Modeling Microbial Transport and Biodegradation in a Dual-porosity System

A mathematical model describing microbial transport and growth in a heterogeneous aquifer domain, composed of overlapping subdomains of high-permeability and low-permeability materials, is developed. Each material is conceptually visualized as a continuum which occupies the entire considered spatial aquifer domain. Based on the assumption that advection in the low-permeability domain is negligible, the mathematical model is solved by using a publically available reactive transport code. The importance of modeling microbial transport and growth in such a dual-porosity system is demonstrated through a hypothetical case study.     

Copper‐Doped CdSe/ZnS Quantum Dots: Controllable Photoactivated Copper(I) Cation Storage and Release Vectors for Catalysis

The first photoactivated doped quantum dot vector for metal‐ion release has been developed. A facile method for doping copper(I) cations within ZnS quantum dot shells was achieved through the use of metal‐dithiocarbamates, with Cu⁺ ions elucidated by X‐ray photoelectron spectroscopy. Photoexcitation of the quantum dots has been shown to release Cu⁺ ions, which was employed as an effective catalyst for the Huisgen [3+2] cycloaddition reaction. The relationship between the extent of doping, catalytic activity, and the fluorescence quenching was also explored.     

Aqueous sonolytic decomposition of polycyclic aromatic hydrocarbons in the presence of additional dissolved species

Sonochemical degradation of aqueous polycyclic aromatic hydrocarbons (PAHs) results in a first-order loss of the PAHs (k=0.010–0.027 s⁻¹). When sonication occurred in the presence of other organic compounds, the degradation rate constant was reduced quite dramatically. This reduction is believed to come about through scavenging of radicals by the matrix chemical. When oxygen was bubbled into the PAH solution before sonication, the degradation rate constant was elevated. Nitrogen purging resulted in decreased rate constants. These results indicate that oxygen was an important precursor in the degradation of the PAHs. Organic compounds, including humic acid, benzoic acid, and sodium dodecyl sulfate, decreased PAH degradation rate constants by scavenging oxygen derived reactive transients.     

Synthesis and characterization of nitrosyl diruthenium complexes. Interaction between NO and CO across the metal-metal bond

Two neutral diruthenium complexes and one anionic diruthenium complex, Ru2(dpf)4(NO), Ru2(dpf)4(NO)2, and [Ru2(dpf)4(NO)]-, where dpf is diphenylformamidinate anion, were synthesized and characterized as to their electrochemical and spectroscopic properties. Two of the compounds, Ru2(dpf)4(NO) and Ru2(dpf)4(NO)2, were also structurally characterized. Ru2(dpf)4(NO) undergoes reversible one-electron reductions under N2 at E1/2=0.06 and -1.24 V in CH2Cl2, 0.1 M TBABr. These processes are shifted to E1/2=0.18 and -0.78 V under CO due to the trans-coordination of a CO molecule which stabilizes the singly and doubly reduced forms of the metal-metal bonded complexes, thus leading to easier reductions. CO does not coordinate to Ru2(dpf)4(NO), but it does bind to the singly reduced species to generate [Ru2(dpf)4(NO)(CO)]- under a CO atmosphere in solution; characteristic NO and CO bands are seen for this compound at nuNO=1674 cm(-1) and nuCO=1954 cm(-1). Ru2(dpf)4(NO)2 displays a reversible one-electron reduction at E1/2=-1.24 V versus SCE and an irreversible reduction at Epc=-1.96 V in CH2Cl2, 0.1 M TBAP under N2. There are also two reversible one-electron oxidations at E1/2=0.24 and 1.15 V. Spectroelectrochemical monitoring of the Ru2(dpf)4(NO)2 oxidation processes in a thin-layer cell shows only a single NO vibration for each electrogenerated product and nuNO is located at 1726 (neutral), 1788 (singly oxidized), or 1834 (doubly oxidized) cm(-1). Finally, a labile CO complex, [Ru2(dpf)4(NO)(CO)]-, could be generated by passing CO into a solution of [Ru2(dpf)4(NO)]-. Formation of the mixed CO/NO adduct was confirmed by electrochemistry and infrared spectroscopy. Analysis of the NO and CO stretching vibration frequencies for [Ru2(dpf)4(NO)(CO)]- by in-situ FTIR spectroelectrochemistry and comparisons with data for Ru2(dpf)4(NO) and Ru2(dpf)4(CO) reveal the presence of a strong interaction between NO and CO across the Ru-Ru bond.     

