Kinetics of dye decolorization in an air–solid system

The photocatalytic decolorization of adsorbed organic dyes (Acid Blue 9, Acid Orange 7, Reactive Black 5 and Reactive Blue 19) in air was examined, applicable to self-cleaning surfaces and catalyst characterization. Dye-coated Degussa P25 titanium dioxide (TiO₂) and dye-coated photo-inert aluminum oxide (Al₂O₃) particles, both of sub-monolayer initial dye coverage, were illuminated with 1.3 mW cm⁻² of near-UV light. Visual evidence of color removal is reported with photographic images. Two methods, Indirect and Direct Analysis, were employed to quantitatively examine the decolorization kinetics of dyes using UV–visible transmission and diffuse reflectance spectroscopy, respectively. A decrease in dye concentration with time was observed with near-UV illumination of dye-coated TiO₂ powders for all dyes. Dyes did not photodegrade significantly on photo-inert Al₂O₃.

UV–visible spectroscopy data was used to model the kinetics of the photocatalytic degradation. Two first-order reactions in series provided the most convincing rate form for the photodegradation of dyes adsorbed to TiO₂, with a first step the conversion of colored dye to colored intermediate, and the second the conversion to colorless product(s). The first rate constant was of similar magnitude for all dyes, averaging k₁ = 0.13 min⁻¹. Similarly, for the second, k₂ = 0.0014 min⁻¹.     

Decolorization of organic dyes on Pilkington Activ™ photocatalytic glass

The air–solid photocatalytic degradation of organic dye films Acid Blue 9 (AB9) and Reactive Black 5 (RBk5) is studied on Pilkington Activ™ glass. The Activ™ glass comprises of a colorless TiO₂ layer deposited on clear glass. The Activ™ glass is characterized using atomic force microscopy (AFM) and X-ray diffraction (XRD). Using AFM, the TiO₂ average agglomerate particle size is 95 nm, with an apparent TiO₂ thickness of 12 nm. The XRD results indicate the anatase phase of TiO₂, with a calculated crystallite size of 18 nm.

Dyes AB9 and RBk5 are deposited in a liquid film and dried on the Activ™ glass to test for photodecolorization in air, using eight UVA blacklight-blue fluorescent lamps with an average UVA irradiance of 1.4 mW/cm². A novel horizontal coat method is used for dye deposition, minimizing the amount of solution used while forming a fairly uniform dye layer. About 35–75 monolayers of dye are placed on the Activ™ glass, with a covered area of 7–10 cm². Dye degradation is observed visually and via UV–vis spectroscopy.

The kinetics of photodecolorization satisfactorily fit a two-step series reaction model, indicating that the dye degrades to a single colored intermediate compound before reaching its final colorless product(s). Each reaction step follows a simple irreversible first-order reaction rate form. The average k₁ is 0.017 and 0.021 min⁻¹ for AB9 and RBk5, respectively, and the corresponding average k₂ is 2.0 × 10⁻³ and 1.5 × 10⁻³ min⁻¹. Variable light intensity experiments reveal a p = 0.44 ± 0.02 exponent dependency of initial decolorization rate on the UV irradiance. Solar experiments are conducted outdoors with an average temperature, water vapor density, and UVA irradiance of 30.8 °C, 6.4 g water/m³ dry air, and 1.5 mW/cm², respectively. For AB9, the average solar k₁ is 0.041 min⁻¹ and k₂ is 5.7 × 10⁻³ min⁻¹.     

Engineering Aspects of the Integration of Chemical and Biological Oxidation: Simple Mechanistic Models for the Oxidation Treatment

Oxidation processes can oxidize biorecalcitrant compounds into biodegradable intermediates, which in turn can be treated less expensively by a subsequent biological process. To design such a two-step (chemical+biological) process to treat poorly characterized wastewaters, it is useful to model the time evolution of characteristic global variables, chemical oxygen demand (COD) and biochemical oxygen demand (BOD), in order to develop a useful treatment strategy based upon these classical variables. We consider two simple model reaction networks, requiring three- and five-rate constants, respectively. The first model, proposed recently, involves conversion of a nonbiodegradable species, C, into a single biodegradable intermediate S. Here, biodegradable compounds are immediate kinetic products of oxidation. In general, it is not probable that a single recalcitrant compound undergoes a single-step reaction to CO2. However, when working with complex undefined wastewaters streams, single-step reactions may be used to simplify. The second new model corresponds to a lag time in BOD formation due to the necessity of multiple partial oxidations to reach a first biodegradable intermediate. The second network includes two intermediates, I and S, which are, respectively, nonbiodegradable and biodegradable. We then compare model behavior with an unfortunately sparse literature on BOD and COD values versus time in chemical reactors, and demonstrate the convenience of the first model, and the occasional necessity of the second, which reflects the presence of early intermediates which are nonbiodegradable.     

