Publications by Year: 2013

M. F. Fanizza, Yoon, H., Zhang, C., Oostrom, M., Wietsma, T. W., Hess, N. J., Bowden, M. E., Strathmann, T. J., Finneran, K. T., and Werth, C. J., “Pore scale evaluation of uranyl phosphate precipitation in a model groundwater system,” Water Resour. Res., {DOI}:, vol. 10., 2013.
H. Liu, Valocchi, A. J., Kang, Q., and Werth, C. J., “

Pore-scale simulations of gas displacing liquid in a homogeneous pore network using the lattice Boltzmann method

,” Transport in Porous Media, vol. 99, no. 3, pp. 555-580, 2013. Publisher's VersionAbstract
A lattice Boltzmann high-density-ratio model, which uses diffuse interface theory to describe the interfacial dynamics and was proposed originally by Lee and Liu (J Comput Phys 229:8045–8063, 2010), is extended to simulate immiscible multiphase flows in porous media. A wetting boundary treatment is proposed for concave and convex corners. The capability and accuracy of this model is first validated by simulations of equilibrium contact angle, injection of a non-wetting gas into two parallel capillary tubes, and dynamic capillary intrusion. The model is then used to simulate gas displacement of liquid in a homogenous two-dimensional pore network consisting of uniformly spaced square obstructions. The influence of capillary number (Ca), viscosity ratio (M), surface wettability, and Bond number (Bo) is studied systematically. In the drainage displacement, we have identified three different regimes, namely stable displacement, capillary fingering, and viscous fingering, all of which are strongly dependent upon the capillary number, viscosity ratio, and Bond number. Gas saturation generally increases with an increase in capillary number at breakthrough, whereas a slight decrease occurs when Ca is increased from   8.66×10−4  to   4.33×10−3 , which is associated with the viscous instability at high Ca. Increasing the viscosity ratio can enhance stability during displacement, leading to an increase in gas saturation. In the two-dimensional phase diagram, our results show that the viscous fingering regime occupies a zone markedly different from those obtained in previous numerical and experimental studies. When the surface wettability is taken into account, the residual liquid blob decreases in size with the affinity of the displacing gas to the solid surface. Increasing Bo can increase the gas saturation, and stable displacement is observed for   Bo>1  because the applied gravity has a stabilizing influence on the drainage process.
Y. Tang, Valocchi, A. J., Werth, C. J., and Liu, H., “An improved pore-scale biofilm model and comparison with a microfluidic flow cell experiment,” Water Resources Research, vol. 49, no. 12, pp. 8370-8382, 2013. Publisher's VersionAbstract
This work presents a pore-scale biofilm model that solves the flow field using the lattice Boltzmann method, the concentration field of chemical species using the finite difference method, and biofilm development using the cellular automaton method. We adapt the model from a previous work and expand it by implementing biofilm shrinkage in the cellular automaton method. The new pore-scale biofilm model is then evaluated against a previously published pore-scale biofilm experiment, in which two microfluidic flow cells, one with a homogeneous pore network and the other with an aggregate pore network, were tested for aerobic degradation of a herbicide. The simulated biofilm distribution and morphology, biomass accumulation, and contaminant removal are generally consistent with the experimental data. Biofilm detachment in this model occurs when the local shear stress is above a critical value. We use the critical value from our previously published modeling study and find it works well in this case, even though we now have a different pore network and a different microbial species. We also use the model to show that the interaction between flow and biofilm growth is important to predict contaminant removal. The computational time of the new model is reduced 90% compared to our prior work due to implementation of biofilm shrinkage in the cellular automaton method. To the best of our knowledge, this is the first time that biofilm shrinkage has been incorporated into a pore-scale model for simulation of pollutant biodegradation in porous media.
A. Kokkinaki, O'Carroll, D. M., Werth, C. J., and Sleep, B. E., “An evaluation of Sherwood–Gilland models for NAPL dissolution and their relationship to soil properties,” Journal of Contaminant Hydrology, vol. 155, pp. 87–98, 2013. Publisher's VersionAbstract
Predicting the longevity of non-aqueous phase liquid (NAPL) source zones has proven to be a difficult modeling problem that has yet to be resolved. Research efforts towards understanding NAPL depletion have focused on developing empirical models that relate lumped mass transfer rates to velocities and organic saturations. These empirical models are often unable to predict NAPL dissolution for systems different from those used to calibrate them, indicating that system-specific factors important for dissolution are not considered. This introduces the need for a calibration step before these models can be reliably used to predict NAPL dissolution for systems of arbitrary characteristics. In this paper, five published Sherwood–Gilland models are evaluated using experimental observations from the dissolution of two laboratory-scale complex three-dimensional NAPL source zones. It is shown that the relative behavior of the five models depends on the system and source zone characteristics. Through a theoretical analysis, comparing Sherwood–Gilland type models to a process-based, thermodynamic dissolution model, it is shown that the coefficients of the Sherwood–Gilland models can be related to measurable soil properties. The derived dissolution model with soil-dependent coefficients predicts concentrations identical to those predicted by the thermodynamic dissolution model for cases with negligible hysteresis. This correspondence breaks down when hysteresis has a significant impact on interfacial areas. In such cases, the derived dissolution model will slightly underestimate dissolved concentrations at later times, but is more likely to capture system-specific dissolution rates than Sherwood–Gilland models.