The crystal and molecular structure of one of the possible conformers of “the smallest piece of ice”—A solid-state isolation of a hydrogen bonded water hexamer trapped within channels of a crystal of a dirhodium molecule

Reexamination of our study of [Rh₂(HNOCCH₃)₄(2H₂O)] 3H₂O (Ahsan, M.Q.; Bernal, I.; Bear, J.L. Inorg. Chem. 1986, 26 260) showed it to be interesting not just because the dirhodium molecule is an antineoplastic but because it contains a hexameric cluster of waters trapped in Rh–Rh lattice cavities. It may well provide an interesting model for the smallest piece of ice (Nauta, K.; Miller, R.E. Science 2000, 287, 293).     

Saltwater Upconing and Decay Beneath a Well Pumping Above an Interface Zone

Saltwater, or brine, underlies freshwater in many aquifers, with a transition zone separating them. Pumping freshwater by a well located above the transition zone produces upconing of the latter, eventually salinizing the pumped water, forcing shut-off. Following the well’s shut-off, the upconed saltwater mound undergoes decay, tending to return to the pre-pumping regime. The FEAS code is used for the simulation of coupled density-dependent flow and salt transport involved in the upconing–decay process. In this code, the flow equation is solved by the Galerkin finite element method (FEM), while the advective–dispersive salt transport equation is solved in the Eulerian–Lagrangian framework. The code does not suffer from the instability constraint on the Peclet number. The code is used to investigate the transient upconing–decay process in an axially symmetric system and to discover how the process is affected by two major factors: the density difference factor (DDF) and the dispersivities. Simulation results show that under certain conditions, pumping essentially freshwater can be maintained for a certain time period, the length of which depends on the dispersivity values used. A recirculating flow cell may occur in the saltwater layer beneath the pumping well, widening the saltwater mound. The decay process is lengthy; it takes a long time for the upconed saltwater to migrate back to its original shape of a horizontal transition zone prior to pumping. However, the wider transition zone caused by hydrodynamic dispersion can never return to the initial one. This indicates that once a pumping well is abandoned because of high salinity, it can be reused for groundwater utilization only after a long time. It is also shown that the upconing–decay process is very sensitive to DDF, which, in our work, ranges from 0 (for an ideal tracer) to 0.2 (for brine). For a DDF of 0.025 (for seawater), local upconing occurs only for low iso-salinity surfaces, while those of high salt concentration remain stable after a short time. For an ideal tracer, all iso-salinity surfaces rise toward the pumping well, whereas for brine only iso-salinity surfaces of very low salinity upcone towards the pumping well. This may imply that the traditional finding that the sharp interface approximation is practically close to the 0.5 iso-salinity surface may not be true for a high DDF solution.     

Evolution of the balance equations in saturated thermoelastic porous media following abrupt simultaneous changes in pressure and temperature

A mathematical model is developed for saturated flow of a Newtonian fluid in a thermoelastic, homogeneous, isotropic porous medium domain under nonisothermal conditions. The model contains mass, momentum and energy balance equations. Both the momentum and energy balance equations have been developed to include a Forchheimer term which represents the interaction at the solid-fluid interface at high Reynolds numbers. The evolution of these equations, following an abrupt change in both fluid pressure and temperature, is presented. Using a dimensional analysis, four evolution periods are distinguished. At the very first instant, pressure, effective stress, and matrix temperature are found to be disturbed with no attenuation. During this stage, the temporal rate of pressure change is linearly proportional to that of the fluid temperature. In the second time period, nonlinear waves are formed in terms of solid deformation, fluid density, and velocities of phases. The equation describing heat transfer becomes parabolic. During the third evolution stage, the inertial and the dissipative terms are of equal order of magnitude. However, during the fourth time period, the fluid's inertial terms subside, reducing the fluid's momentum balance equation to the form of Darcy's law. During this period, we note that the body and surface forces on the solid phase are balanced, while mechanical work and heat conduction of the phases are reduced.     

On the movement of an LNAPL lens on the water table

The penetration of light nonaqueous phase liquids (LNAPLs) in quantities that lead to an accumulation in the form of a lens above the water table is considered. First, the three-phase vertical gravity-capillary equilibrium of water, NAPL, and air above the water table is specified. The hypothesis of ‘vertical equilibrium phase distribution’ is used to derive averaged asymptotic equations describing NAPL flow as a thin lens floating above the water table. Some problems of unsteady NAPL lens movement and the development of a NAPL mound, spreading along an inclined or horizontal phreatic surface are discussed and the analytical solutions are obtained.