Density functional theory computations at the B3LYP/SDDp//B3LYP/Lanl2DZ level were performed on model complexes derived from [(Me(2)C(2)S(2))Mo(O)(2)-S-CuSMe](2-) or its oxo protonated form to gain insight into the reaction steps involved in substrate oxidation of a Mo-/Cu-dependent CO dehydrogenase. Only the bisoxo but not the hydroxo oxo complex was found to oxidize CO exothermically. A thiocarbamate complex structurally characterized as the reaction product of the enzyme with the inhibitor n-butylisonitrile corresponds to a thermodynamic well on the potential energy surface. For the formation of the analogous thiocarbonate complex from CO oxidation, however, we do not find a significant thermodynamic driving force. In the protein matrix of the enzyme this species should be further destabilized, as it requires the metal centers to move apart considerably from each other.

Sea‐level rise and increases in the frequency and intensity of ocean surges caused by climate change are likely to exacerbate adverse effects on low‐lying coastal areas. The landward flow of water during ocean surges introduces salt to surficial coastal aquifers and threatens groundwater resources. Coastal topographic features (e.g., ponds, dunes, barrier islands, and channels) likely have a strong impact on overwash and salinization processes, but are generally highly simplified in modeling studies. To understand topographic impacts on groundwater salinization, we modeled a theoretical overwash event and variable‐density groundwater flow and salt transport in 3‐D using the fully coupled surface and subsurface numerical simulator, HydroGeoSphere. The model simulates the coastal aquifer as an integrated system considering overland flow, coupled surface and subsurface exchange, variably saturated flow, and variable‐density groundwater flow. To represent various coastal landscape types, we simulated both synthetic fields and real‐world coastal topography from Delaware, USA. The groundwater salinization assessment suggested that the topographic connectivity promoting overland flow controls the volume of aquifer that is salinized. In contrast, the amount of water that can be stored in surface depressions determines the amount of seawater that infiltrates the subsurface and the time for seawater to flush from the aquifer. Our study suggests that topography has a significant impact on groundwater salinization due to ocean surge overwash, with important implications for coastal land management and groundwater vulnerability assessment.

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This article examines the required spatial discretization perpendicular to the fracture-matrix interface (FMI) for numerical simulation of solute transport in discretely fractured porous media. The discrete-fracture, finite-element model HydroGeoSphere (Therrien et al. 2005) and a discrete-fracture implementation of MT3DMS (Zheng 1990) were used to model solute transport in a single fracture, and the results were compared to the analytical solution of Tang et al. (1981). To match analytical results on the relatively short timescales simulated in this study, very fine grid spacing perpendicular to the FMI of the scale of the fracture aperture is necessary if advection and/or dispersion in the fracture is high compared to diffusion in the matrix. The requirement of such extremely fine spatial discretization has not been previously reported in the literature. In cases of high matrix diffusion, matching the analytical results is achieved with larger grid spacing at the FMI. Cases where matrix diffusion is lower can employ a larger grid multiplier moving away from the FMI. The very fine spatial discretization identified in this study for cases of low matrix diffusion may limit the applicability of numerical discrete-fracture models in such cases.

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