Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer

The development of a new high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is reported. The high-resolution capabilities of this instrument allow the direct separation of most ions from inorganic and organic species at the same nominal m/z, the quantification of several types of organic fragments (CxHy, CxHyOz, CxHyNp, CxHyOzNp), and the direct identification of organic nitrogen and organosulfur content. This real-time instrument is field-deployable, and its high time resolution (0.5 Hz has been demonstrated) makes it well-suited for studies in which time resolution is critical, such as aircraft studies. The instrument has two ion optical modes: a single-reflection configuration offers higher sensitivity and lower resolving power (up to approximately 2100 at m/z 200), and a two-reflectron configuration yields higher resolving power (up to approximately 4300 at m/z 200) with lower sensitivity. The instrument also allows the determination of the size distributions of all ions. One-minute detection limits for submicrometer aerosol are <0.04 microg m(-3) for all species in the high-sensitivity mode and <0.4 microg m(-3) in the high-resolution mode. Examples of ambient aerosol data are presented from the SOAR-1 study in Riverside, CA, in which the spectra of ambient organic species are dominated by CxHy and CxHyOz fragments, and different organic and inorganic fragments at the same nominal m/z show different size distributions. Data are also presented from the MIRAGE C-130 aircraft study near Mexico City, showing high correlation with independent measurements of surrogate aerosol mass concentration.     

TiO2-photocatalyzed As(III) oxidation in a fixed-bed, flow-through reactor

Compliance with the U.S. drinking water standard for arsenic (As) of 10 microg L(-1) is required in January 2006. This will necessitate implementation of treatment technologies for As removal by thousands of water suppliers. Although a variety of such technologies is available, most require preoxidation of As(III) to As(V) for efficient performance. Previous batch studies with illuminated TiO2 slurries have demonstrated that TiO2-photocatalyzed AS(III) oxidation occurs rapidly. This study examined reaction efficiency in a flow-through, fixed-bed reactor that provides a better model for treatment in practice. Glass beads were coated with mixed P25/sol gel TiO2 and employed in an upflow reactor irradiated from above. The reactor residence time, influent As(III) concentration, number of TiO2 coatings on the beads, solution matrix, and light source were varied to characterize this reaction and determine its feasibility for water treatment. Repeated usage of the same beads in multiple experiments or extended use was found to affect effluent As(V) concentrations but not the steady-state effluent As(III) concentration, which suggests that As(III) oxidation at the TiO2 surface undergoes dynamic sorption equilibration. Catalyst poisoning was not observed either from As(V) or from competitively adsorbing anions, although the higher steady-state effluent As(III) concentrations in synthetic groundwater compared to 5 mM NaNO3 indicated that competitive sorbates in the matrix partially hinder the reaction. A reactive transport model with rate constants proportional to incident light at each bead layer fit the experimental data well despite simplifying assumptions. TiO2-photocatalyzed oxidation of As(III) was also effective under natural sunlight. Limitations to the efficiency of As(III) oxidation in the fixed-bed reactor were attributable to constraints of the reactor geometry, which could be overcome by improved design. The fixed-bed TiO2 reactor offers an environmentally benign method for As(III) oxidation.     

Engineering of Micro‐ and Nanostructured Surfaces with Anisotropic Geometries and Properties

Widespread approaches to fabricate surfaces with robust micro‐ and nanostructured topographies have been stimulated by opportunities to enhance interface performance by combining physical and chemical effects. In particular, arrays of asymmetric surface features, such as arrays of grooves, inclined pillars, and helical protrusions, have been shown to impart unique anisotropy in properties including wetting, adhesion, thermal and/or electrical conductivity, optical activity, and capability to direct cell growth. These properties are of wide interest for applications including energy conversion, microelectronics, chemical and biological sensing, and bioengineering. However, fabrication of asymmetric surface features often pushes the limits of traditional etching and deposition techniques, making it challenging to produce the desired surfaces in a scalable and cost‐effective manner. We review and classify approaches to fabricate arrays of asymmetric 2D and 3D surface features, in polymers, metals, and ceramics. Analytical and empirical relationships among geometries, materials, and surface properties are discussed, especially in the context of the applications mentioned above. Further, opportunities for new fabrication methods that combine lithography with principles of self‐assembly are identified, aiming to establish design principles for fabrication of arbitrary 3D surface textures over large areas.     

Synthesis of hydroxyapatite nanoparticles with tailorable morphologies and carbonate substitutions using a wet precipitation method

Hydroxyapatite (HA) nanoparticles with different morphologies and variant levels of carbonate substitutions were synthesized using a wet precipitation method by adjusting the heating temperature and/or the initial ion concentration of the reaction system. Within the particles, crystalline domains with different lengths were aligned along each other and formed into nanoparticles with different sizes, shapes and topographies. Different from most reported studies, the nucleation, growth and morphology of the crystalline domains were found sensitive to heating temperature, but not significantly influenced by initial ion concentration within the studied range. The OH- and PO4(3-) ions within the HA particles were partially substituted by CO3(2-) ions. The substitution was dominated by the replacement of OH- instead of PO4(3-) in HA. The carbonate substitution was found to decrease with increasing heating temperature and/or initial ion concentration. Therefore, both the morphology and composition of the HA particles can be tailored by controlling the heating temperature and/or the initial ion concentration in the reaction system. Such synthesized HA nanoparticles can be used as biomaterials for bone tissue engineering.     

