This research investigated reduction of trichloroethylene (TCE) at boron-doped diamond (BDD) film cathodes using a rotating disk electrode reactor. Rates of TCE reduction were determined as functions of the electrode potential and TCE concentration over a temperature range between 2 and 32 degrees C. Reduction of TCE resulted in production of acetate and chloride ions with no detectable intermediate products. At a current density of 15 mA/cm2 and concentrations below 0.75 mM, reaction rates were first order with respect to TCE concentration, with surface area normalized rate constants 2 orders of magnitude greater than those for iron electrodes. Density functional theory (DFT) simulations were used to evaluate activation barriers for reduction by direct electron transfer, and for reaction with four functional groups commonly found on BDD surfaces. The DFT calculated activation barrier for direct electron transfer was more than 4 times greater than the experimentally measured value of 22 kJ/mol. In contrast, the DFT activation barrier for reaction at a deprotonated hydroxyl site on a tertiary carbon atom (triple bond C-O(-)) of 24 kJ/mol was in close agreement with the experimental value. Both experiments and quantum mechanical simulations support a TCE reduction mechanism that involves chemically adsorbed intermediates.

The key to advancing the predictability of rainfall-triggered landslides is to use physically based slope-stability models that simulate the transient dynamical response of the subsurface moisture to spatiotemporal variability of rainfall in complex terrains. TRIGRS (transient rainfall infiltration and grid-based regional slope-stability analysis) is a USGS landslide prediction model, coded in Fortran, that accounts for the influences of hydrology, topography, and soil physics on slope stability. In this study, we quantitatively evaluate the spatiotemporal predictability of a Matlab version of TRIGRS (MaTRIGRS) in the Blue Ridge Mountains of Macon County, North Carolina where Hurricanes Ivan triggered widespread landslides in the 2004 hurricane season. High resolution digital elevation model (DEM) data (6-m LiDAR), USGS STATSGO soil database, and NOAA/ NWS combined radar and gauge precipitation are used as inputs to the model. A local landslide inventory database from North Carolina Geological Survey is used to evaluate the MaTRIGRS' predictive skill for the landslide locations and timing, identifying predictions within a 120-m radius of observed landslides over the 30-h period of Hurricane Ivan's passage in September 2004. Results show that within a radius of 24 m from the landslide location about 67% of the landslide, observations could be successfully predicted but with a high false alarm ratio (90%). If the radius of observation is extended to 120 m, 98% of the landslides are detected with an 18% false alarm ratio. This study shows that MaTRIGRS demonstrates acceptable spatiotemporal predictive skill for landslide occurrences within a 120-m radius in space and a hurricane-event-duration (h) in time, offering the potential to serve as a landslide warning system in areas where accurate rainfall forecasts and detailed field data are available. The validation can be further improved with additional landslide information including the exact time of failure for each landslide and the landslide's extent and run out length.

No abstract

An early warning system has been developed to predict rainfall-induced shallow landslides over Java Island, Indonesia. The prototyped early warning system integrates three major components: (1) a susceptibility mapping and hotspot identification component based on a land surface geospatial database (topographical information, maps of soil properties, and local landslide inventory, etc.); (2) a satellite-based precipitation monitoring system (http://trmm.gsfc.nasa.gov) and a precipitation forecasting model (i.e., Weather Research Forecast); and (3) a physically based, rainfall-induced landslide prediction model SLIDE. The system utilizes the modified physical model to calculate a factor of safety that accounts for the contribution of rainfall infiltration and partial saturation to the shear strength of the soil in topographically complex terrains. In use, the land-surface "where" information will be integrated with the "when" rainfall triggers by the landslide prediction model to predict potential slope failures as a function of time and location. In this system, geomorphologic data are primarily based on 30-m Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data, digital elevation model (DEM), and 1-km soil maps. Precipitation forcing comes from both satellite-based, real-time National Aeronautics and Space Administration (NASA) Tropical Rainfall Measuring Mission (TRMM), and Weather Research Forecasting (WRF) model forecasts. The system's prediction performance has been evaluated using a local landslide inventory, and results show that the system successfully predicted landslides in correspondence to the time of occurrence of the real landslide events. Integration of spatially distributed remote sensing precipitation products and in-situ datasets in this prototype system enables us to further develop a regional, early warning tool in the future for predicting rainfall-induced landslides in Indonesia.

The effect of current density on dosing rates and energy requirements for iron and aluminum electrodes in a bench-scale electrocoagulation (EC) reactor have been investigated. Dissolution rates of the iron and aluminum anodes were independent of bulk solution pH values. Iron dosing rates followed Faraday's law, but aluminum dosing rates averaged 83% greater than those predicted by Faraday's law. Chemical corrosion of both the anode and cathode contributed to the extra-faradaic aluminum dosing. A method was developed to determine the faradaic power consumption as a function of the current density. An equation describing power dissipation by ohmic and faradaic mechanisms was derived and used to estimate energy consumption per unit coagulant dose for EC reactors operating over a wide range of conditions. The derived equation can be used to compare the operational costs for EC with those using chemical additives, such as alum or ferric chloride.

This research investigated oxidation of perfluorobutane sulfonate (PFBS) at a boron-doped diamond (BDD) film anode. PFBS oxidation produced carbon dioxide, sulfate, fluoride, and trace amounts of trifluoroacetic acid (TFA). Rate constants for PFBS oxidation as a function of current density and temperature were measured using a rotating disk electrode (RDE) reactor. Reaction rates in the RDE reactor were zeroth order with respect to PFBS concentration, which is indicative of a reaction limited by the availability of reactive sites. The apparent electron transfer coefficient and apparent activation energy were used to evaluate the rate-limiting step for PFBS oxidation. Density functional simulations were used to calculate the reaction energies and activation barriers for PFBS oxidation by hydroxyl radicals and by direct electron transfer. Simulation results indicated that the experiments were performed at sufficiently high overpotentials that the rate-limiting step was an activationless direct electron transfer reaction.

No abstract

Conformational order indicators for perdeuterated alkyl chain systems are identified in the Raman spectra of nonadecane-d40, polyethylene-d4, and stearic acid-d35. Six spectral indicators are identified: I[nu(a)(CD2)2196]/I[nu(a)(CD2)2172], I[nu(C-C)G]/I[nu(C-C)T], I[nu(s)(CD3)]/I[nu(a)(CD2)2172], I[nu(s)(CD2)]/I[nu(a)(CD2)2172], and the full width at half-maximum (fwhm) and frequency of the nu(s)(CD2) mode. Among these indicators, the ratio of I[nu(a)(CD2)2196]/I[nu(a)(CD2)2172] is considered a primary indicator of conformational order, since it responds to alkyl chain conformational changes in a manner similar to the I[nu(a)(CH2)]/I[nu(s)(CH2)] primary indicator for hydrogenated systems. Other indicators are correlated to this primary indicator to derive a better understanding of the effect of structural attributes on conformational order in perdeuterated alkyl chain systems. These Raman spectral order indicators are applicable to any perdeuterated alkyl-containing system including lipids, biological membranes, alkylsilane-based chromatographic stationary phases, and self-assembled monolayers.