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.
Y. - S. Jun, Giammar, D. E., and Werth, C. J., “Impacts of geochemical reactions on geologic carbon sequestration,” Environ. Sci. Technol., Feature Article, vol. 47, pp. 3–8, 2013.
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, pp. 453–463, 2013.
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, pp. 313–321, 2013.
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, pp. 91–101, 2013.
H. Liu, Valocchi, A. J., Werth, C. J., and Kang, Q., “

Pore-scale simulations of gas displacing liquid in a homogeneous micromodel

,” vol. 99, no. 3, pp. 555-580, 2013.
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.
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.