Design of a high-temperature and high-pressure liquid flow cell for x-ray absorption fine structure measurements under catalytic reaction conditions

The design and performance of a new high-pressure and high-temperature cell for measurement of x-ray absorption fine structure (XAFS) spectra of solid catalysts working in a flowing liquid are presented. The cell has flat, high-purity sintered cubic boron nitride (c-BN) windows which can tolerate high temperature (900 K) and high pressure (10 MPa). The c-BN is a new material which has the highest tensile strength, second only to diamond, and is also chemically and thermally stable. The use of the cell is demonstrated for measurements of PtPdAl(2)O(3) and Ni(2)PSiO(2) hydrodesulfurization catalysts at reaction conditions. A technique called delta chi (Deltachi), involving determining the difference between XAFS spectra of the sample at reaction conditions and the bare sample, is introduced.     

Fungal Infection Reduces Herbivore-Induced Plant Volatiles of Maize but does not Affect Naïve Parasitoids

Plants attacked by insects release volatile compounds that attract the herbivores' natural enemies. This so-called indirect defense is plastic and may be affected by an array of biotic and abiotic factors. We investigated the effect of fungal infection as a biotic stress agent on the emission of herbivore-induced volatiles and the possible consequences for the attraction of two parasitoid species. Maize seedlings that were simultaneously attacked by the fungus Setosphaeria turcica and larvae of Spodoptera littoralis emitted a blend of volatiles that was qualitatively similar to the blend emitted by maize that was damaged by only the herbivore, but there was a clear quantitative difference. When simultaneously challenged by fungus and herbivore, the maize plants emitted in total 47% less of the volatiles. Emissions of green leaf volatiles were unaffected. In a six-arm olfactometer, the parasitoids Cotesia marginiventris and Microplitis rufiventris responded equally well to odors of herbivore-damaged and fungus- and herbivore-damaged maize plants. Healthy and fungus-infected plants were not attractive. An additional experiment showed that the performance of S. littoralis caterpillars was not affected by the presence of the pathogen, nor was there an effect on larvae of M. rufiventris developing inside the caterpillars. Our results confirm previous indications that naïve wasps may respond primarily to the green leaf volatiles.     

Projection of hazardous air pollutant emissions to future years

Projecting a hazardous air pollutant (HAP) emission inventory to future years can provide valuable information for air quality management activities such as prediction of program successes and helping to assess future priorities. We have projected the 1999 National Emission Inventory for HAPs to numerous future years up to 2020 using the following tools and data: the Emissions Modeling System for Hazardous Air Pollutants (EMS-HAP), the National Mobile Inventory Model (NMIM), emission reduction information resulting from national standards and economic growth data. This paper discusses these projection tools, the underlying data, limitations and the results. The results presented include total HAP emissions (sum of pollutants) and toxicity-weighted HAP emissions for cancer and respiratory noncancer effects. Weighting emissions by toxicity does not consider fate, transport, or location and behavior of receptor populations and can only be used to estimate relative risks of direct emissions. We show these projections, along with historical emission trends. The data show that stationary source programs under Section 112 of the Clean Air Act Amendments of 1990 and mobile source programs which reduce hydrocarbon and particulate matter emissions, as well as toxic emission performance standards for reformulated gasoline, have contributed to and are expected to continue to contribute to large declines in air toxics emissions, in spite of economic and population growth. We have also analyzed the particular HAPs that dominate the source sectors to better understand the historical and future year trends and the differences across sectors.     

Theory and practice of ubiquitous quantitative chemical analysis using conventional computer optical disk drives

We demonstrate a new attractive approach for ubiquitous quantitative chemical or biological sensing when analog signals are acquired from conventional optical disk drives, and these signals are used for quantitative detection of optical changes of sensing films deposited on conventional CD and DVD optical disks. Our developed analytical model of the operation of this Lab-on-DVD system describes the optical response of sensing films deposited onto the read surface of optical disks by taking into account the practical aspects of system performance that include possible reagent leaching effects, water sampling (delivering) efficiency, and possible changes of the film morphology after water removal. By applying a screen-printing process, we demonstrated a laboratory-scale automated production of sensing films with an average thickness of approximately 10 microm and a thickness relative standard deviation of <3% across multiple films. Finally, we developed a system for delivery of water-sample volumes to sensing films on the disk that utilized a multifunctional jewel case assembly.     