A. Kokkinaki, O'Carroll, D. M., Werth, C. J., and Sleep, B. E., “Coupled simulation of DNAPL infiltration and dissolution in three-dimensional heterogeneous domains: Process model validation,” Water Resources Research, vol. 49, no. 10, pp. 7023-7036, 2013. Publisher's VersionAbstract
A three-dimensional multiphase numerical model was used to simulate the infiltration and dissolution of a dense nonaqueous phase liquid (DNAPL) release in two experimental flow cells containing different heterogeneous and well-characterized permeability fields. DNAPL infiltration was modeled using Brooks-Corey-Burdine hysteretic constitutive relationships. DNAPL dissolution was simulated using a rate-limited mass transfer expression with a velocity-dependent mass transfer coefficient and a thermodynamically based calculation of DNAPL-water interfacial area. The model did not require calibration of any parameters. The model predictions were compared to experimental measurements of high-resolution DNAPL saturations and effluent concentrations. The predicted concentrations were in close agreement with measurements for both domains, indicating that important processes were effectively captured by the model. DNAPL saturations greatly influenced mass transfer rates through their effect on relative permeability and velocity. Areas with low DNAPL saturation were associated with low interfacial areas, which resulted in reduced mass transfer rates and nonequilibrium dissolution. This was captured by the thermodynamic interfacial area model, while a geometric model overestimated the interfacial areas and the overall mass transfer. This study presents the first validation of the thermodynamic dissolution model in three dimensions and for high aqueous phase velocities; such conditions are typical for remediation operations, especially in heterogeneous aquifers. The demonstrated ability to predict DNAPL dissolution, only requiring prior characterization of soil properties and DNAPL release conditions, represents a significant improvement compared to empirical dissolution models and provides an opportunity to delineate the relationship between source zone architecture and the remediation potential for complex DNAPL source zones.
Y. - S. Jun, Giammar, D. E., and Werth, C. J., “Impacts of geochemical reactions on geologic carbon sequestration,” Environmental Science & Technology, vol. 47, no. 1, pp. 3–8, 2013. Publisher's VersionAbstract
In the face of increasing energy demands, geologic CO2 sequestration (GCS) is a promising option to mitigate the adverse effects of climate change. To ensure the environmental sustainability of this option, we must understand the rates and mechanisms of key geochemical reactions and their impacts on GCS performance, the multiphase reactive transport of CO2, and the management of environmental risks. Strong interdisciplinary collaborations are required to minimize environmental impacts and optimize the performance of GCS operations.
J. K. Choe, Mehnert, M. H., Guest, J. S., Strathmann, T. J., and Werth, C. J., “Comparative assessment of the environmental sustainability of existing and emerging perchlorate treatment technologies for drinking water,” Environmental Science & Technology, vol. 47, no. 9, pp. 4644–4652, 2013. Publisher's VersionAbstract
Environmental impacts of conventional and emerging perchlorate drinking water treatment technologies were assessed using life cycle assessment (LCA). Comparison of two ion exchange (IX) technologies (i.e., nonselective IX with periodic regeneration using brines and perchlorate-selective IX without regeneration) at an existing plant shows that brine is the dominant contributor for nonselective IX, which shows higher impact than perchlorate-selective IX. Resource consumption during the operational phase comprises >80% of the total impacts. Having identified consumables as the driving force behind environmental impacts, the relative environmental sustainability of IX, biological treatment, and catalytic reduction technologies are compared more generally using consumable inputs. The analysis indicates that the environmental impacts of heterotrophic biological treatment are 2–5 times more sensitive to influent conditions (i.e., nitrate/oxygen concentration) and are 3–14 times higher compared to IX. However, autotrophic biological treatment is most environmentally beneficial among all. Catalytic treatment using carbon-supported Re–Pd has a higher (ca. 4600 times) impact than others, but is within 0.9–30 times the impact of IX with a newly developed ligand-complexed Re–Pd catalyst formulation. This suggests catalytic reduction can be competitive with increased activity. Our assessment shows that while IX is an environmentally competitive, emerging technologies also show great promise from an environmental sustainability perspective.
