) a one-dimensional (1D) model using either specific NAPL–water interfacial area values estimated from MR images at each time step (i.e., 1D quasi-steady state model), or an empirical mass transfer (Sh′) correlation (i.e., 1D transient model), (iii and iv) a multiple analytical source superposition technique (MASST) using either the NAPL distribution determined from MR images at each time step (i.e., MASST steady state model), or the NAPL distribution determined from mass balance calculations (i.e., MASST transient model), (v) an equilibrium streamtube model, and (vi) a 3D grid-scale pool dissolution model (PDM) with a dispersive mass flux term. The 1D quasi-steady state model and 3D PDM captured effluent concentration values most closely, including some concentration fluctuations due to changes in the extent of flow reduction. The 1D transient, MASST steady state and transient, and streamtube models all showed a monotonic decrease in effluent concentration values over time, and the streamtube model was the most computationally efficient. Changes during dissolution of the effective NAPL–water interfacial area estimated from imaging data are similar to changes in effluent concentration values. The 1D steady state model incorporates estimates of the effective NAPL–water interfacial area directly at each time point; the 3D PDM does so indirectly through mass balance and a relative permeability function, which causes reduced water flow through high saturation NAPL regions. Hence, when model accuracy is required, the results indicate that a surrogate of this effective interfacial area is required. Approaches to include this surrogate in the MASST and streamtube models are recommended.
The objectives of this work were to determine if a pore-scale model could accurately capture the physical and chemical processes that control transverse mixing and reaction in microfluidic pore structures (i.e., micromodels), and to directly evaluate the effects of porous media geometry on a transverse mixing-limited chemical reaction. We directly compare pore-scale numerical simulations using a lattice-Boltzmann finite volume model (LB-FVM) with micromodel experiments using identical pore structures and flow rates, and we examine the effects of grain size, grain orientation, and intraparticle porosity upon the extent of a fast bimolecular reaction. For both the micromodel experiments and LB-FVM simulations, two reactive substrates are introduced into a network of pores via two separate and parallel fluid streams. The substrates mix within the porous media transverse to flow and undergo instantaneous reaction. Results indicate that (i) the LB-FVM simulations accurately captured the physical and chemical process in the micromodel experiments, (ii) grain size alone is not sufficient to quantify mixing at the pore scale, (iii) interfacial contact area between reactive species plumes is a controlling factor for mixing and extent of chemical reaction, (iv) at steady state, mixing and chemical reaction can occur within aggregates due to interconnected intra-aggregate porosity, (v) grain orientation significantly affects mixing and extent of reaction, and (vi) flow focusing enhances transverse mixing by bringing stream lines which were initially distal into close proximity thereby enhancing transverse concentration gradients. This study suggests that subcontinuum effects can play an important role in the overall extent of mixing and reaction in groundwater, and hence may need to be considered when evaluating reactive transport.
An existing multiphase flow simulator was modified in order to determine the effects of four mechanisms on NAPL mass removal in a strongly layered heterogeneous vadose zone during soil vapor extraction (SVE): a) NAPL flow, b) diffusion and dispersion from low permeability zones, c) slow desorption from sediment grains, and d) rate-limited dissolution of trapped NAPL. The impacts of water and NAPL saturation distribution, NAPL-type (i.e., free, residual, or trapped) distribution, and spatial heterogeneity of the permeability field on these mechanisms were evaluated. Two different initial source zone architectures (one with and one without trapped NAPL) were considered and these architectures were used to evaluate seven different SVE scenarios. For all runs, slow diffusion from low permeability zones that gas flow bypassed was a dominant factor for diminished SVE effectiveness at later times. This effect was more significant at high water saturation due to the decrease of gas-phase relative permeability. Transverse dispersion contributed to fast NAPL mass removal from the low permeability layer in both source zone architectures, but longitudinal dispersion did not affect overall mass removal time. Both slow desorption from sediment grains and rate-limited mass transfer from trapped NAPL only marginally affected removal times. However, mass transfer from trapped NAPL did affect mass removal at later time, as well as the NAPL distribution. NAPL flow from low to high permeability zones contributed to faster mass removal from the low permeability layer, and this effect increased when water infiltration was eliminated. These simulations indicate that if trapped NAPL exists in heterogeneous porous media, mass transfer can be improved by delivering gas directly to zones with trapped NAPL and by lowering the water content, which increases the gas relative permeability and changes trapped NAPL to free NAPL.
Magnetic resonance imaging (MRI) was used to visualize the NAPL source zone architecture before and after surfactant-enhanced NAPL dissolution in three-dimensional (3D) heterogeneously packed flowcells characterized by different longitudinal correlation lengths: 2.1 cm (aquifer 1) and 1.1 cm (aquifer 2). Surfactant flowpaths were determined by imaging the breakthrough of a paramagnetic tracer (MnCl2) analyzed by the method of moments. In both experimental aquifers, preferential flow occurred in high permeability materials with low NAPL saturations, and NAPL was preferentially removed from the top of the aquifers with low saturation. Alternate flushing with water and two surfactant pulses (5–6 pore volumes each) resulted in ∼ 63% of NAPL mass removal from both aquifers. However, overall reduction in mass flux (Mass Flux 1) exiting the flowcell was lower in aquifer 2 (68%) than in aquifer 1 (81%), and local effluent concentrations were found to increase by as high as 120 times at local sampling ports from aquifer 2 after surfactant flushing. 3D MRI images of NAPL revealed that NAPL migrated downward and created additional NAPL source zones in previously uncontaminated areas at the bottom of the aquifers. The additional NAPL source zones were created in the direction transverse to flow in aquifer 2, which explains the higher mass flux relative to aquifer 1. Analysis using a total trapping number indicates that mobilization of NAPL trapped in the two coarsest sand fractions is possible when saturation is below 0.5 and 0.4, respectively. Results from this study highlight the potential impacts of porous media heterogeneity and NAPL source zone architecture on advanced in-situ flushing technologies.
The identification and characterization of carbonaceous materials (CMs) that control hydrophobic organic chemical (HOC) sorption is essential to predict the fate and transport of HOCs in soils and sediments. The objectives of this paper are to determine the types of CMs that control HOC sorption in the oxidized and reduced zones of a glacially deposited groundwater sediment in central Illinois, with a special emphasis on the roles of kerogen and black carbon. After collection, the sediments were treated to obtain fractions of the sediment samples enriched in different types of CMs (e.g., humic acid, kerogen, black carbon), and selected fractions were subject to quantitative petrographic analysis. The original sediments and their enrichment fractions were evaluated for their ability to sorb trichloroethene (TCE), a common groundwater pollutant. Isotherm results and mass fractions of CM enrichments were used to calculate sorption contributions of different CMs. The results indicate that CMs in the heavy fractions dominate sorption because of their greater mass. Black carbon mass fractions of total CMs in the reduced sediments were calculated and used to estimate the sorption contribution of these materials. Results indicate that in the reduced sediments, black carbon may sequester as much as 32% of the sorbed TCE mass, but that kerogen and humin are the dominant sorption environments. Organic carbon normalized sorption coefficients (KOC) were compared to literature values. Values for the central Illinois sediments are relatively large and in the range of values determined for materials high in kerogen and humin. This work demonstrates the advantage of using both sequential chemical treatment and petrographic analysis to analyze the sorption contributions of different CMs in natural soils and sediments, and the importance of sorption to natural geopolymers in groundwater sediments not impacted by anthropogenic sources of black carbon.
The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability–liquid saturation–capillary pressure (k–S–P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.