Introducing Enantioselective Ultrahigh-Pressure Liquid Chromatography (eUHPLC): Theoretical Inspections and Ultrafast Separations on a New Sub-2-μm Whelk-O1 Stationary Phase

A new chiral stationary phase for ultrahigh-pressure liquid chromatography (UHPLC) applications was prepared by covalent attachment of the Whelk-O1 selector to spherical, high-surface-area 1.7-μm porous silica particles. Columns of varying dimensions (lengths of 50, 75, 100, and 150 mm and internal diameters of 3.0 or 4.6 mm) were packed and characterized in terms of permeability, efficiency, retention, and enantioselectivity, using both organic and water-rich mobile phases. A conventional HPLC Whelk-O1 column based on 5.0-μm porous silica particles and packed in a 250 mm × 4.6 mm column was used as a reference. Van Deemter curves, generated with low-molecular-weight solutes on a 100 mm × 4.6 mm column packed with the 1.7-μm particles, showed H(min) (μm) and μ(opt) (mm/s) values of 4.10 and 5.22 under normal-phase and 3.74 and 4.34 under reversed-phase elution conditions. The flat C term of the van Deemter curves observed with the 1.7-μm particles allowed the use of higher-than-optimal flow rates without significant efficiency loss. Kinetic plots constructed from van Deemter data confirmed the ability of the column packed with the 1.7-μm particles to afford subminute separations with good efficiency and its superior performances in the high-speed regime, compared to the column packed with 5.0-μm particles. Resolutions in the time scale of seconds were obtained using a 50-mm-long column in the normal phase or polar organic mode. The intrinsic kinetic performances of 1.7-μm silica particles are retained in the Whelk-O1 chiral stationary phase, clearly demonstrating the potentials of enantioselective UHPLC in terms of high speed, throughput, and resolution.     

Combined extended and superimposed finite element method for cracks

A combination of the extended finite element method (XFEM) and the mesh superposition method (s‐version FEM) for modelling of stationary and growing cracks is presented. The near‐tip field is modelled by superimposed quarter point elements on an overlaid mesh and the rest of the discontinuity is implicitly described by a step function on partition of unity. The two displacement fields are matched through a transition region. The method can robustly deal with stationary crack and crack growth. It simplifies the numerical integration of the weak form in the Galerkin method as compared to the s‐version FEM. Numerical experiments are provided to demonstrate the effectiveness and robustness of the proposed method. Copyright © 2004 John Wiley & Sons, Ltd.     

A multiscale projection method for macro/microcrack simulations

We present a new multiscale method for crack simulations. This approach is based on a two‐scale decomposition of the displacements and a projection to the coarse scale by using coarse scale test functions. The extended finite element method (XFEM) is used to take into account macrocracks as well as microcracks accurately. The transition of the field variables between the different scales and the role of the microfield in the coarse scale formulation are emphasized. The method is designed so that the fine scale computation can be done independently of the coarse scale computation, which is very efficient and ideal for parallelization. Several examples involving microcracks and macrocracks are given. It is shown that the effect of crack shielding and amplification for crack growth analyses can be captured efficiently. Copyright © 2007 John Wiley & Sons, Ltd.     

The extended/generalized finite element method: An overview of the method and its applications

An overview of the extended/generalized finite element method (GEFM/XFEM) with emphasis on methodological issues is presented. This method enables the accurate approximation of solutions that involve jumps, kinks, singularities, and other locally non‐smooth features within elements. This is achieved by enriching the polynomial approximation space of the classical finite element method. The GEFM/XFEM has shown its potential in a variety of applications that involve non‐smooth solutions near interfaces: Among them are the simulation of cracks, shear bands, dislocations, solidification, and multi‐field problems. Copyright © 2010 John Wiley & Sons, Ltd.     

Retail alcohol monopolies, underage drinking, and youth impaired driving deaths

OBJECTIVE: To explore associations of state retail alcohol monopolies with underage drinking and alcohol-impaired driving deaths. DATA: Surveys on youth who drank alcohol and binge-drank recently and their beverage choices; census of motor vehicle fatalities by driver blood alcohol level. METHODS: Regressions estimated associations of monopolies with under-21 drinking, binge drinking, alcohol-impaired driving deaths, and odds a driver under 21 who died was alcohol-positive. RESULTS: About 93.8% of those ages 12-20 who consumed alcohol in the past month drank some wine or spirits. In states with a retail monopoly over spirits or wine and spirits, an average of 14.5% fewer high school students reported drinking alcohol in the past 30 days and 16.7% fewer reported binge drinking in the past 30 days than high school students in non-monopoly states. Monopolies over both wine and spirits were associated with larger consumption reductions than monopolies over spirits only. Lower consumption rates in monopoly states, in turn, were associated with a 9.3% lower alcohol-impaired driving death rate under age 21 in monopoly states versus non-monopoly states. Alcohol monopolies may prevent 45 impaired driving deaths annually. CONCLUSIONS: Continuing existing retail alcohol monopolies should help control underage drinking and associated harms.