D. Shuai, McCalman, D. C., Choe, J. K., Shapley, J. R., Schneider, W. F., and Werth, C. J., “Structure sensitivity study of waterborne contaminant hydrogenation using shape- and size-controlled Pd nanoparticles,” ACS Catalysis, vol. 3, no. 3, pp. 453–463, 2013. Publisher's VersionAbstract
Catalytic reduction with Pd has emerged as a promising technology to remove a suite of contaminants from drinking water, such as oxyanions, disinfection byproducts, and halogenated pollutants, but low activity is a major challenge for application. To address this challenge, we synthesized a set of shape- and size-controlled Pd nanoparticles and evaluated the activity of three probe contaminants (i.e., nitrite, N-nitrosodimethylamine (NDMA), and diatrizoate) as a function of facet type (e.g., (100), (110), (111)), ratios of low- to high-coordination sites, and ratios of surface sites to total Pd (i.e., dispersion). Reduction results for an initial contaminant concentration of 100 μM show that initial turnover frequency (TOF0) for nitrite increases 4.7-fold with increasing percent of (100) surface Pd sites (from 0% to 95.3%), whereas the TOF0 for NDMA and for diatrizoate increases 4.5- and 3.6-fold, respectively, with an increasing percent of terrace surface Pd sites (from 79.8% to 95.3%). Results for an initial nitrite concentration of 2 mM show that TOF0 is the same for all shape- and size-controlled Pd nanoparticles. Trends for TOF0 were supported by results showing that all catalysts but one were stable in shape and size up to 12 days; for the exception, iodide liberation in diatrizoate reduction appeared to be responsible for a shape change of 4 nm octahedral Pd nanoparticles. Density functional theory (DFT) simulations for the free energy change of hydrogen (H2), nitrite, and nitric oxide (NO) adsorption and a two-site model based on the Langmuir–Hinshelwood mechanism suggest that competition of adsorbates for different Pd sites can explain the TOF0 results. Our study shows for the first time that catalytic reduction activity for waterborne contaminant removal varies with the Pd shape and size, and it suggests that Pd catalysts can be tailored for optimal performance to treat a variety of contaminants for drinking water.
R. Zhang, Shuai, D., Guy, K. A., Shapley, J. R., Strathmann, T. J., and Werth, C. J., “Elucidation of nitrate reduction mechanisms on a Pd-In bimetallic catalyst using isotope labeled nitrogen species,” ChemCatChem, vol. 5, no. 1, pp. 313–321, 2013. Publisher's VersionAbstract
To understand nitrate reduction pathway and to improve selectivity towards dinitrogen (N2) over toxic ammonia species (NH4+, NH3), aqueous reduction experiments with an Al2O3‐supported Pd‐In bimetallic catalyst were conducted by using isotope‐labeled nitrite (15NO2−). Nitrite is the first reduction intermediate of nitrate. Experiments were performed using nitrite alone and in combination with unlabeled proposed reduction intermediates (N2O, NO), and using only N2O and NO alone, each as a starting reactant. Use of 15N‐labeled species eliminates interference from ambient N2 when assessing mass balances and product distributions. Simultaneous catalytic reduction of 15NO2− and 14N2O shows no isotope mixing in the final N2 product, demonstrating that N2O does not react with other NO2− reduction intermediates; N2O reduction alone yielded only N2. In contrast, simultaneous catalytic reduction of 15NO2− and 14NO yielded mixed‐labeled 15/14N2 (MW: 29), whereas reduction of 15NO alone yields a mixture N2 and NH4+, the ratio of which varies with initial 15NO concentration. These findings, along with those from a new kinetic model we propose, indicate that highly reactive adsorbed NO (NO*), or other unspecified adsorbed N species (Nads), is a key intermediate involved in determining final product selectivity.
J. Liu, Choe, J. K., Sasnow, Z., Shapley, J. R., Werth, C. J., and Strathmann, T. J., “Application of a Re-Pd bimetallic catalyst for treatment of perchlorate in waste ion-exchange regenerant brine,” Water Research, vol. 47, no. 1, pp. 91–101, 2013. Publisher's VersionAbstract
Concentrated sodium chloride (NaCl) brines are often used to regenerate ion-exchange (IX) resins applied to treat drinking water sources contaminated with perchlorate (ClO4−), generating large volumes of contaminated waste brine. Chemical and biological processes for ClO4− reduction are often inhibited severely by high salt levels, making it difficult to recycle waste brines. Recent work demonstrated that novel rhenium–palladium bimetallic catalysts on activated carbon support (Re–Pd/C) can efficiently reduce ClO4− to chloride (Cl−) under acidic conditions, and here the applicability of the process for treating waste IX brines was examined. Experiments conducted in synthetic NaCl-only brine (6–12 wt%) showed higher Re–Pd/C catalyst activity than in comparable freshwater solutions, but the rate constant for ClO4− reduction measured in a real IX waste brine was found to be 65 times lower than in the synthetic NaCl brine. Through a series of experiments, co-contamination of the IX waste brine by excess NO3− (which the catalyst reduces principally to NH4+) was found to be the primary cause for deactivation of the Re–Pd/C catalyst, most likely by altering the immobilized Re component. Pre-treatment of NO3− using a different bimetallic catalyst (In–Pd/Al2O3) improved selectivity for N2 over NH4+ and enabled facile ClO4− reduction by the Re–Pd/C catalyst. Thus, sequential catalytic treatment may be a promising strategy for enabling reuse of waste IX brine containing NO3− and ClO4−.