Physiological down-regulation and positive emotion in marital interaction.

Previous studies have demonstrated that 1 function of positive emotion is the undoing of physiological arousal produced by negative emotions. These studies have used single-subject paradigms, in which emotions were induced by films in college-age individuals. In the present study, we examined the relationship between physiological down-regulation and positive emotion in a sample of 149 middle-aged and older married couples engaged in a 15-min discussion of an area of marital conflict. During the conversation, autonomic and somatic physiological activity was measured, and emotional behaviors were recorded and subsequently coded. We found that during 20-s periods of down-regulation (where physiology transitioned from high arousal to low arousal), couples showed an increase in positive emotional behavior compared with periods without down-regulation. The finding was quite robust, suggesting that the undoing effect of positive emotion generalizes across age, sex, and marital satisfaction. The advantages of using positive emotion as an emotion regulation strategy are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Effects of family foundations on parents and children: 3.5 years after baseline.

This study investigated the ability of a psychosocial prevention program implemented through childbirth education programs to enhance the coparental and couple relationship, parental mental health, the parent-child relationship, and child outcomes. A sample of 169 heterosexual, adult couples expecting their first child was randomized to intervention and control conditions. The intervention families participated in Family Foundations, a series of eight classes delivered before and after birth, which was designed as a universal prevention program (i.e., applicable to all couples, not just those at high risk). Intent-to-treat analyses utilizing data collected from child age 6 months through 3 years indicated significant program effects on parental stress and self-efficacy, coparenting, harsh parenting, and children's emotional adjustment among all families, and maternal depression among cohabiting couples. Among families of boys, program effects were found for child behavior problems and couple relationship quality. These results indicate that a universal prevention approach at the transition to parenthood focused on enhancing family relationships can have a significant and substantial positive impact on parent and child well-being. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

An evaluation of the effectiveness of a chemical additive based on sodium benzoate,potassium sorbate,and sodium nitrite on the fermentation and aerobic stability of corn silage

We evaluated the effectiveness of an additive comprising sodium benzoate, potassium sorbate, and sodium nitrite (SSL) as active ingredients for its ability to improve the aerobic stability of corn silages made in North America. In experiment 1, treatment with SSL (1.5 and 2.0 L/t) on whole-plant corn (WPC) was compared with treatment with an additive containing buffered propionic acid and citric acid (BPA; 2 L/t) on corn harvested at 32 and 38% dry matter and ensiled for 120 d. Silage treated with BPA was higher in ammonia-N and propionic acid relative to other treatments. Treatments with all of the additives had numerically, but not statistically, fewer yeasts compared with untreated silage. Both application rates of SSL resulted in lower concentrations of ethanol compared with untreated and BPA silages. Treatment with BPA improved the aerobic stability of silages compared with untreated silage, but the effect from SSL was markedly greater. In experiment 2, WPC was untreated or treated with 2 or 3 L of SSL/t or a microbial inoculant containing Enterococcus faecium M74, Lactobacillus plantarum CH6072, and Lactobacillus buchneri LN1819 (final total lactic acid bacteria application rate of 150,000 cfu/g of fresh forage). Silages were air stressed for 24 h at 28 and 42 d of storage and ensiled for 49 d before opening. Inoculation had no effect on acid end products, ethanol, number of yeasts, or aerobic stability compared with other treatments. Treatment with SSL decreased the amount of ethanol, had no effect on number of yeasts, and improved aerobic stability in a dose-dependent manner compared with other treatments. In experiment 3, WPC was untreated or treated with 2 L of SSL/t and ensiled for 5, 15, and 30 d. Treatment with SSL resulted in silage with fewer yeasts and lower concentrations of ethanol after all times of ensiling compared with untreated silage. In addition, SSL improved aerobic stability after each period of ensiling, but the effect was more at 15 and 30 d compared with 5 d of storage. Treating WPC with SSL can improve the aerobic stability of corn silage made in North America, and the effect can be observed as soon as 5 d after ensiling.     

Understanding the Effect of Grain Boundary Character on Dynamic Recrystallization in Stainless Steel 316L

Dynamic recrystallization (DRX) occurs during high-temperature deformation in metals and alloys with low to medium stacking fault energies. Previous simulations and experimental research have shown the effect of temperature and grain size on DRX behavior, but not the effect of the grain boundary character distribution. To investigate the effects of the distribution of grain boundary types, experimental testing was performed on stainless steel 316L specimens with different initial special boundary fractions (SBF). This work was completed in conjunction with computer simulations that used a modified Monte Carlo method which allowed for the addition of anisotropic grain boundary energies using orientation data from electron backscatter diffraction (EBSD). The correlation of the experimental and simulation work allows for a better understanding of how the input parameters in the simulations correspond to what occurs experimentally. Results from both simulations and experiments showed that a higher fraction of so-called “special” boundaries (e.g., Σ3 twin boundaries) delayed the onset of recrystallization to larger strains and that it is energetically favorable for nuclei to form on triple junctions without these so-called “special” boundaries.