Salmonella spp. shedding by alberta beef cattle and the detection of Salmonella spp. in ground beef

Breeder cows, cattle recently arrived at feedlots, and cattle about to be shipped for slaughter were tested for Salmonella spp. No Salmonella spp. were detected in fecal samples from breeding cows. Nineteen of 1,000 (1.9%) fecal samples from recently arrived feedlot cattle were positive for Salmonella spp. compared to only 2 of 1,000 (0.2%) fecal samples taken within 2 weeks of slaughter. The positive fecal samples were collected in 5 of 50 (10%) "recent arrival" pens tested and in 1 of 50 (2%) pens tested within 2 weeks of slaughter. The serotypes isolated were Salmonella Agona, Salmonella Enteritidis, Salmonella Typhimurium DT104, and Salmonella 4,5,12:i:-. Ground beef samples purchased from retail outlets throughout Alberta were processed for Salmonella spp. Thirteen of 1,002 (1.3%) samples were positive for Salmonella spp. The serotypes isolated from ground beef were Salmonella Anatum, Salmonella Heidelberg, Salmonella Montevideo, Salmonella Typhimurium, Salmonella Typhimurium var. Copenhagen, and Salmonella Rough-O:i:1,2. The antibiotic resistance and pulsed-field electrophoresis gel macrorestriction patterns of all isolates were compared.     

Crystal structure of cytoplasmic Escherichia coli peptidyl-prolyl isomerase: evidence for decreased mobility of loops upon complexation

Ryanodine receptors (RyRs), a class of intracellular calcium release channels, are the largest ion channels known. Recently, cryoelectron microscopy and image reconstructions of isolated receptors have shown that most of the protein mass forms a porous, multidomain cytoplasmic assembly. Evidence is mounting that suggests that the cytoplasmic assembly communicates with the transmembrane regions over distances of 100 or greater. RyRs are centrally important in excitation-contraction coupling, which occurs at specialized regions where the sarcoplasmic reticulum, containing the RyRs, and the plasma membrane/transverse-tubule system form junctions. Numerous proteins are present at these junctions, some of which interact directly with the RyR.     

Quantitative photocatalyzed soot oxidation on titanium dioxide

We report here the titanium dioxide (TiO₂) photocatalyzed oxidation of deposited hurricane lamp soot. Sol–gel derived TiO₂ was coated on quartz crystal microbalance (QCM) elements. Characterization by spectroscopic ellipsometry (SE) and atomic force microscopy (AFM) revealed low surface roughness of 0–17%, and SE showed a linear variation of the TiO₂ thickness versus the number of sol–gel spin coats.Soot was deposited on the calcined TiO₂ film using an analytical rotor passing through a hurricane lamp flame, and subsequently irradiated with near-UV light. Varying the soot mass on the TiO₂-coated QCM crystals revealed behaviors over 20,000 min ranging from total soot destruction of a single pass soot layer to minimal oxidation of an eight pass soot layer, the latter caused by soot screening of the incident UV light. A series/parallel reaction mechanism [P. Chin, G.W. Roberts, D.F. Ollis, Industrial & Engineering Chemistry Research 46 (2007) 7598] developed to describe previous literature data on TiO₂-catalyzed soot photooxidation was successfully employed to capture the longer time changes in presumably graphitic soot mass as a function of UV illumination time from 1000 to 20,000 min and of soot layer thickness. Short time soot mass loss is attributed to oxidation of organic carbons deposited on the graphitic soot components. This kinetic model can be used to predict the rate of TiO₂-catalyzed soot destruction as a function of near-UV illumination time and initial soot layer thickness.     

Sequential Ozonation and Biological Oxidation of Wastewaters: A Model Including Biomass Inhibition by Residual Oxidant

We modeled the potential impact of a residual oxidant (ozone in the present case, known to be a strong bactericide) on the performance of a combined chemical and biological water treatment. This model is fashioned by adapting a recent model for the kinetics of ozone disinfection to an activated sludge system performing in the presence of ozone residuals. Our new model allows prediction of the bioreactor performance under different substrate loadings and residual oxidant concentrations, helping to identify regimes where air stripping would be necessary before the second step.     

Heterogeneous Catalysis by Optically Selective Surfaces

Abstract

Addition of promoters to heterogeneous catalysts in order to influence the overall selectivity favorably is a tradition in catalyst development. Well-studied examples include Fisher-Tropsch catalysis and mixed metal catalysts of the refining industry. The modification of metal surfaces to yield optically selective hydrogenation catalysts represents a relatively recent development in this tradition. This review concerns the synthesis of such catalysts, their reported selectivities versus preparation conditions (promoter o r modifier loading, temperature and pH of modification, etc.), and an attempted semiquantitative model, derived largely from IR and electrochemical studies, which may rationalize the corresponding catalyst selectivity variations.